KR100299078B1 - Unsaturated copolymers, processes for preparing the same, and compositions containing the same - Google Patents

Abstract

PURPOSE: An unsaturated copolymer, its preparation method and an elastomer composition containing the copolymer are provided, to improve weather resistance, heat resistance, low temperature resistance, crosslinking efficiency and modifying efficiency and to obtain a low glass transition temperature. CONSTITUTION: The unsaturated copolymer is a copolymer of an α-olefin of C2-C12 and a conjugated diene monomer represented by CH2=CH-CR1=CH2 (wherein R1 is an alkyl or aryl group of C1-C8), wherein the 1,2-adduct (containing 3,4-adduct) derived from the conjugated diene monomer forms a double bond at the side chain of the copolymer, the 1,4-adduct derived from the conjugated diene monomer forms a double bond at the main chain of the copolymer, and the ratio of the double bond of side chain derived from 1,2-adduct to the double bond of the main chain derived from 1,4-adduct is 5/95 to 99/1. The elastomer composition comprises the unsaturated copolymer; and a crosslinking agent and/or a filler.

Description

Unsaturated copolymer, preparation method of this copolymer and composition containing this copolymer {UNSATURATED COPOLYMERS, PROCESSES FOR PREPARING THE SAME, AND COMPOSITIONS CONTAINING THE SAME}

The present invention relates to an unsaturated copolymer, a method for producing the copolymer and a composition containing the copolymer. In particular, the present invention relates to an unsaturated copolymer having excellent weather resistance, heat resistance, low temperature resistance, crosslinking efficiency and oil resistance, and also to a method for producing the copolymer and a composition containing the copolymer.

Conventionally, soft resins, such as butadiene rubber (BR), isoprene rubber (IR), and styrene-butadiene rubber (SBR), have been used in molded products such as tires. However, when this soft resin is used in molded products requiring weather resistance, heat resistance, and low temperature resistance (for example, various automotive parts), the resin tends to deteriorate due to oxidation, thereby deteriorating physical properties. Therefore, there is an urgent need to improve the weather resistance, heat resistance and low temperature resistance of the resin.

The reason for the poor physical properties when using a molded product of a soft resin under severe conditions is that the double bond of the main chain of the resin causes deterioration by oxidation. Therefore, it is necessary to reduce the double bond amount of the main chain to a minimum.

When soft resins such as SBR, EPR and ethylene / propylene / nonconjugated diene copolymers (EPT) are used in rubber molded products, the soft resins cause peroxide crosslinking or radical denaturation. Therefore, an inexpensive elastomer having a high crosslinking efficiency and a high reaction efficiency and hardly deteriorating physical properties after the reaction is desired.

Particularly in the case of peroxide crosslinking, a large amount of peroxide is required if the crosslinking efficiency of the soft resin is low. If a large amount of peroxide is used, the decomposition reaction of the main chain of the soft resin can be caused. In addition, when a large amount of peroxide is used, there arises a problem that the peroxide remains in the resulting crosslinked product.

Conventional EPT has insufficient crosslinking efficiency, and in particular, in the case of peroxide crosslinking thereof, the resulting crosslinked product may not be satisfactory, and improvement of physical properties such as compression set is required.

The present inventors have diligently studied to solve the above-mentioned problems, and as a result, unsaturated copolymers obtained by random copolymerization of α-olefins, specific conjugated diene monomers and aromatic vinyl compounds as necessary, are derived from the following physical properties: dienes 1,2-addition unit (including 3, 4-addition unit) is high, there is a double bond in a specific ratio in the main chain and side chain of the copolymer, a 5-membered ring is present in the copolymer, The double bond and the 5-membered ring are present in a specific ratio, and thus, an unsaturated copolymer having excellent physical properties such as compatibility, weather resistance, heat resistance, low temperature resistance, crosslinking efficiency, and modification efficiency has been found. The inventors have also found that the copolymer has a low glass transition temperature and is industrially efficient. The present invention has been completed based on the above findings.

As for the ethylene / 1,3-butadiene copolymer, the following documents (1) to (5) are known.

(1) Journal of Polymer Science, Part B, Polymer Physics, Vol. 26, 2113-2126 (1988) discloses ethylene / 1,3-butadiene copolymers prepared using supported Ziegler catalysts. According to this document, the copolymer has a butadiene-butadiene bond and is a block copolymer. The catalytic activity is low (10 kg / g-Ti or less). The butadiene unit is mainly a trans-1,4-addition unit, and a graft polymer of MMA is prepared by grafting methyl methacrylate (MMA) or maleic anhydride to the double bond position of this addition unit.

(2) Makromol. Chem. 179, 2173-2185 (1978) disclose ethylene / 1,3-butadiene copolymers prepared using vanadium catalysts. According to this document, almost no 1,2-addition units derived from 1,3-butadiene are contained in the copolymerization, butadiene units are mainly trans 1,4-addition units. In addition, the catalytic activity is low.

(3) Polymer Bulletin 31, 271-278 (1993) discloses ethylene / propylene / 1,3-butadiene copolymers prepared using Ziegler catalysts. According to this document, it is confirmed that 1,2-addition units derived from 1,3-butadiene, 1,4-addition units and propylene units are present in the copolymer, and the catalytic activity is low (10 kg / g-Ti or less). ).

The catalysts described in the documents (1) to (3) have low activity, and the resulting copolymers do not have 5- or 3-membered rings. The copolymers described in documents (1) and (2) do not have 1,2-addition units derived from butadiene.

(4) Makromol. Chem. 192, 2591-2601 (1991) disclose ethylene / 1,3-butadiene copolymers and ethylene / propylene / 1,3-butadiene copolymers prepared using biscyclopentadienyl metallocene catalysts. According to this document, 1,4-addition unit and 5-membered ring are present in the copolymer, but 1,2-addition unit and 3-membered ring are not present. In addition, each catalytic activity is low (5 kg / mM-Zr).

(5) International Publication W088 / 04672 (filed in 1986; corresponding to 1993, 3, 2 US Patent No. 5,191,052, 1994, 7, 7 European Patent No. EP0275676B1), has a biscyclopentadienyl-based Ethylene / 1,3-butadiene copolymers prepared using metallocene catalysts are disclosed. According to this publication, although 1,2-addition unit, 1,4-addition unit, and 5-membered ring exist in a copolymer, the ratio between them is not described. In the examples, the amount of particularly useful 1,2-additional units is extremely small, and there is no mention of the structure of a three-membered ring. In addition, the catalytic activity is extremely low (1 kg / mM-Zr · hr or less).

The present invention has been made to solve the above-mentioned problems related to the prior art, and an object of the present invention is to exhibit excellent compatibility with other polar group-containing resins, and to have weather resistance, heat resistance, low temperature resistance, crosslinking efficiency, and modification efficiency. It is to provide an unsaturated copolymer which is excellent, has a low glass transition temperature and is economically advantageous.

Another object of the present invention is to provide a method capable of efficiently and industrially producing unsaturated copolymers having the above excellent physical properties.

Another object of the present invention is to provide a modified product of the unsaturated copolymer.

The first unsaturated copolymer according to the present invention (which may be simply referred to as 'first copolymer') is a copolymer of an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the following general formula (Ia), Properties are:

(a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (Ia) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (Ia) 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of the ratio of heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of main chains derived from 1,4-addition units) is in the range of 10/90 to 99/1,

(b) a 5-membered ring is present in the main chain of the copolymer,

(c) The amount ratio (total / 5-membered ring of double bonds derived from all addition units) to double-membered rings derived from all addition units is in the range of 20/80 to 90/10.

In formula, R <^2> is a hydrogen atom, a C1-C8 alkyl group, or an aryl group.

In the first unsaturated copolymer, the conjugated diene monomer is preferably 1,3-butadiene.

In an embodiment of the first unsaturated copolymer, the α-olefin is a combination of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms, in which case the molar ratio of ethylene to an α-olefin having 3 to 12 carbon atoms is The range of 99/1-40/60 is preferable.

In an embodiment of the present invention, it is preferable that a cyclopropane ring is further present in the main chain of the copolymer.

In the embodiment of the present invention, it is preferable that the copolymer contains 0.01 to 30 mol% of the total amount of structural units derived from the conjugated diene monomer.

In an embodiment of the present invention, the copolymer has an intrinsic viscosity (η) of 1 to 50 g / 100 g of Oxogawa, 135 ° C., 0.01 to 10 dl / g measured at decalin, and a glass transition temperature (Tg) of 25 ° C. or less. It is preferable to have.

The first modified unsaturated copolymer according to the present invention is a modified unsaturated copolymer obtained by graft modification of the copolymer with at least one compound selected from the group consisting of (i) unsaturated carboxylic acids or derivatives thereof, and (ii) aromatic vinyl compounds, The graft ratio of an unsaturated carboxylic acid or its derivative is 0.01 to 30 weight% here.

The first unsaturated copolymer containing elastomer composition is:

(a) the copolymer

(b) crosslinking agent and / or filler.

The method for producing an unsaturated copolymer according to the present invention is to prepare a first unsaturated copolymer by copolymerizing an α-olefin having 2 to 12 carbon atoms and at least one conjugated diene monomer represented by the general formula (Ia) in the presence of a catalyst. In the process, at least one catalyst system composed of the following component (a) and at least one compound selected from the following components (b), (c) and (d) is used as the catalyst.

(a) the transition metal complex represented by the following general formula (II) or (III):

Wherein M is Ti, Zr, Hf, Rn, Nd, Sm or Ru; Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof π-bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms

(b) a compound which reacts with the transition metal (M) of component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxanes.

The second unsaturated copolymer according to the present invention is a copolymer of an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the following general formula (I-b):

In formula, R <^1> is a C1-C8 alkyl group or an aryl group.

In an embodiment of the second unsaturated copolymer, the copolymer is a copolymer of an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the general formula (I-b), and its physical properties are:

(a) In the copolymer, 1,2-added units (including 3,4-addition units) derived from conjugated diene monomers (Ib) form double bonds in the side chains of the copolymer, and conjugated diene monomers (Ib) 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of heavy to heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of main chains derived from 1,4-addition units) ranges from 5/95 to 99/1.

In an embodiment of the second unsaturated olefin copolymer, the copolymer is a copolymer of an α-olefin having 2 to 12 carbon atoms and a conjugated diene monomer represented by the above general formula (I-b), and its physical properties are:

(a) In the copolymer, 1,2-added units (including 3,4-addition units) derived from conjugated diene monomers (Ib) form double bonds in the side chains of the copolymer, and conjugated diene monomers (Ib) 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of the ratio of heavy bonds (double bonds of the side chains derived from 1,2-addition units / double bonds of the main chain derived from 1,4-addition units) is in the range of 5/95 to 99/1;

(b) a 5-membered ring is present in the main chain of the copolymer,

(c) It is preferable that the ratio of the ratio of the double bonds derived from all the additional units to the five-membered ring (the sum of five-membered rings of the double bonds derived from all the additional units) is in the range of 20/80 to 90/10 .

In the second unsaturated copolymer, the conjugated diene monomer is preferably isoprene. In the present invention, the α-olefin is preferably a combination of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms, and in the combination, the molar ratio of ethylene to an α-olefin having 3 to 12 carbon atoms is 99/1 to It is in the range of 40/60.

In the second unsaturated copolymer, it is preferable that a cyclopropane ring is further present in the main chain of the copolymer.

In the second unsaturated copolymer, the copolymer preferably contains 0.01 to 30 mol% of the total amount of the structural units derived from the conjugated diene monomer.

In the example of the second unsaturated copolymer, the copolymer has an intrinsic viscosity (η) of 1 to 50 g / 100 g of oxo value, 135 ° C., 0.01 to 10 dl / g measured at decalin, and 25 ° C. measured by DSC. It is preferable to have the following glass transition temperatures (Tg).

The second unsaturated copolymer-containing elastomer composition according to the present invention is:

(a) a second unsaturated copolymer (second copolymer),

(b) crosslinking agent and / or filler.

In the method for producing an unsaturated copolymer according to the present invention, a second unsaturated copolymer is prepared by copolymerizing an α-olefin having 2 to 12 carbon atoms and at least one conjugated diene monomer represented by the general formula (Ib) in the presence of a catalyst. In the method, the catalyst system described above is used as the catalyst.

The third unsaturated (random) copolymer according to the present invention is a copolymer of an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a conjugated diene monomer.

In an embodiment of the third unsaturated copolymer, the copolymer is a copolymer of an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a conjugated diene monomer represented by the following general formula (I), and its physical properties are:

(a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (I 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The amount ratio for heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of main chains derived from 1,4-addition units) ranges from 10/90 to 99/1.

In formula, R <^1> and R <^2> is respectively independently a hydrogen atom, a C1-C8 alkyl group, or an aryl group, At least one of R <^1> and R <^2> is a hydrogen atom.

In an embodiment of the third unsaturated copolymer, the copolymer is a copolymer of an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a conjugated diene monomer represented by the general formula (I), and its physical properties are:

(a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (I 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of heavy to heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of backbones derived from 1,4-addition units) ranges from 10/90 to 99/1:

(b) a 5-membered ring is present in the main chain of the copolymer,

(c) the ratio of the amount of double bonds derived from the total addition units to the 5-membered rings (total / 5-membered rings of the double bonds derived from the total addition units) is in the range of 20/80 to 90/10;

(d) It is preferable to contain 0.1-60 mol% of structural units derived from an aromatic vinyl compound.

In the third unsaturated copolymer (third copolymer), the copolymer preferably contains 0.01 to 30 mol% of the total amount of the structural units derived from the conjugated diene monomer.

In the third unsaturated copolymer, the conjugated diene monomer is preferably 1,3-butadiene or isoprene.

In the third unsaturated copolymer, the α-olefin is preferably a combination of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms, in which case the molar ratio of ethylene to an α-olefin having 3 to 12 carbon atoms is 99. It is the range of / 1-40/60.

In the third unsaturated copolymer, the aromatic vinyl compound is preferably styrene.

In the third unsaturated copolymer, it is preferable that a cyclopropane ring is further present in the main chain of the copolymer.

The third unsaturated copolymer preferably has an oxo value of 1 to 50 g / 100 g, an intrinsic viscosity (η) of 0.01 to 10 dl / g measured at 135 ° C and decalin, and a glass transition temperature (Tg) of 25 ° C. or less. Do.

The peak melting point (Tm) of the third unsaturated copolymer is preferably 120 ° C. or less as measured by DSC.

The third modified copolymer according to the present invention is a modified copolymer obtained by graft modification of the third unsaturated copolymer with at least one compound selected from the group consisting of (i) unsaturated carboxylic acids or derivatives thereof and (ii) aromatic vinyl compounds, The graft ratio here is 0.01 to 30% by weight.

The third unsaturated copolymer-containing elastomer composition according to the present invention is:

(a) a third unsaturated copolymer and

(b) crosslinking agent and / or filler.

In the method for producing an unsaturated copolymer according to the present invention, a third unsaturated air is obtained by copolymerizing an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and at least one conjugated diene monomer represented by the general formula (I) in the presence of a catalyst. A method of preparing coalesce wherein the catalyst uses the catalyst system described above.

The crosslinked product according to the present invention is a crosslinked product obtained by crosslinking the above-mentioned composition. In the present invention, the crosslinking agent used for crosslinking the composition is preferably an organic peroxide.

The film or sheet according to the present invention is composed of the aforementioned crosslinked product.

The unsaturated copolymer according to the present invention is excellent in weather resistance, heat resistance, low temperature resistance, compatibility, oil resistance, crosslinking efficiency and modification efficiency, has a low transition temperature, and is economically advantageous.

According to the manufacturing method of this invention, the unsaturated copolymer which has the said outstanding physical property can be manufactured efficiently and industrially.

The modified unsaturated copolymer according to the present invention has good compatibility with other elastomers and resins.

The first, second and third unsaturated copolymers according to the present invention (simply collectively referred to as 'unsaturated copolymers') will be described in detail.

Unsaturated copolymer

The first unsaturated copolymer (also referred to simply as the 'first copolymer') according to the invention is a copolymer of at least one C2-C12 α-olefin and at least one conjugated diene monomer (Ia) described below. .

The second unsaturated copolymer (also referred to simply as the 'second copolymer') according to the present invention is a copolymer of at least one C2-C12 α-olefin and at least one conjugated diene monomer (Ib) described below. .

The third unsaturated copolymer according to the present invention (which may be simply referred to as a 'third copolymer') has at least one C2-C12 alpha -olefin, an aromatic vinyl compound, and at least one conjugated diene monomer described below ( Copolymer of I).

The conjugated diene monomer (I) is a conjugated diene equivalent (I-a) and / or a conjugated diene monomer (I-b).

The alpha -olefin used in the production of the unsaturated copolymer is not particularly limited as long as the alpha -olefin has 2 to 12 carbon atoms. The alpha -olefin may be straight chain or may have a branch.

Examples of α-olefins are ethylene, propylene, 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene , 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1 -Pentene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. These alpha-olefins can be used individually or in combination of 2 or more types.

When using alpha-olefin independently, a C2-C5 alpha olefin is preferable and ethylene is especially preferable. When using 2 or more types of alpha-olefins in combination, the combination of ethylene and alpha-olefin of 3 or more carbon atoms is preferable. The molar ratio of ethylene to α-olefin having 3 or more carbon atoms (ethylene / α 3 or more having 3 or more carbon atoms) is preferably in the range of 99/1 to 40/60. Considering the possibility of lowering the glass transition temperature (Tg) of the product copolymer, the molar ratio is preferably in the range of 90/10 to 60/40. The molar ratio is more preferably in the range of 85/15 to 70/30. When using the produced copolymer as an elastomer, the molar ratio is particularly preferably 80/20 to 55/45.

The conjugated diene monomer used in the present invention is represented by the following general formula (I):

In formula, R <^1> and R <^2> is respectively independently a hydrogen atom, a C1-C8 alkyl group, or an aryl group, and at least one of R <^1> and R <^2> is a hydrogen atom.

There is no restriction | limiting in particular in conjugated diene monomer (I), What is necessary is just an aromatic conjugated diene monomer or an aliphatic conjugated diene monomer.

Examples of the conjugated diene monomer (I) include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1-phenyl-1,3- Butadiene, 1-phenyl-2,4-pentadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1 , 3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene. A conjugated diene monomer can be used individually or in combination of 2 or more types.

Especially in a 1st unsaturated copolymer, the conjugated diene monomer represented with the following general formula (I-a) is used as a conjugated diene monomer.

In formula, R <^2> is a hydrogen atom, a C1-C8 alkyl group, or an aryl group.

There is no restriction | limiting in particular in conjugated diene monomer (I-a), What is necessary is just an aromatic conjugated diene monomer or an aliphatic conjugated diene monomer.

Examples of the conjugated diene monomer (Ia) include 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene and 1-phenyl- among the above-exemplified examples. 1,3-butadiene and 1-phenyl-2,4-pentadiene are mentioned. Among them, 1,3-butadiene is particularly preferred because it has excellent copolymerizability and crosslinking efficiency.

Especially in a 2nd unsaturated copolymer, the conjugated diene monomer represented with the following general formula (I-b) is used as conjugated diene monomer.

In formula, R <^1> is a C1-C8 alkyl group or an aryl group.

There is no restriction | limiting in particular in conjugated diene monomer (I-b), What is necessary is just an aromatic conjugated diene monomer or an aliphatic conjugated diene monomer.

Examples of the conjugated diene monomer (Ib) include isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-butyl-1,3-butadiene, 2-pentyl-1, 3-butadiene, 2-hexyl-1,3-butadiene, 2-heptyl-1,3-butadiene, 2-octyl-1,3-butadiene, 2-phenyl-1,3-butadiene are mentioned. Among these, isoprene is particularly preferable because it has excellent copolymerizability and crosslinking efficiency.

In the third unsaturated copolymer, the conjugated diene monomer (I) described above can be used. 1,3-butadiene and isoprene are particularly preferable in the above examples because they have excellent copolymerizability.

The aromatic vinyl compound used as needed in the present invention is a compound having one carbon-carbon double bond (C = C) per one substituent bonded to the aromatic ring. Examples of such compounds include styrene; mono or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene; Functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-chloro styrene and vinyl benzene; Other compounds, such as 3-phenylpropylene, 4-phenylbutene, and (alpha) -methylstyrene, are mentioned.

Among these, styrene or 4-methoxy styrene is preferable.

An aromatic vinyl compound can be used individually or in combination of 2 or more types.

The first and second unsaturated copolymers of the present invention are generally:

structural units derived from α-olefins (raw materials) and

It contains 1,2-added units (including 3,4-added units) derived from conjugated dienes (raw materials) and structural units of 1,4-added units.

It is preferable that a 1st and 2nd unsaturated copolymer further contain the 5-membered ring (cyclopentane ring) formed in the main chain.

As with the first and second unsaturated copolymers, the third unsaturated copolymers (unsaturated terpolymers, α-olefins / aromatic vinyl compounds / conjugated diene copolymers) of the present invention are generally:

structural units derived from α-olefins (raw materials) and

It contains 1,2-added units (including 3,4-added units) derived from conjugated dienes (raw materials) and structural units of 1,4-added units.

It is preferable that a 3rd unsaturated copolymer further contains the structural unit derived from the 5-membered ring (cyclopentane ring) formed in the main chain, and an aromatic vinyl compound.

The unsaturated olefin copolymer of the present invention may further contain a cyclopropane structural unit in addition to the structural unit described above.

In the present specification, '1,2-additional unit' and '3,4-additional unit' are collectively referred to as '1,2-additional unit'.

The unsaturated copolymers (first, second and third unsaturated copolymers) of the present invention have the following physical properties.

(a) In the unsaturated copolymer of the present invention, 1,2-addition units derived from conjugated diene monomers (including 3,4-addition units) form double bonds in the side chains of the copolymer and are derived from conjugated diene monomers. 1,4-addition unit is formed in the main chain of the copolymer to form a double bond of cis or trans.

In particular, in the first unsaturated copolymer (first copolymer) of the present invention, the double bond of the side chain derived from 1,2-addition unit and the double bond of the main chain derived from 1,4-addition unit are 1,2 The molar ratio of the double bonds of the main chain derived from the side chain derived from the addition unit to the double bonds of the main chain derived from the unit (double bonds of the side chain derived from the 1,2-addition unit / 1,4-addition) It is desired that the double bond of the main chain derived from the unit) be present in an amount ranging from 10/90 to 99/1, preferably from 12/88 to 90/10.

In particular, in the second unsaturated copolymer (second copolymer) of the present invention, the double bond is a double bond of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit. The molar ratio to (double bond of side chain derived from 1,2-addition unit / 1 double bond of main chain derived from 1,4-addition unit) is 5/95 to 99/1, preferably 10/90 -99/1, More preferably, it exists to exist in the quantity of the range of 20/80-90/10.

In particular, in the third unsaturated copolymer (third copolymer) of the present invention, the double bond is a double bond of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit. The molar ratio to (double bond of side chain derived from 1,2-addition unit / 1 double bond of main chain derived from 1,4-addition unit) is 5/95 to 99/1, preferably 10/90 It is desired to exist in an amount in the range of -99/1. When the conjugated diene monomer is a conjugated diene monomer having the general formula (I) wherein R ¹ is a hydrogen atom and R ² is a hydrogen atom or an alkyl group, for example butadiene, the molar ratio is in the range of 12/88 to 90/10. More preferred. When the conjugated diene monomer is a conjugated diene monomer having the general formula (I) wherein R ¹ is an alkyl group and R ² is a hydrogen atom, for example isoprene, the molar ratio is more preferably in the range of 20/80 to 90/10. Do.

When the double bond (C = C) is present in each of the copolymers in the above molar ratio, the weather resistance, heat resistance, crosslinking efficiency, low temperature resistance and modification efficiency of each copolymer are improved.

(b) The 5-membered ring (cyclopentane ring) exists in the principal chain of the unsaturated copolymer of this invention.

(c) In unsaturated copolymers, the double bonds and five-membered rings derived from addition units are the five-membered double bonds derived from all addition units (all 1,2-, 3,4 and 1,4-addition units). When the molar ratio to the ring (total / 5-membered ring of double bonds derived from the total addition units) is 20/80 to 90/10, and also considering the equilibrium between the glass transition temperature (Tg) of the resulting copolymer and the oxo value The molar ratio is preferably present in an amount of 30/70 to 80/20.

Five-membered rings present in unsaturated copolymers include cis and trans forms.

The mechanism of formation of the five-membered ring is not yet clear, but in the case of the first unsaturated copolymer in which the late α-olefin is ethylene and the conjugated diene is 1,3-butadiene, the α-olefin (ethylene) and the conjugated diene monomer ( 1,3-butadiene (conjugated diene) is 1,2-added to the oligomeric chain (P) or prepolymer chain (P) formed by the reaction of 1,3-butadiene, and then ethylene (α-olefin) is further added. It is assumed that by addition and then intramolecular cyclization, a five-membered ring is produced. This production mechanism is shown in the chart below, where the symbol 'Cat' represents the catalyst and the symbol 'P' represents the oligomeric chain or prepolymer chain.

Cyclopropane rings (three-membered rings) are believed to be produced by intramolecular cyclization after conjugated dienes such as butadiene are added 1,2-added to the oligomer chain or prepolymer chain as indicated above. A 5-membered ring and a cyclopropane ring contribute to the improvement of the compatibility of a copolymer, and make the compatibility of a copolymer and styrene elastomer, such as SBR, favorable. The copolymer also has good processability.

The molar formation ratio (cyclopropane ring / 5 member ring) with respect to the 5-membered ring of a cyclopropane ring becomes like this. Preferably it is the range of 0.1 / 99.9-50 / 50, More preferably, it is the range of 0.1 / 99.9-30 / 70.

Identification and determination of the 5-membered ring and the cyclopropane ring (3-membered ring) can be made by ¹³ C-NMR.

More specifically, in the case of the ethylene / 1,3-butadiene copolymer, the identification of the copolymer is carried out using a hexachlorobutadiene solvent under conditions of 110 ° C and 100 MHz by an NMR measuring instrument (manufactured by Japan Electron Optics Laboratoy Co., Ltd.). By measuring the NMR. Chem. ' 192, 2591-2601 (1991) by the chart produced by the chemical shift.

Identification and determination of the following 1,2-addition units can be made by ¹ H-NMR, ¹³ C-NMR and binary HMR of ¹ H and ¹³ C.

The chemical shift of each NMR is shown in Table 1a.

1 2 3 Chemical shift of ¹³ C-NMR 110-115ppm, 140-145ppm, 40-45ppm Chemical shift of ¹ H-NMR 4.9 to 5.0 ppm, 5.2 to 5.9 ppm, 1.6 to 2.0 ppm

The identification and determination of the following cyclopropane rings can be determined by CH bond constants unique to ¹³ C-NMR and ¹ H-NMR as well as the cyclopropane ring as described above.

The chemical shift of each NMR is shown in Table 2a.

One 2 Chemical shift of ¹³ C-NMR 16 to 22 ppm 10-15 ppm Chemical shift of ¹ H-NMR 0.2 to 0.4 ppm 0.0-0.2ppm Coupling Integer (J _CH ) 154 156

The amount ratio between the component ratio and the structure derived from the conjugated diene is determined by the ratio between the peak areas of ¹ H-NMR and / or ¹³ C-NMR.

In addition, a five-membered ring is present in the second unsaturated copolymer, and the formation mechanism of the five-membered ring is not yet clear, but isoprene (conjugated diene) is added to the oligomer chain or the prepolymer chain formed by the reaction of the α-olefin and the conjugated diene. It is estimated that a 5-membered ring is produced by intramolecular cyclization after further addition of ethylene (? -Olefin) after addition of 2,2-addition or 3,4-addition.

Identification and determination of the 5-membered ring can be made by ¹³ C-NMR as described above.

Identification and determination of the following 3,4-addition unit can be made by ¹ H-NMR, ¹³ C-NMR, and ¹ H and ¹³ C binary NMR.

The chemical shift of each NMR is shown in Table 1b.

One 2 Chemical shift of ¹³ C-NMR 110 to 115 ppm 40 to 45 ppm Chemical shift of ¹ H-NMR 4.9 to 5.0 ppm 1.6 to 2.0 ppm

Identification of the 1,2-addition unit and determination of the quantification can be carried out in the same manner as described above because it exhibits the same chemical shift as that of the 3,4-addition unit.

The amount ratio between the component ratio and the structure derived from the conjugated diene is determined by the ratio between the peak areas of ¹ H-NMR and / or ¹³ C-NMR as above.

In addition, in the case of ethylene / styrene / 1,3-butadiene which is a 3rd unsaturated copolymer, identification and determination of an addition unit etc. can be performed according to the method mentioned above.

The sympathy of styrene 'Makromol. Chem. Phys. ' 197, 1071-1083 (1996) and 'Macromolecules' 28, 4665-4667 (1995).

The amount ratio between the component ratio and the structure derived from the conjugated diene is determined by the ratio between the peak areas of ¹ H-NMR and / or ¹³ C-NMR as above.

In the first unsaturated copolymers of the present invention, structural units derived from conjugated diene monomers, i.e., 1,2-addition units (including 3,4-addition units, are the same), 1,4-addition units and 5-membered rings ( It is desired that the total amount of the cyclopentane structure) and the cyclopropane (3-membered ring) be contained in an amount of 0.01 to 30 mol%, preferably 0.1 to 20 mol%. The remaining structural units are structural units derived from α-olefins such as ethylene.

In the second unsaturated copolymer of the present invention, structural units derived from conjugated diene monomers, i.e., 1,2-addition units (including 3,4-addition units), 1,4-addition units and 5-membered rings (cyclopentane structures It is desired that the total amount of) be contained in an amount of 0.01 to 30 mol%, preferably 0.1 to 15 mol%. The remaining structural units are structural units derived from α-olefins such as ethylene.

In the third unsaturated copolymer of the present invention, a structural unit derived from a conjugated diene monomer, that is, 1,2-addition unit (including 3,4-addition unit), 1,4-addition unit, 5-membered ring (cyclopentane structure ) And a cyclopropane ring (three-membered ring) are desired to be contained in an amount of 0.01 to 30 mol%, preferably 0.1 to 15 mol%. The remaining structural units are structural units derived from α-olefins such as ethylene and aromatic vinyl compounds such as styrene.

In the third unsaturated copolymer, the structural unit derived from the aromatic vinyl compound is contained in an amount of 0.1 to 60 mol%, preferably 0.1 to 40 mol%, more preferably 0.5 to 30 mol%; Structural units derived from α-olefins such as ethylene are contained in an amount of 10 to 99.9 mol%, preferably 45 to 99.8 mol%, and more preferably 50 to 99.6 mol%.

When the first, second and third unsaturated copolymers contain the above-mentioned structural units, they have excellent surface hardness, abrasion resistance, vibration insulation and buffering properties, and have good compatibility with other polar resins and fillers.

It is desired that the unsaturated copolymer of the present invention have an oxo number of usually 1 to 50, preferably 3 to 50, and more preferably 3 to 40. If the oxo number of the copolymer is within the above range, the copolymer exhibits high crosslinking efficiency when crosslinking the copolymer to form a rubber, and the resulting crosslinked product has excellent low temperature resistance.

The unsaturated copolymer of the present invention usually has an intrinsic viscosity (?) Of 0.01 to 10.0 dl / g, measured at 135 ° C and decalin. When the copolymer is used as a beeswax, beeswax additive, release agent, lubricant or rheology, the intrinsic viscosity (η) is preferably in the range of 0.01 to 1.0 dl / g. When the copolymer is applied to other uses, the intrinsic viscosity (η) is preferably in the range of 1.0 to 7.0 dl / g, more preferably 1.0 to 5.0 dl / g. When the intrinsic viscosity (η) of the copolymer is within the above range, the copolymer exhibits excellent weather resistance, ozone resistance, heat aging resistance, low temperature and dynamic fatigue resistance.

The unsaturated copolymer according to the present invention has a single glass transition temperature, which is usually 25 ° C. or less, preferably 10 ° C. or less, more preferably 0 ° C. as measured by a differential scanning calorimeter (DSC). Hereinafter, particularly preferably -30 deg. C or less, most preferably -35 deg. C or less is desired. The minimum of Tg is -150 degreeC normally.

When the glass transition temperature (Tg) of the copolymer is within the above range, the copolymer has excellent low temperature resistance and low temperature characteristics.

In some cases, the unsaturated copolymer which does not have more than the unsaturated copolymer which has an aromatic vinyl compound unit from a viewpoint of glass transition temperature and low temperature characteristic is preferable.

As the amount of ring structural units in each copolymer increases, the glass transition temperature also tends to increase. On the other hand, with increasing cis 1,4-addition units, 1,2-addition units (or 3,4-addition units) and the amount of α-olefin units, the glass transition temperature tends to decrease. The component ratio of depends largely on the setting range of the glass transition temperature.

In the present invention, at least of the ratio between the α-olefins in the case of using two or more α-olefins, the oxo number of the copolymer, the intrinsic viscosity (η) of the copolymer, and the glass transition temperature (Tg) of the copolymer It is preferable that one is in the said range, It is still more preferable if two or more of said are in the said range, It is especially preferable if all the said are in the said range.

As for Mw / Mn value (polystyrene conversion) of each copolymer, 3.0 or less are measured by GPC. Melting | fusing point (Tm) of each copolymer is 120 degrees C or less normally, measured by DSC, Preferably it is 110 degrees C or less, More preferably, it is 70 degrees C or less. When using a copolymer as an elastomer, melting | fusing point is 40 degrees C or less is especially preferable.

The degree of crystallinity of each copolymer is measured by an X-ray diffractometer, preferably 15% or less, and more preferably 10% or less. However, when using the copolymer of this invention for a film, it does not necessarily need to have above-mentioned Tm and crystallinity.

Each unsaturated copolymer of the present invention, in particular an ethylene / C _3-12 α-olefin / conjugated diene copolymer having a melting point (Tm) of 40 ° C. or less, has the same degree of oil swelling as that of the copolymer of the present invention. Swelling of ethylene / C _3-12 α-olefin / 5-ethylidene-2-norbornene copolymer (X) having intrinsic viscosity (η), oxo number, and ethylene content and α-olefin content of 3 to 12 carbon atoms 90% or less is preferable and 85% or less is more preferable on an induction basis. The degree of encapsulation is an index of crosslinking reactivity and is measured by a later method.

As used herein, the expression "copolymer (X) has the same intrinsic viscosity (η), oxo, and ethylene content as that of the copolymer of the present invention" indicates that the intrinsic viscosity (η), oxo value and ethylene content of the copolymer The intrinsic viscosity (η), oxo number and ethylene content of the unsaturated copolymer of the present invention are each in the range of ± 10%. When monomers other than the said monomer are copolymerized in the unsaturated copolymer of this invention, swelling degree is measured using the copolymer (X) which further contains the same monomer.

In the measurement of the swelling degree, 70 parts by weight of the unsaturated copolymer of the present invention or the reference copolymer (X), 30 parts by weight of homopolypropylene (MFR at 10 ° C .: 10 to 20 g / min), and divinylbenzene 0.1 Parts by weight and 0.15 parts by weight of 2,5-dimethyl-2,5- (tert-butylperoxyhexane) are homogeneously mixed, and the mixture is mixed with a melt kneader such as Labo Plastomil (Toyo Seiki Seisaku). And kneading at 200 ° C. for 5 minutes to obtain an olefin thermoplastic elastomer. Next, the swelling degree of the elastomer is measured.

Preparation of Unsaturated Copolymers

The first unsaturated copolymer of the present invention is an olefin polymerization catalyst, preferably a later-described metallocene catalyst, in which at least one of α-olefins having 2 to 12 carbon atoms and at least one conjugated diene monomer represented by general formula (Ia) It can obtain by copolymerizing in presence.

The second unsaturated copolymer of the present invention is an olefin polymerization catalyst, preferably a later-described metallocene catalyst, in which at least one of α-olefins having 2 to 12 carbon atoms and at least one conjugated diene monomer represented by general formula (Ib) Copolymerization in presence, Preferably it can obtain by random copolymerization.

The third unsaturated copolymer (or terpolymer) of the present invention comprises at least one of an α-olefin having 2 to 12 carbon atoms, an aromatic vinyl compound, and a general formula (I) (that is, a conjugated diene monomer (Ia) and / or a conjugated diene monomer). The conjugated diene monomer represented by (Ib)) can be copolymerized in the presence of an olefin polymerization catalyst, preferably a metallocene catalyst described later, preferably by random copolymerization.

The metallocene catalyst used here is at least one catalyst comprising a transition metal complex represented by the following general formula (II) or (III) and at least one compound selected from the following compounds (b), (c) and (d): to be.

In formulas (II) and (III) M is Ti, Zr, Hf, Rn, Nd, Sm or Ru; Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof π-bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms

(b) a compound which reacts with the transition metal (M) of component (a) to form an ionic complex,

(c) an organoaluminum compound, and

(d) aluminoxanes.

The transition metal complex (a) used in the present invention and represented by the following general formula (II) is described below.

Wherein M is a transition metal of Group 4 or lanthanum series of the periodic table, specifically Ti, Zr, Hf, Rn, Nd, Sm or Ru, preferably Ti, Zr or Hf; C pi is a cyclopentadienyl group, indenyl group, fluorenyl group, or any derivative thereof π-bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; Z is carbon, oxygen, sulfur, boron or an element of group 14 of the periodic table (ie silicon, germanium or tin), preferably carbon, oxygen or silicon and Z may have a substituent and Z and Y are condensed together It can form a ring.

More specifically, Cpl is a ligand for a transition metal, and has a cyclopentadienyl skeleton such as cyclopentadienyl group, indenyl group, fluorenyl group or derivatives thereof. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group or a halogen atom.

Z is an atom selected from C, O, B, S, Ge, Si and Sn, and may have a substituent such as an alkyl group or an alkoxy group. Substituents of Z may be bonded to each other to form a ring.

X ¹ and X ² are anionic ligands or neutral Lewis base ligands, respectively, which may be the same or different, and each a hydrogen group, a halogen atom, a hydrocarbon group containing up to 20 carbon atoms, a silicon atom or a germanium, a silyl group or It is a germil.

As an example of a compound represented by general formula (II);

(Dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride,

(t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl) titanium dichloride,

(Dimethyl (phenylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride,

(Dimethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dimethyl,

(Dimethyl (4-methylphenylamido) (tetramethyl-η ⁵ -cyclopentadienyl) silylene) titanium dichloride,

(Dimethyl (t-butylamido) (η ⁵ -cyclopentadienyl) silylene) titanium dichloride, and

(Tetramethyl (t-butylamido) (tetramethyl-η ⁵ -cyclopentadienyl) disylylene) titanium dichloride is mentioned.

In the present invention, a transition metal compound represented by the following general formula (III) can be used.

Wherein M is Ti, Zr, Hf, Rn, Nd, Sm or Ru, preferably Ti, Zr or Hf; Cp1 and Cp2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups or derivatives thereof which are? -Bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms

In general formula (III), the bonding group Z is preferably one atom selected from C, O, B, S, Ge, Si and Sn, and may have a substituent such as an alkyl group or an alkoxy group. Substituents of Z may be bonded to each other to form a ring.

Cpl and Cp2 are ligands coordinated to the transition metal, and are ligands having a cyclopentadienyl skeleton such as cyclopentadienyl group, indenyl group, 4,5,6,7-tetrahydroindenyl group or fluorenyl group. The ligand having a cyclopentadienyl skeleton may have a substituent such as an alkyl group, a cycloalkyl group, a trialkylsilyl group or a halogen atom.

Each of X ¹ and X ² negative ionic ligand or a neutral Lewis base ligand, in particular an alkoxy group, an aryloxy group having 1 to 12 carbon atoms or a hydrocarbon group, a sulfonic acid-containing group (-SO ₃ Ra Ra in formula is an alkyl group, a halogen An alkyl group substituted with an atom, an aryl group, an aryl group substituted with a halogen atom or an aryl group substituted with an alkyl group), a halogen atom or a hydrogen atom.

Examples of metallocene compounds containing zirconium as M and also having a cyclopentadienyl skeleton include:

Cyclohexylidene-bis (indenyl) dimethylzirconium,

Cyclohexylidene-bis (indenyl) zirconium dichloride,

Isopropylidene-bis (indenyl) zirconium dichloride,

Isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride,

Diphenylsilylene-bis (indenyl) zirconium dichloride,

Methylphenylsilylene-bis (indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2-methyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride,

rac-dimethylsilylene-bis (2-methyl-4- (1-anthyl) -1-indenyl) zirconium dichloride is mentioned.

In the compound, a metallocene compound in which zirconium is replaced with titanium or hafnium may be exemplified.

The metallocene compound mentioned above can be used individually or in combination of 2 or more types.

The metallocene compound can be used by being supported on a particulate carrier.

Examples of the particulate carrier include inorganic carriers such as SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, ZrO ₂ , CaO, TiO ₂ , ZnO, SnO ₂ , BaO, ThO; And organic carriers such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, and styrene / divinylbenzene copolymers. These particulate carriers can be used individually or in combination of 2 or more types.

Next, the following compounds (b), (c) and (d) for forming a metallocene catalyst will be described.

(b) reacts with the transition metal (M) of component (a) to form an ionic complex, i.e. an ionizing ionic compound,

(c) an organoaluminum compound, and

(d) Aluminoxanes (aluminum oxy-compounds).

(b) ionized ionic compounds

The ionizing ionic compound is a compound which reacts with the transition metal M of the transition metal complex component (a) to form an ionic complex. Examples of the ionizing ionic compound include Lewis acids, ionic compounds, borane compounds, and carborane compounds. There is a number.

Lewis acids are, for example, compounds represented by the general formula BR ₃ (R is a phenyl group or a fluorine atom which may have a substituent such as fluorine, methyl or trifluoromethyl). Examples of such compounds include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (penta) Fluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts and triarylphosphonium salts. Specific examples of the trialkyl-substituted ammonium salt include triethylammonium tetra (phenyl) boron, tripropyl ammonium tetra (phenyl) boron and tri (n-butyl) ammonium tetra (phenyl) boron. As a specific example of dialkyl ammonium, di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexyl ammonium tetra (phenyl) boron are mentioned. In addition, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferrocenium tetra (pentafluorophenyl) borate can also be used as ionic compounds. have.

Examples of borane compounds include decaborane (14), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decarborate, and bis [tri (n-butyl) ammonium] -bis ( And metal borane anion salts such as dodecahydridododecarborate) nickelate (III).

Examples of the carborane compound include 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), and bis [tri (n-butyl) ammonium] bis (undecahydrido-7-carba). And metal carborane anion salts such as undecaborate) and nickelate (IV).

The ionizing ionic compound mentioned above can be used individually or in combination of 2 or more types.

The organoaluminum oxy-compound and the ionizing ionic compound can be supported on the particulate carrier and used.

In the preparation of the catalyst, the following organoaluminum compound (c) can be used together with an organoaluminum oxy-compound and / or an ionizing ionic compound.

(c) organoaluminum compounds

As the organoaluminum compound (c), a compound having at least one Al-carbon bond in the molecule can be used. Compound (c) is, for example, an organoaluminum compound represented by the following general formula:

(R ¹ ) _m Al (O (R ² )) _n H _p X _q

In formula, R <^1> and R <^2> is the same or different, and they are respectively a C1-C15 hydrocarbon group, Preferably they are a C1-C4 hydrocarbon group; X is a halogen atom; m, n, p and q are numbers satisfying the conditions of 0 ≦ m ≦ 3, 0 ≦ n ≦ 3, 0 ≦ p ≦ 3, 0 ≦ q ≦ 3 and m + n + p + q = 3.

(d) organoaluminum oxy compounds (aluminoacids)

The organoaluminum oxycompound (d) may be a conventional aluminoxane or a benzene insoluble organoaluminum oxycompound as exemplified in Japanese Patent Laid-Open No. 2-78687.

Conventional aluminoxanes (alumoxanes) are represented by the general formula:

In which R is a hydrocarbon group such as methyl, ethyl, propyl or butyl, preferably methyl or ethyl, particularly preferably methyl; m is an integer of 2 or more, Preferably it is an integer of 5-40.

Aluminoxanes are mixed alkyloxyaluminum units (R ¹ and R ²⁾ consisting of alkyloxyaluminum units represented by the general formula (OAl (R ¹ )) and alkyloxyaluminum units represented by the general formula (OAl (R ² )). Each is the same hydrocarbon group as described for R above, and R ¹ and R ² are different from each other).

The organoaluminum oxycompound may contain a small amount of an organic compound of a metal other than aluminum.

In the present invention, it is preferable to use the metallocene catalyst described above as the olefin polymerization catalyst, but depending on the situation, (1) a known titanium catalyst or (2) soluble vanadium compound containing a solid titanium catalyst component and an organoaluminum compound And a known vanadium catalyst containing an organoaluminum compound can be used.

In the present invention, (iii) the α-olefin, (ii) the conjugated diene and, if necessary, (iii) the aromatic vinyl compound can be copolymerized in the usual liquid phase, preferably in the presence of the metallocene compound described above. . In this copolymerization, a hydrocarbon solvent is usually used, but α-olefin may be used as the solvent. The copolymerization can be carried out in either batch or continuous manner.

When the copolymerization is carried out batchwise in the presence of a metallocene catalyst, the metallocene compound is usually used in an amount of 0.00005 to 1 mmol, preferably 0.0001 to 0.5 mmol per liter of the polymerization volume.

The organoaluminum oxy compound is used in an amount such that the molar ratio (Al / M) of the aluminum atom (Al) to the transition metal atom (M) in the metallocene compound is 1 to 10,000, preferably 10 to 5,000.

The ionizable ionic compound is used in an amount such that the molar ratio of the ionized ionic compound (ionized ionic compound / metallocene compound) to the metallocene compound is 0.5 to 20, preferably 1 to 10.

In the case of using an organoaluminum compound, the amount is usually about 0 to 5 mmol, preferably about 0 to 2 mmol, based on 1 liter of the polymerization volume.

The copolymerization reaction is usually -20 to 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, and more than 0 kg / cm 2 to 80 kg / cm 2 or less, preferably more than 0 kg / cm 2 50 It is carried out under conditions of a pressure of kg / cm 2 or less.

The reaction time (average residence time in the case of the continuous polymerization method) varies depending on the conditions such as the catalyst concentration and the polymerization temperature, but is usually in the range of 5 minutes to 3 hours, preferably 10 minutes to 1.5 hours.

(alpha) -olefin (iii), conjugated diene (ii), and an aromatic vinyl compound (iii) are supplied to a polymerization reaction system in the quantity which can obtain the unsaturated copolymer which has the said specific component ratio as needed. In copolymerization, molecular weight regulators, such as hydrogen, can be used.

When copolymerizing (alpha)-olefin (i), conjugated diene (ii), and an aromatic vinyl compound (iii) as needed, the said unsaturated copolymer is obtained as a polymerization solution containing the said copolymer. This polymerization solution is treated by a conventional method to obtain an unsaturated copolymer.

Since the copolymer of this invention has a double bond in a main chain and a side chain, it can be variously modified. By peroxide modification, double bonds can be epoxidized to introduce highly reactive epoxy groups into the copolymer. In this way, a copolymer can be used as a thermosetting resin or a reactive resin. The double bond can also be used for the Diels-Alder reaction and the Michael addition reaction. In addition, by selectively hydrogenating the double bonds in the main chain and saturating them, the heat resistance and ozone resistance of the copolymer can be further improved.

The unsaturated copolymer of the present invention can be partially or completely modified with an unsaturated carboxylic acid, a derivative thereof or an aromatic vinyl compound, and the modification ratio is preferably 0.01 to 30% by weight.

Particularly in the unsaturated copolymer, since the reactive double bond is present in the side chain, it is possible to reduce the amount of radical initiator used for modification. In contrast, in resins without double bonds in the side chain, the radicals generated by the hydrogen drawing reaction are the starting point. Since not all initiators induce hydrogen draw reactions, a large amount of initiator is required. In addition, since the decomposition reaction also occurs, the molecular weight is usually lowered.

In the unsaturated copolymer of the present invention, since the highly reactive terminal double bonds are present in the side chain, the amount of initiator can be reduced. In addition, since the generated radicals mainly react with the double bonds of the side chains, the decomposition reaction of the main chain can be suppressed, thereby reducing the molecular weight decrease.

Monomers used for modification (hereinafter referred to as 'graft monomers') include unsaturated carboxylic acids, derivatives thereof and aromatic vinyl compounds. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid. Examples of derivatives of unsaturated carboxylic acids include anhydrides, esters, amides, imides and metal salts of unsaturated carboxylic acids. Specifically, maleic anhydride, citraconic anhydride, itaconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glyc Cydyl methacrylate, mono ethyl maleate, diethyl maleate, monomethyl fumarate, dimethyl fumarate, monomethyl itaconate, diethyl itaconate, acrylamide, methacrylamide, maleic acid monoamide, maleic acid dia Mid, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N- Monoethylamide, fumaric acid-N, N-diethylamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butylmale Imide, N- phenylmaleimide, there may be mentioned the sodium acrylate, sodium methacrylate, potassium acrylate and potassium methacrylate. It is preferable to use maleic anhydride among these graft monomers.

Examples of the aromatic vinyl compound include styrene;

mono or polyalkylstyrenes such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene;

Functional group-containing styrene derivatives such as methoxy styrene, ethoxy styrene, vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, o-chloro styrene, p-chloro styrene and divinyl benzene; And

Other compounds, such as 3-phenylpropylene, 4-phenylbutene, and (alpha) -methylstyrene, are mentioned.

Among these, styrene or 4-methoxy styrene is preferable.

In order to graft copolymerize each of said unsaturated copolymer with a graft monomer, various well-known methods can be used.

For example, graft copolymerization is carried out by heating the unsaturated copolymer and graft monomer at high temperature in the presence or absence of a solvent, in the presence or absence of a radical initiator. The graft copolymerization reaction may be carried out in the presence of another vinyl monomer such as styrene.

In order to prepare partially or fully graft modified unsaturated copolymers having a graft ratio of 0.01 to 30% by weight, from the viewpoint of industrial production, first, a graft modified unsaturated copolymer having a high graft ratio is prepared. Next, the graft ratio is adjusted by adding the graft modified unsaturated copolymer to the unmodified unsaturated copolymer. In this method, the concentration of the graft monomer in the composition can be appropriately adjusted. The copolymer obtained in this way is called 'partially graft modified unsaturated copolymer'. In addition, graft modification may be performed by blending a predetermined amount of graft monomer with the unsaturated copolymer from the beginning. The polymer obtained in this way is referred to as 'fully graft modified unsaturated copolymer'.

As for the degree of modification by the graft monomer of the unsaturated copolymer, the graft ratio with respect to the total resin is preferably in the range of 0.01 to 30% by weight, particularly preferably 0.05 to 10% by weight.

The modified unsaturated copolymer obtained above (hereinafter referred to as 'modified copolymer') may be blended with an ethylene / α-olefin copolymer and / or an ethylene / vinyl acetate copolymer to prepare a modified unsaturated copolymer-containing composition. .

By blending the modified unsaturated copolymer with an ethylene / α-olefin copolymer and / or ethylene / vinyl acetate copolymer, the melt viscosity of the resulting composition can be reduced, thereby improving the moldability of the composition. In addition, the adhesion can be further improved after the retort treatment and the adhesion strength to the polyolefin can be increased.

As the ethylene / α-olefin copolymer, an ethylene / α-olefin copolymer having random copolymerization of ethylene and α-olefin and having an ethylene content of 45 to 95 mol%, preferably 45 to 90 mol% is used.

The ethylene / α-olefin copolymer has a melt flow rate (ASTM D 1238, condition E) of usually 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes, and a density of usually 0.850 to 0.900 g / 10 minutes, preferably 0.850 to 0.890 g / cm 3, and the crystallinity measured by the X-ray diffraction method is usually less than 30%, preferably less than 25%.

Examples of α-olefins that form ethylene / α-olefin copolymers include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene and 1-octa C3-C20 alpha olefins, such as decene, are mentioned. These alpha -olefins are used individually or as a mixture of 2 or more types.

The melting point (ASTM D 3418) of the ethylene / α-olefin copolymer is usually 100 ° C. or lower.

The ethylene / vinyl acetate copolymer has a vinyl acetate content of 5 to 45% by weight, preferably 10 to 35% by weight. The ethylene / vinyl acetate copolymers have a melt flow rate (ASTM 1238 D, condition E) of usually 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes.

The modified unsaturated copolymer-containing composition, in addition to the graft modified unsaturated copolymer, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer, crystalline ethylene polymer, crystalline propylene polymer, modified products of these polymers and It may further comprise a tackifier.

The crystalline ethylene polymer is a homopolymer of ethylene or a copolymer of ethylene and a small amount of other α-olefins and has an ethylene content of more than 90 mol% and 100 mol% or less, preferably 95 to 100 mol%.

The crystalline ethylene polymer has a melt flow rate (ASTM D 1238, condition E) of typically 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes, and a density of usually 0.900 to 0.980 g / cm 3, preferably Preferably from 0.920 to 0.970 g / cm 3.

Examples of α-olefins that form crystalline ethylene copolymers include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, and the like. C3-C20 alpha-olefin can be mentioned. These alpha -olefins can be used individually or in combination of 2 or more types.

The crystalline ethylene polymer may be modified with an unsaturated carboxylic acid, a derivative thereof or an aromatic vinyl compound. Examples of unsaturated carboxylic acids, derivatives and aromatic compounds are as described above. The modified ethylene polymer can be produced by various methods.

The composition containing the crystalline ethylene polymer is excellent in adhesion.

The crystalline propylene polymer is a homopolymer of propylene or a copolymer of propylene with a small amount of other α-olefins, with a propylene content of greater than 55 mol% and up to 100 mol%, preferably 80 to 100 mol%.

The crystalline propylene polymer has a melt flow rate (ASTM D 1238, condition E) of usually 0.1 to 50 g / 10 minutes, preferably 0.3 to 30 g / 10 minutes, melting point (Tm) is usually 110 ~ 165 ℃, Preferably it is 120-165 degreeC.

Examples of the α-olefins forming the crystalline propylene copolymer include ethylene and 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene, and the like. C4-C20 alpha-olefin can be mentioned. These alpha -olefins can be used individually or in combination of 2 or more types.

The crystalline propylene polymer may be modified with an unsaturated carboxylic acid, a derivative thereof or an aromatic vinyl compound. Examples of unsaturated carboxylic acids, derivatives and aromatic compounds are as described above. The modified propylene polymer can be produced by various methods.

The composition containing the crystalline propylene polymer is excellent in adhesion.

A tackifier is added to adjust the melt viscosity of the modified unsaturated copolymer-containing composition and to improve hot tack and wettability. Examples of preferred tackifiers include alicyclic hydrogenated tackifiers, rosin, modified rosin, esters of rosin or modified rosin, aliphatic petroleum resins, alicyclic petroleum resins, aromatic petroleum resins, copolymers containing aliphatic / aromatic components And petroleum resins, low molecular weight styrene resins, isoprene resins, alkyd resins, phenolic resins, terpene resins and coumarone-indene resins. These tackifiers can be used individually or in combination of 2 types of paper.

The modified unsaturated copolymer-containing composition (sometimes referred to as a 'resin composition') is 1 to 100 parts by weight of the graft modified unsaturated copolymer (sometimes referred to as a 'modified copolymer'), preferably 1 To 80 parts by weight, more preferably 10 to 80 parts by weight, and 0 to 99 parts by weight of the soft polymer, preferably 20 to 99 parts by weight, more preferably 20 to 90 parts by weight, provided that the modified copolymer and the soft The total of the polymer is 100 parts by weight).

Examples of the soft polymers include the ethylene / α-olefin copolymers, the ethylene / vinyl acetate copolymers, and mixtures thereof.

Preferred embodiments of the composition include 10 to 80 parts by weight of the modified copolymer, and 20 to 90 parts by weight (total: 100 parts by weight) of the ethylene / α-olefin copolymer and / or the ethylene / vinyl acetate copolymer.

More specifically, the following may be mentioned:

10 to 80 parts by weight of the modified copolymer, preferably 30 to 80 parts by weight, and 20 to 90 parts by weight of the ethylene / α-olefin copolymer, preferably 20 to 70 parts by weight (total: 100 parts by weight) Composition,

10 to 80 parts by weight of the modified copolymer, preferably 30 to 80 parts by weight, and 20 to 90 parts by weight of the ethylene / vinyl acetate copolymer, preferably 20 to 70 parts by weight (total: 100 parts by weight) , And

10 to 80 parts by weight of modified copolymer, preferably 30 to 80 parts by weight, and 5 to 60 parts by weight of ethylene / α-olefin copolymer, preferably 10 to 50 parts by weight, and 5 to ethylene / vinyl acetate copolymer A composition comprising 40 parts by weight, preferably 10 to 30 parts by weight (total: 100 parts by weight).

As described above, the modified unsaturated copolymer-containing composition of the present invention, in addition to the modified copolymer, ethylene / α-olefin copolymer and ethylene / vinyl acetate copolymer, ethylene polymer, its modified product, propylene polymer, modified product thereof And tackifiers.

When adding an ethylene polymer or its modified substance, 0.1-50 weight part, Preferably 1-30, with respect to a total of 100 weight part of the said modified copolymer, ethylene / alpha-olefin copolymer, and ethylene / vinyl acetate copolymer. Used in parts by weight.

When adding a propylene polymer or its modified product, 0.1-50 weight part, Preferably 1-30, with respect to a total of 100 weight part of the said modified copolymer, ethylene / alpha-olefin copolymer, and ethylene / vinyl acetate copolymer. Used in parts by weight.

When adding a tackifier, the amount of 0.5 to 25 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the total copolymer, the ethylene / α-olefin copolymer and the ethylene / vinyl acetate copolymer. Used as

As described above, the modified unsaturated copolymer-containing composition (sometimes referred to as 'modified copolymer-containing composition') essentially includes the graft modified unsaturated copolymer, and the graft ratio of the total resin composition is usually 0.01 30 wt%, preferably 0.05-10 wt%. The composition has an MFR of 0.1-50 g / 10 minutes, preferably 0.2-40 g / 10 minutes, and a crystallinity of less than 35%.

The modified unsaturated copolymer-containing composition can be prepared by various methods. For example, using a Henschel mixer, a V-type blender, a ribbon blender, a tumbling blender, etc. to mix the components at the above mixing ratio, and mixing as described above, and then mixing the mixture as a single screw extruder, twin screw extruder, kneader, It can be manufactured by melt-kneading using a Banbury mixer or the like and granulating or powdering the kneaded product.

To the modified copolymer-containing composition, additives such as heat stabilizers, weather stabilizers, antistatic agents, pigments, dyes, and corrosion inhibitors may be added in amounts not to impair the object of the present invention.

The modified copolymer-containing composition can be advantageously used as an adhesive between these resins because of its excellent adhesiveness to polyester resins, polycarbonate resins, saponified olefins / vinyl acetate copolymers and polyolefins.

For example, when the laminate is manufactured by adhering a polycarbonate resin layer or a polyester resin layer to a saponified ethylene / vinyl acetate copolymer resin layer using the modified copolymer-containing composition, the laminate has excellent gas permeability. And high temperature charging or retort treatment does not cause delamination. Since the laminate has low gas permeability such as oxygen, it shows very excellent properties when used as a retort packaging material or a hot packing material.

When the unsaturated copolymer of the present invention (sometimes referred to as 'α-olefin / conjugated diene copolymer' or 'unsaturated terpolymer') is used as the elastomer, the unsaturated copolymer (A) is used as a crosslinking agent (B) and Preference is given to blending with at least one component selected from filler (C) to produce an unsaturated copolymer-containing elastomer composition (sometimes referred to as an 'elastomer composition'). An ethylene / α-olefin copolymer can be further added to this elastomer composition.

The crosslinking agent (B) used in the present invention is, for example, sulfur, sulfur compound or organic peroxide.

Examples of sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface treated sulfur and insoluble sulfur.

Examples of sulfur compounds include sulfur chloride, sulfur dichloride and high molecular weight polysulfides. In addition, crosslinking of the unsaturated copolymer by releasing active sulfur at crosslinking temperatures such as morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulphide and selenium dimethyldithiocarbamate Sulfur compounds may be used.

When using sulfur or a sulfur compound as a crosslinking agent, it is preferable to use combining a crosslinking promoter.

Examples of the organic peroxide include dicumyl peroxide (DCP), di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di- t-amyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, α, α ' Alkyl peroxides such as -bis (t-butylperoxy-m-isopropyl) benzene and t-butyl hydroperoxide; t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-butyl peroxymaleate, t-butyl peroxyneodecanoate, t-butyl peroxybenzoate and di peroxy esters such as -t-butyl peroxyphthalate; And ketone peroxides such as dicyclohexanone peroxide. These organic peroxides can be used alone or in combination of two species.

Among the organic peroxides, those having a half-life of 1 minute have a temperature of 130 to 200 ° C. Examples of such organic peroxides are dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, di-t-amyl peroxide Oxides and t-butyl hydroperoxides. When using an organic peroxide as a crosslinking agent, it is preferable to use combining a crosslinking adjuvant.

Among the various crosslinking agents described above, sulfur or a sulfur compound, particularly sulfur, is preferable because a crosslinked product having excellent properties can be obtained. However, organic peroxide is more preferable because the crosslinking efficiency is particularly excellent.

Since the unsaturated copolymer of the present invention can be crosslinked with sulfur or any of the above peroxides, it is very economically excellent. Especially, the copolymer containing the structural unit derived from the conjugated diene monomer of general formula (I-b) is effectively bridge | crosslinked by sulfur or the said peroxide.

When the crosslinking agent (B) is sulfur or the sulfur compound, the amount is usually 0.5 to 10 parts by weight, preferably 1 to 10 parts by weight, and more preferably 1 to 5 parts by weight based on 100 parts by weight of the unsaturated copolymer (A). Used as When the crosslinking agent (B) is the organic peroxide, the amount is usually 0.00005 to 0.1 mol, preferably 0.0005 to 0.05 mol, based on 100 g of the unsaturated copolymer (A). Filler (C) includes fillers (reinforced fillers) that exhibit reinforcing effects and fillers (non-reinforced fillers) that do not exhibit reinforcing effects.

The reinforcing filler has an effect of improving mechanical properties such as tensile strength, tear strength and wear resistance of the crosslinked product. Examples of such fillers include carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT and MT; Carbon black surface-treated with a silane coupling agent or the like; Silica; Activated calcium carbonate; And finely powdered talc. When carbon black is used as the filler, any carbon black commonly used in rubber can be used without particular limitation.

Unreinforced fillers are used to increase the hardness of a rubber product while not affecting its properties or reducing its cost. Such fillers include talc, clay and calcium carbonate.

The filler (C) is usually used in an amount of 300 parts by weight or less, preferably 10 to 300 parts by weight, and more preferably 10 to 200 parts by weight with respect to 100 parts by weight of the unsaturated copolymer (A).

The unsaturated copolymer-containing elastomer composition can be prepared by a known method. For example, the unsaturated copolymer (A) is blended with other components containing at least one component selected from a crosslinking agent (B) and a filler (C), and with other rubber compounding components and the mixture is banbury mixer, kneader Or it can manufacture by the method which knead | mixes by internal mixers, such as an intermixer.

Although the unsaturated copolymer-containing elastomer composition according to the present invention can be used in an uncrosslinked state, its properties are most prominent when the composition is used as a crosslinked product. That is, the unsaturated copolymer (A) serves to increase the crosslinking rate of the composition or to improve the strength properties of the crosslinked product.

In order to produce a crosslinked product from a composition that does not contain a crosslinking agent (B), similarly to the case of crosslinking a conventional rubber, an unsaturated copolymer-containing elastomer composition is first prepared, and then molded into a predetermined shape and crosslinked. Crosslinking can be performed by irradiating an electron beam.

In order to produce a crosslinked product from a composition containing a crosslinking agent (B), similarly to the case of crosslinking with a conventional rubber, an unsaturated copolymer-containing elastomer composition is first prepared, then molded into a predetermined shape and crosslinked by heating or the like.

Uncrosslinked compounded rubber (uncrosslinked unsaturated copolymer-containing elastomer composition), in addition to unsaturated copolymer (A), crosslinking agent (B) and filler (C), crosslinking accelerator, crosslinking aid, softener, tackifier, anti-aging agent, foaming agent, Various rubber compounding components, such as processing aids, tackifiers, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, flame retardants, and antifogging agents, may be further included in an amount that does not impair the object of the present invention.

Examples of crosslinking accelerators include N-cyclohexyl-2-benzothiazole sulfenamide (CBZ), N-oxydiethylene-2-benzothiazole sulfenamide, N, N-diisopropyl-2-benzothiazole sulfen Amide, 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole and dibenzo Thiazole compounds such as thiazyl disulfide; Guanidine compounds such as diphenylguanidine (DPG), triphenylguanidine, diolsonitrile guanidine, olsonnitrile biguanide and diphenylguanidine phthalate; Aldehyde amine compounds or aldehyde ammonia compounds such as acetaldehyde-aniline reaction product, butylaldehyde-aniline condensate, hexamethylenetetramine and acetaldehyde ammonia; Imidazoline compounds such as 2-mercaptoimidazoline; Thiourea compounds such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, and diolsoolylthiourea; Thiuram compounds such as tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and pentamethylenethiuram tetrasulphide; Zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithi Dithioate compounds such as ocarbamate and selenium dimethyldithiocarbamate; Xanthate compounds such as zinc dibutyl xanthate; And other compounds such as zincation. The crosslinking accelerator is used in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A).

Examples of the crosslinking aid include sulfur; quinone dioxime compounds such as p-quinone dioxime; Polyfunctional monomers such as methacrylate compounds (eg, trimethylolpropane triacrylate and polyethylene glycol dimethylacrylate); And allyl compounds (such as diallyl phthalate and triallyl cyanurate), maleimide compounds (such as m-phenylenebismaleimide), and divinylbenzene. The crosslinking aid is preferably 0.5 to 2 mol, more preferably about the same mole number, per 1 mol of the organic peroxide.

As the softener, those which are widely added to rubber in general can be used. Examples of the softener include petroleum softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt and petroleum jelly; Coultar softeners such as coultar and coultar pitch; Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, and coconut oil; Tall oil; Factis; Waxes such as beeswax, carnauba wax and lanolin; Fatty acids and fatty acid salts such as ricinolic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; And petroleum resins, atactic propylene, and coumarone-indene resins. Among them, petroleum-based softeners are preferably used, and process oil is particularly preferably used. The softening agent is preferably 200 parts by weight or less, more preferably 5 to 200 parts by weight, particularly preferably 10 to 150 parts by weight, still more preferably 10 to 100 parts by weight of the unsaturated copolymer (A). It is used in the amount of 100 parts by weight.

As a blowing agent, what is normally used for foaming of rubber | gum can be used widely. Examples of the blowing agent include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate and ammonium nitrite; Nitroso compounds such as N, N'-dimethyl-N, N'-dinitrosoterephthalamide and N, N'-dinitrosopentamethylenetetramine; Azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene and barium azodicarboxylate; And sulfonylhydrazine compounds such as benzenesulfonylhydrazide, toluenesulfonylhydrazide, p, p'-oxybis (benzenesulfonylhydrazide) and diphenylsulfon-3,3'-disulfonylhydrazide; And azide compounds such as calcium azide, 4,4-diphenyldisulfonyl azide and p-toluenesulfonyl azide. Of these, nitroso compounds, azo compounds and azide compounds are preferable.

The blowing agent is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the unsaturated copolymer (A). From the unsaturated copolymer-containing elastomer composition containing the blowing agent in the above amount, a foamed product having an apparent density of 0.03 to 0.8 g / cm 3 can be obtained.

Foaming aids may be used in combination with foaming agents. When the blowing aid is used in combination, it is possible to lower the decomposition temperature of the blowing agent, to promote the decomposition of the blowing agent and to generate uniform bubbles. Examples of the foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid; Urea and derivatives of urea. The foaming aid is used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the unsaturated copolymer (A).

As the processing aid, those commonly added to rubber can be used. Examples of processing aids include higher fatty acids such as ricinolic acid, stearic acid, palmitic acid and lauric acid; Salts of higher fatty acids such as barium stearate, zinc stearate and calcium stearate; And esters of higher fatty acids. The processing aid is used in an amount of 10 parts by weight or less, more preferably 5 parts by weight or less, based on 100 parts by weight of the unsaturated copolymer (A).

The tackifier improves adhesion between the crosslinked material and a decorative layer such as a coating film, and is, for example, an organotin compound, a tertiary amine compound, a hydroxyl group-containing (co) polymer or a metal hydroxide.

Examples of the organotin compound include dialkyltin dicarboxylates such as dibutyltin diacetate, dibutyltin dioctanoate, dibutyltin dilauate and dioctyltin dilaurate;

Dialkyl tin maleates such as dibutyl tin dimethyl maleate, dibutyl tin dioctyl maleate, dibutyl tin dioleyl maleate, dibutyl tin dimethoxymethyl maleate and dibutyl tin laurate methyl maleate; Dialkyltin dithioglycolates such as dibutyltin dioctylthioglycolate and dioctyltin dioctylthioglycolate; Dialkyl tin dimercaptides such as dibutyltin dilauryl mercaptide and dioctyltin dilauryl mercaptide; Dialkyltin dithiocarboxylates such as dibutyltin dithioacetate, dibutyltin dithiooctanoate, dibutyltin dithiolaurate and dioctyltin dithiolaurate; Dialkyl tin dimercaptocarboxylates such as dibutyl tin dimercaptopropionate; Dialkylhydroxytin chlorides such as dibutylhydroxytin chloride; Alkyl tin trilaurate such as butyl tin trilaurate and octyl tin trilaurate; Alkyl tin trimaleate such as butyl tin trimethyl maleate and butyl tin trioctyl maleate; Alkyl hydroxytin dichlorides such as butylhydroxytin dichloride; Triaralkyltin maleates such as tribenzyltin octyl maleate and tribenzyltin methyl maleate; And dialkyl tin maleate polymers such as dioctyl tin maleate polymer. The organotin compound is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight based on 100 parts by weight of the unsaturated copolymer (A).

The tertiary amine compound is a low molecular weight tertiary amine compound, for example. Examples of such compounds include monoamines such as triethylamine, dimethylpropylamine, diethylpropylamine and N, N-dimethylcyclohexane; Triethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropane-1,3-diamine and N, N, N ', N'-tetra Diamines such as methylhexane-1,6-diamine; N, N, N ', N', N ', N'-hexamethyldiethylenetriamine, N, N, N', N ', N', N'-hexamethyldipropylenetriamine and tetramethylguanidine, etc. Triamine of; N, N'-dimethylpiperazine, N-methyl-N '-(2-dimethylamino) -ethylpiperazine, N-methylmorpholine, N- (N', N'-dimethylaminoethyl) -morpholine, Cyclic amines such as 1,2-dimethylimidazole, 1,4-diazabicyclo- [2.2.2] -octane and 1,8-diazabicyclo- [5,4,0] -7-undecene; Dimethylaminoethanol, methylaminodiethanol, dimethylaminoethoxyethanol, N, N, N'-trimethylaminoethylethanolamine, N-methyl-N '-(2-hydroxyethyl) -piperazine and N- (2 Alcohol amines such as hydroxyethyl) morpholine; Phenolamines such as tris (dimethylamino) methylphenol; Etheramines such as bis (2-dimethylaminoethyl) ether and ethylene glycol bis (3-dimethyl) aminopropyl ether; And 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, 2- (diethylamino) ethyl methacrylate, 2- (dibutyl And tertiary amino group-containing unsaturated compounds such as amino) ethyl acrylate, 2- (dibutylamino) ethyl methacrylate, 2- (dimethylamino) propylacrylamide, and 2- (dimethylamino) propylmethacrylamide. .

As the tertiary amine compound, a high molecular weight compound such as a tertiary amino group-containing olefin (co) polymer can be used.

The tertiary amino group-containing olefin (co) polymer has a structure in which tertiary amino group-containing unsaturated compounds are copolymerized regularly or irregularly in a branched or linear hydrocarbon chain or have a side chain grafted structure having a tertiary amine structure. Moreover, 0.1-50 weight% of tertiary amino-group containing unsaturated compounds are contained. The tertiary amino group-containing olefin (co) polymer can be produced by known methods, for example, by copolymerizing tertiary amino group-containing unsaturated compounds or by graft polymerization of polyolefins with tertiary amino group-containing unsaturated compounds. Among the above-mentioned tertiary amine compounds, it is preferable to use 1,4-diazabicyclo- [2.2.2] -octane. The tertiary amine compound is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight per 100 parts by weight of the unsaturated copolymer (A).

The hydroxyl group-containing (co) polymers are, for example, saponified of ethylene / vinyl acetate copolymers; Conjugated diene polymers having a hydroxyl group at the terminal of a molecule such as polybutadiene having a hydroxyl group at the terminal and a polyisoprene having a hydroxyl group at the terminal; Hydrides of conjugated diene polymers having a hydroxyl group at the terminal of a molecule, such as a hydride of polybutadiene having a hydroxyl group at the terminal and a hydride of a polyisoprene having a hydroxyl group at the terminal; Of a hydroxyl group-containing unsaturated compound such as ethylene / hydroxyethyl acrylate copolymer, ethylene / hydroxyethyl methacrylate copolymer, ethylene / hydroxyoctyl acrylate copolymer and ethylene / hydroxyoctyl methacrylate copolymer Copolymers; And polyethylene, polypropylene, ethylene / α-olefin graft modified with hydroxyl group-containing unsaturated compounds (eg, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxyoctyl acrylate and hydroxyoctyl methacrylate). Graft modified α-olefin (co) polymers such as copolymers and ethylene / α-olefin / polyene copolymers. Among these, hydrides of polybutadiene having a hydroxyl group at the molecular terminal and polyisoprene hydrides having a hydroxyl group at the terminal are preferable. The addition of hydroxyl group-containing (co) polymers may increase the adhesive strength between the crosslinked product and the coating film of the urethane resin. The hydroxyl group-containing (co) polymer is preferably used in an amount of 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

Metal hydroxides are, for example, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, iron hydroxide and nickel hydroxide. Of these, aluminum hydroxide and magnesium hydroxide are preferred, and magnesium hydroxide is particularly preferred. The metal hydroxide is preferably used in an amount of 20 to 200 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 50 to 150 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

There is no particular limitation on the method for preparing the crosslinked product from the unsaturated copolymer-containing elastomer composition of the present invention. For example, the following method can be used.

In a mixer such as a Banbury mixer, the unsaturated copolymer (A) and, if necessary, the filler (C), liquid softener (D) and other rubber compounding ingredients are kneaded at 80-170 ° C. for 3-10 minutes. Then, using a roll such as an open roll, a crosslinking agent (B) and, if necessary, a crosslinking accelerator are added, and the mixture is kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes and then sprayed to give a ribbon or sheet shape. Uncrosslinked compounded rubber is prepared. When the kneading temperature in the mixer is low, the crosslinking agent (B), the crosslinking accelerator and the blowing agent can be kneaded simultaneously.

The uncrosslinked compounded rubber is then molded into the desired shape by an extruder, calendar roll or press. Simultaneously with molding, the compounded rubber is heated at a temperature of 150 to 270 ° C. for 1 to 30 minutes or after molding, the molded product is placed in a crosslinking bath and heated at a temperature of 150 to 270 ° C. for 1 to 30 minutes to obtain a crosslinked product. Crosslinking may be performed in a mold, or may be performed without using a mold. When a mold is not used, a molding process and a crosslinking process are generally performed continuously. Various heating means such as hot air, glass grain fluidized bed, UHF (ultra high frequency electromagnetic wave) and steam (heating bath) can be used to heat the molded article in the crosslinking bath.

The following method can be used to prepare the crosslinked product by electron beam irradiation. In an mixer such as a Banbury mixer, the unsaturated olefin copolymer (A) and, if necessary, the filler (C) and other rubber compounding components are kneaded at a temperature of 80 to 170 ° C. for 3 to 10 minutes and then ejected to give uncrosslinked ribbon or sheet. Prepare compound rubber. The uncrosslinked compounded rubber is then molded into the desired shape by an extrusion machine, calendar roll or press, and then the molded product is irradiated with an electron beam to obtain a crosslinked product. The molded article is preferably irradiated with an electron beam having an energy of 0.1 to 10 Mev (megaelectron volt), preferably 0.3 to 2 Mev so that the absorption amount is 0.5 to 35 Mrad (megarad), preferably 0.5 to 10 Mrad.

Unsaturated copolymers of the present invention are excellent because they have a high crosslink density, especially when they crosslink with organic peroxides, especially when they crosslink with organic peroxides.

The crosslinks obtained above are widely used for automotive parts, general industrial parts and civil and building materials. In particular, for example, tire floors, tire floor modifiers, automotive engine parts, rubber vibration insulating materials, rubber rolls, heat-resistant belts, hoses, wiper blades, electric wires, various packaging materials, negative electrode caps, and grommets that require oil resistance and dynamic fatigue resistance Electrical insulating materials, such as building gaskets and building sheets, civil engineering and building materials, and rubberized fibers can be used. Crosslinks are used in particular for automotive insulation, such as engine mounted insulation, center bearing insulation and rack and pinion steering gear insulation. The crosslinked product has excellent tear resistance.

Foams can also be prepared from the unsaturated copolymer-containing elastomer compositions of the invention. In preparing the foam, the composition is foamed by adding a foaming agent commonly used for rubber and a foaming aid used as necessary to the elastomer composition. The blowing agent is preferably used in an amount of 0.5 to 30 parts by weight, more preferably 1 to 20 parts by weight, per 100 parts by weight of the unsaturated copolymer (A). The apparent specific gravity of the resulting foam is usually 0.03 to 0.7. Foams can be used for thermal insulation, cushioning, sealing and hoses.

From the unsaturated copolymer containing elastomer composition (compound rubber containing uncrosslinked and crosslinked) of this invention, the crosslinked molded article which has a surface decoration layer can be manufactured. The crosslinked molded article having the surface decoration layer can be obtained by coating the surface of the above-mentioned crosslinked product or by adhering the crosslinked product using a member of another material such as metal or resin and an adhesive material to form a decorative layer. It is also possible to form a decorative layer on the uncrosslinked compounded rubber and then crosslink the compounded rubber to obtain a crosslinked molded article having a surface decoration layer.

When the unsaturated copolymer-containing elastomer composition is a third unsaturated copolymer-containing elastomer composition, for example, an α-olefin / aromatic vinyl compound / conjugated diene polymer-containing elastomer composition, the content of the aromatic vinyl compound is 0.1 to based on the total elastomer composition. It is preferable that it is 40 mol%, especially 0.5-30 mol%. If the content of the aromatic vinyl compound is within the above range, the elastomer composition exhibits excellent coating properties.

As the coating material for coating the crosslinked or uncrosslinked compound rubber, those which are widely used at present can be used. For example, acrylic resin paint, epoxy resin paint, polyester resin paint, urethane resin paint, alkyd resin paint, melamine resin paint, silicone resin paint and the like.

Acrylic resin paints are prepared by polymerizing or copolymerizing comonomers selected from acrylic acid, methacrylic acid and esters thereof and other comonomers, if necessary, by solution polymerization or emulsion polymerization, and, if necessary, diluents, A paint used as a transparent lacquer obtained by adding a resin and other additives, or a paint used as an enamel obtained by adding a pigment to the transparent lacquer.

Polyester resin paint is a paint hardened | cured by making a vinyl compound etc. act on the unsaturated polyester obtained by polycondensing polybasic acid and polyhydric alcohol. Polyhydric alcohols usable here are, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and the like. Polybasic acids usable here are, for example, phthalic anhydride, maleic anhydride, fumaric anhydride and adipic anhydride and the like. Vinyl compounds usable here are styrene, methacrylic acid and the like. Of these, propylene glycol, phthalic anhydride and styrene are most often used.

A urethane resin paint is generally a paint which forms a coating film by reaction between a polyisocyanate and a polyol compound. Urethane resin paints are available in 1-pack type and 2-pack type, and there are also powder coatings using block-type isocyanates.

Melamine resin paints are produced by combining butylated melamine resins etherified with butanol as a thermosetting paint with a phthalic acid resin or a butylated urea resin. As the phthalic acid resin, one modified with an undried oil or semi-dry oil such as castor oil or coconut oil is usually used.

Silicone resin paint is a paint using curable silicone resin or curable silicone resin modified with alkyd, epoxy, phenol, acrylic, melamine or urethane.

Among the paints, acrylic resin paints, melamine resin paints, polyester resin paints, urethane resin paints and silicone resin paints are preferred. This is because the resulting coating film has excellent adhesion. In particular, a urethane resin paint and a silicone resin paint are good. This is because the resulting coating film has excellent adhesion.

Coating may be by spray, brush and roller coating.

There is no particular limitation on the thickness of the coating and the thickness can be varied depending on the intended use of the molded article. Generally, the thickness is usually about 1 to 500 mu m.

Crosslinked articles having a surface decoration layer can be used for automotive industry components such as windshields, door glass traveling channels and window frames and for building materials such as grading gaskets, joint gaskets and air tight gaskets.

When the cross-linked product is used for a sponge wind sponge, it is preferable to use two kinds of α-olefins composed of ethylene and α-olefins having 3 or more carbon atoms as olefins in the unsaturated copolymer, in which case the molar ratio of ethylene and other α-olefins (ethylene / Other α-olefin) is preferably 80/20 to 60/40 (100 mol in total).

In particular, when a crosslinked molded article using a third unsaturated copolymer (unsaturated terpolymer) is used for a wind blowing sponge, two kinds composed of ethylene and an α-olefin having 3 or more carbon atoms in the above-described molar ratio as the olefin in the third unsaturated copolymer. It is preferable to use the α-olefin. When styrene is copolymerized as an aromatic vinyl compound, the styrene content is preferably 1 to 7 mol%, preferably 2 to 6 mol%.

The intrinsic viscosity (η) of each of the unsaturated copolymers of the present invention used for the sponge wind sponge is preferably 2.5 to 4.5 dl / g. Moreover, sulfur crosslinking is preferable as crosslinking. If the ethylene / α-olefin molar ratio, intrinsic viscosity (η) and crosslinking scheme are as described above, excellent tensile strength, flexibility and compression set can be obtained.

In the low frequency region, the melt viscosity η * should be as high as possible. This is because the compression set is lowered. For example, an unsaturated copolymer having a long branched chain or an unsaturated copolymer containing a high molecular weight component is preferable.

When the crosslinked molded article is used for the door glass traveling channel, it is preferable to use two kinds of α-olefins composed of ethylene and an α-olefin having 3 or more carbon atoms as the olefin in the unsaturated copolymer, in which case ethylene and other α-olefins are used. The molar ratio of (ethylene / other α-olefin) is preferably 90/10 to 75/25 (total: 100). When used for the door glass traveling channel, the unsaturated copolymer preferably has an intrinsic viscosity (η) of 2.5 to 4.5 dl / g and an oxo value of 20 to 50. If the molar ratio, intrinsic viscosity η and oxo value of ethylene / α-olefin are within the above-mentioned ranges, the strength, elongation and hardness can be increased and the compression set can be reduced.

The crosslinked molded article, especially the crosslinked molded article using the third unsaturated copolymer, can be preferably used for the tire bottom.

When the crosslinked molded article is used as a tire flooring material, it is preferable to use two kinds of α-olefins composed of ethylene and an α-olefin having 3 or more carbon atoms as the olefin in an unsaturated copolymer (particularly unsaturated terpolymer). In this case, the molar ratio of ethylene and an α-olefin having 3 or more carbon atoms (ethylene / α-olefin having 3 or more carbon atoms) is 99/1 to 75/25, preferably 85/15 to 75/25, more preferably 85/15 80/20 is good. When styrene is copolymerized as an aromatic vinyl compound to be used as necessary, the content of the styrene unit is preferably 5 to 20 mol%, preferably 7 to 15 mol%. In addition, it is preferable that the value of tan δ (0 ° C.) tends to increase and the value of tan δ (50 ° C.) tends to decrease.

If the unsaturated copolymers of the present invention have the following physical properties, they can be used for shrink films.

That is, the unsaturated copolymer usefully used for the shrink film is 99.89 to 58 mol% of structural units derived from ethylene, 0 to 30 mol% of structural units derived from α-olefins having 3 to 12 carbon atoms, It consists of 0.1-12 mol% of structural units derived from aromatic vinyl compounds and 0.01-10 mol% of structural units derived from conjugated dienes (particularly butadiene or isoprene), and has an intrinsic viscosity (η) of 0.1-10 dl / g and 60- It has a melting point of 125 ° C. When used for a shrink film, it is preferable to stretch the resulting film in at least one direction.

It is good to add 1-50 weight part of adhesives per 100 weight part of unsaturated copolymers to resin for films. In addition, the resulting film is oriented in two directions, and the shrinkage ratio of the film is preferably 20 or more at 80 ° C.

Suitable compositions for films, sheets, tubes and hoses are compositions comprising from 0.5 to 100 parts by weight of an antifoaming agent and from 0.5 to 10 parts by weight of nucleating agent, if necessary, per 100 parts by weight of unsaturated copolymer. Such films and sheets are specifically, for example, agricultural film, stretch film, packaging film, and packaging sheet.

Specific examples of the tubes are, for example, shrink tubes, piping tubes and medical tubes.

When an unsaturated copolymer is used for the said use, melting | fusing point of a copolymer is good in the range of 70-125 degreeC measured by DSC.

In the case of the above use, in the unsaturated copolymer, 99.89 to 83 mol% of structural units derived from ethylene, 0 to 10 mol% of structural units derived from α-olefins having 3 or more carbon atoms, and aromatic vinyl compounds used as necessary It is preferable to contain 0.1 to 7 mol% of derived structural units and 0.01 to 5 mol% of structural units derived from butadiene or isoprene.

Heated melt adhesive

When using the unsaturated copolymer of the present invention, in particular the third unsaturated copolymer (hereinafter sometimes referred to as 'unsaturated terpolymer' or 'α-olefin / aromatic vinyl compound / conjugated diene copolymer'), The composition can be used as a hot melt adhesive.

That is, a hot melt adhesive becomes (A) base polymer, (B) adhesive, (C) unsaturated copolymer mentioned above, and (D) low molecular weight polyolefin as needed.

A base polymer (A), an adhesive (B), and a low molecular weight polyolefin (D) are demonstrated below.

(A) base polymer

There is no particular limitation on the base polymer usable in the present invention, and polymers commonly used for hot melt adhesives can be used. Such polymers are, for example, (a-1) polyolefins, (a-2) polar group-containing polymers, and (a-3) aromatic vinyl compounds / conjugated diene copolymers.

(a-1) Polyolefin:

Polyolefins (a-1) are, for example, polyethylene (eg HDPE, LDPE, LLDPE) and polypropylene (eg atactic polypropylene, syndiotactic polypropylene) and ethylene / propylene copolymers.

(a-2) Polar group-containing polymer:

A polar group containing polymer (a-2) is as follows, for example.

(1) Ethylene / Vinyl Acetate Copolymer (EVA)

(2) modified EVA polymers such as gummed EVA and graft modified EVA

(3) ethylene / (meth) acrylate copolymers, eg ethylene / ethyl (meth) acrylate copolymers (EEA)

(4) Ionomer resins obtained by partially neutralizing an ethylene / (meth) acrylic acid copolymer such as Himilan (trade name, manufactured by Mitsui DuPont Polychemical)

(5) ethylene / propylene / (meth) acrylic acid terpolymers

(6) polyamides; Reaction products of dibasic acids and diamines, eg reaction products of dimer acids (dimers of fatty acids from soymilk, tung oil, tall oil, etc.) with alkyldiamines such as ethyredamine or diethylenetriamine and nylons such as nylon 12 (poly Amides are, for example, diamide (trade name, manufactured by Daicel Chemical Industries, Ltd.), brackicon (trade name, manufactured by Toagosei Chemical Industries, Ltd.), and amiran (trade name, manufactured by Toray Industries, Inc.).

(7) Polyester, for example, ester resin 200, 300 (brand name, the Toyobo Corporation), vital 200, 300 (brand name, Goodyear tire and rubber company make)

(8) vinyl acetate copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / phthalic anhydride copolymer, vinyl acetate / vinylpyrrolidone copolymer, cellulose derivative polymer, polymethyl methacrylate polymer, polyvinyl ether polymer , Polyurethane polymers and thermosetting polymers

(a-3) Aromatic vinyl compound / conjugated diene copolymer:

The aromatic vinyl compound / conjugated diene copolymer (a-3) is a copolymer of an aromatic vinyl compound and a conjugated diene compound or a hydride thereof.

Such copolymers and their hydrides include, for example, styrene / butadiene random copolymers, styrene / isoprene random copolymers, butadiene / polystyrene block copolymers, polystyrene / polyisoprene block copolymers, polystyrene / polyisoprene / polystyrene triblock airborne copolymers. Copolymer (SIS), polystyrene / polybutadiene / polystyrene triblock copolymer (SBS), poly (α-methylstyrene) / polybutadiene / poly (α-methylstyrene) triblock copolymer, and hydrides of these copolymers to be. These polymers are commercially available, for example Kaliflex TR-1101, TR-1107, TR-4113 (trade name, manufactured by Shell Chemicals), Kraton G-6500, G-6521, G-1650, G-1652 and G-1657 (trade name, manufactured by Shell Chemical Co., Ltd.), and styrene and hydrogenated styrene (trade name, manufactured by Philips).

In the hot melt adhesive, the base polymer described above may be used alone or in combination of two or more thereof. Preferred are aromatic vinyl compounds / conjugated diene copolymers and their hydrides in the base polymer, particularly aromatic vinyl compounds / conjugated diene copolymers.

(B) pressure-sensitive adhesive

The pressure-sensitive adhesive (B) used for the hot melt adhesive serves to adjust the melt viscosity of the base polymer (A) and to improve the heat adhesion and the wet properties. There is no particular limitation on the adhesive (B) as long as it can improve the heat adhesion and the wet physical properties of the base polymer (A) during heating. The adhesive (B) used here is the above-mentioned thing, for example.

(D) low molecular weight polyolefin

The low molecular weight polyolefin (D) used as needed to form the hot melt adhesive is:

(i) a polyolefin having a homopolymer of 2 to 12 carbon atoms or a copolymer of two or more α-olefins and having an intrinsic viscosity (η) of 0.01 to 0.6 dl / g, or

(ii) saturated straight or branched hydrocarbons having an intrinsic viscosity η of 0.01 to 0.6 dl / g.

The α-olefins having 2 to 12 carbon atoms in the polyolefin (i) are, for example, those described above.

Polyolefin (i) can be manufactured according to a known method. For example, the polyolefin (i) can be produced by high pressure radical polymerization or medium or low pressure polymerization in the presence of a transition metal compound catalyst such as Ziegler catalyst. The polyolefin (i) is prepared by the pyrolysis method in which first, a high molecular weight homopolymer or copolymer is prepared by the polymerization method, and then a high molecular weight homopolymer or copolymer is made into a low molecular weight by thermal decay or radical decay with a peroxide. can do.

Hydrocarbons (ii) are, for example, straight chain hydrocarbons such as paraffin wax and azole wax; Branched hydrocarbons such as micro waxes, and the like. These waxes are generally known and commercially available. Among the waxes, the solazole wax can be prepared by the following method.

Coal is vaporized using steam and oxygen to obtain a synthesis gas consisting mainly of carbon monoxide and hydrogen, and then the synthesis gas is removed by vacuum distillation from the reactants obtained through a fixed bed catalytic reactor known as ARGE method. Sorbazole wax by dividing into first class (C18 to C23), second class (C22 to C36), and third class (C33 or more), and then hydrogenating the third class of these classes to remove all unsaturated hydrocarbons and oxygen compounds. Is obtained.

The hot melt adhesive is made of base polymer (A), pressure-sensitive adhesive (B) and unsaturated copolymer (C) (preferably α-olefin / aromatic vinyl compound / conjugated diene copolymer, ie unsaturated terpolymer)

(A) 100 parts by weight of the base polymer,

(B) 10 to 300 parts by weight of the adhesive, preferably 50 to 200 parts by weight, and

(C) 10 to 400 parts by weight of unsaturated copolymer, preferably 30 to 300 parts by weight

To manufacture.

A low molecular weight polyolefin (D) may be added to the hot melt adhesive in an amount of 1 to 100 parts by weight, preferably 10 to 80 parts by weight, per 100 parts by weight of the base polymer (A). If the low molecular weight polyolefin (D) is added, the melt viscosity of the hot melt adhesive can be reduced to improve workability. When adding a low molecular weight polyolefin (D), it is preferable that the intrinsic viscosity ((eta)) of an unsaturated copolymer (C) is 0.6-10 dl / g.

In addition to the base polymer (A), pressure-sensitive adhesive (B), unsaturated copolymer (C) and low molecular weight polyolefin (D), the hot melt adhesive impairs various additives such as softeners, stabilizers, fillers and antioxidants. It may be contained selectively within the range which is not.

Hot melt adhesives can be produced by methods known to date. For example, the base polymer (A), the pressure-sensitive adhesive (B), the unsaturated copolymer (C) and, if necessary, low molecular weight polyolefin (D) and a prescribed amount of additives are fed to a mixer such as a brabender mill and then hot melted. After mixing, they are shaped into the desired shape, such as particles, flakes or bar shapes.

When using a hot melt adhesive, the hot melt adhesive is melted and then conventionally applied to various materials such as cloth, kraft paper, metal foil (e.g., aluminum foil) or resin molded article (e.g., polyester film) to form an adhesive layer. do. Hot melt adhesives exhibit good adhesion when bonding styrene polymers and polyolefins.

Latex composition

Moreover, each unsaturated copolymer of this invention can be used in the form of a latex composition.

The latex composition is a group consisting of 100 parts by weight of an unsaturated copolymer (A), a low molecular weight polyethylene, a low molecular weight ethylene / α-olefin copolymer, an unsaturated carboxylic acid compound-modified low molecular weight polyethylene and an unsaturated carboxylic acid compound-modified low molecular ethylene / α-olefin copolymer 2 to 50 parts by weight of the at least one low molecular weight polymer (B) selected from can be prepared by homogeneously dispersing in the receiving medium in the presence of a surfactant.

It is preferable that the solid component of a latex composition is 0.1-3.0 micrometers in average molecular diameter. It is preferable that a solid component has bridge | crosslinking and a high temperature toluene insoluble substance is 30 weight% or more. Low molecular weight polymers are waxy or liquid polymers at room temperature.

As for low molecular weight polyethylene, polyethylene wax and low molecular weight polyethylene are measured in 135 degreeC decalin, for example, It is preferable that intrinsic viscosity ((eta)) is 0.01-0.3 dl / g. Examples of the low molecular weight ethylene / α-olefin copolymers include ethylene / α-olefin copolymers such as ethylene / propylene copolymers and ethylene / 1-butene copolymers. As for the low molecular weight ethylene / alpha-olefin copolymer, it is measured in 135 degreeC decalin, and its intrinsic viscosity ((eta)) is preferable 0.01-0.3 dl / g.

The unsaturated carboxylic acid compound-modified low molecular weight polyethylene and the unsaturated carboxylic acid compound-modified low molecular weight ethylene / α-olefin copolymer are low molecular weight polyethylene and low molecular weight ethylene / α-olefin air containing unsaturated carboxylic acid as a comonomer or graft-modified with unsaturated carboxylic acid. It is coalescing.

Examples of the unsaturated carboxylic acid compound include unsaturated carboxylic acids having 3 to 20 carbon atoms, anhydrides, amides, imides, and unsaturated carboxylic acid esters.

Specifically, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, norbornene dicarboxylic acid, tetrahydrophthalic acid and bicyclo [2.2.1] hept-2-ene-5,6-dicarboxylic acid Unsaturated carboxylic acid mentioned above; Unsaturated carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and bicyclo [2.2.1] hept-en-5,6-dicarboxylic anhydride; Unsaturated carboxylic acid amides or imides such as maleic acid monoamide, maleic acid diamide and maleimide; Methyl acrylate, methyl methacrylate, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyltetrahydrophthalate, dimethyl bicyclo [2.2. 1] unsaturated carboxylic acid esters such as hept-2-ene-5,6-dicarboxylate and glycidyl (meth) acrylate.

Of these, maleic acid, maleic anhydride, maleic acid monoamide, maleic acid diamide, maleimide, monomethyl maleate, diethyl maleate, glycidyl (meth) acrylate, and the like are preferable.

Each of the low molecular weight polyethylene, low molecular weight ethylene / α-olefin copolymer copolymerized with an unsaturated carboxylic acid compound, and the low molecular weight polyethylene and low molecular weight ethylene / α-olefin copolymer graft modified with an unsaturated carboxylic acid compound may be prepared from an unsaturated carboxylic acid compound. It is preferable that the derived structural unit contains 0.2 to 50% by weight, preferably 0.2 to 30% by weight.

Each of the low molecular weight polyethylene and low molecular weight ethylene / α-olefin copolymer copolymerized with the unsaturated carboxylic acid compound, and the low molecular weight polyethylene and the low molecular weight ethylene / α-olefin copolymer graft-modified with the unsaturated carboxylic acid compound are in 135 ° C decalin. It is preferable that the intrinsic viscosity η is measured to be 0.01 to 0.3 dl / g.

Said low molecular weight polymer (B) may be used individually or in combination of 2 or more types.

The low molecular weight polymer (B) has the function of micronizing the unsaturated copolymer (A) in the preparation of copolymer latex compositions (hereinafter sometimes referred to as 'latex compositions').

The copolymer latex composition contains an unsaturated copolymer (A) as a solid component. In addition, the copolymer latex composition contains a low molecular weight polymer (B). The low molecular weight polymer (B) may contain 2 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the unsaturated copolymer (A). When the low molecular weight polymer (B) is contained in this amount, the solid component is micronized and the resulting copolymer latex composition shows excellent storage stability. In addition, when the latex composition is used as a resin modifier, impact resistance is improved.

The copolymer latex composition can be produced by homogeneously dispersing an unsaturated copolymer (A) and a low molecular weight polymer (B) in an aqueous solvent in the presence of a surfactant. More specifically, hydrocarbon solvents, such as an unsaturated copolymer (A) and hexane, and the low molecular weight polymer (B) were mixed and stirred, and the homogeneous solution was obtained. The homogeneous solution is then added to the aqueous medium in which the surface active agent is dispersed, and these are mixed and stirred to obtain an emulsion. The emulsion is heated to a temperature of 50 to 100 ° C. to evaporate the organic solvent to obtain a copolymer latex composition.

In the above process, the aqueous medium is used so that the concentration of the solid component in the resulting copolymer latex composition is from 5 to 65% by weight. When the aqueous medium is used in this amount, the resulting copolymer latex composition has good operating characteristics.

There is no particular limitation on the surface active agent, and any of anionic surface active agent, cationic surface active agent and nonionic surface active agent can be used. It is preferable to use an anionic surface active agent in this invention, and it is especially preferable to use fatty acid metal salts, such as fatty acid sodium salt and fatty acid potassium. The amount of the surface active agent varies depending on the type of polymer component used, but the surface active agent per 100 parts by weight of the unsaturated copolymer (A) is usually 0.2 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

The copolymer latex composition can be prepared by phase inversion of a high shearing emulsion using a twin screw extruder as described in Japanese Patent Laid-Open No. 61-123664.

As for the average particle diameter of the solid component of the copolymer latex composition obtained above, the range of 0.1-3.0 micrometers is preferable.

The copolymer latex composition obtained above may be crosslinked. The crosslinking treatment is performed by a known method such as ionizing radiation crosslinking or organic peroxide crosslinking.

Examples of ionizing radiation used for the ionizing radiation crosslinking include α rays, β rays, γ rays, electron rays, X rays, and the like. The irradiation amount of the ionizing radiation is preferably in the range of 1 to 50 Mrad. In ionizing radiation crosslinking, polyfunctional monomers can be added to the copolymer latex composition. As the polyfunctional monomer, a monomer having two or more ethylenically unsaturated groups, particularly vinyl groups, may be used. Examples of such monomers include divinylbenzene, tetramethylene diacrylate, glyceryl triacrylate, ethylene glycol dimethacrylate, 1,2,4-trivinylcyclohexane, tetraallyloxyethane and the like. The polyfunctional monomer is preferably 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

The organic peroxide crosslinking is performed by homogeneously dispersing the organic peroxide in the copolymer latex composition and heating the dispersion at a temperature equal to or higher than the decomposition temperature of the organic peroxide. As the organic peroxide, it is preferable to use an organic peroxide having a temperature corresponding to half life of 10 hours at 0 to 100 ° C. Examples of such organic peroxides include 1,1-bis (t-butylperoxy) cyclohexane, t-butyl peroxypivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisopropyl carbonate , 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide , Isobutyl peroxide, diisobutyl peroxydicarbonate, di (2-ethylhexyl) peroxycarbonate, and the like. These organic peroxides can be used individually or in combination of 2 or more types. The organic peroxide is usually used in an amount of 0.3 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

In organic peroxide crosslinking, polyfunctional monomers can be added to the copolymer latex composition. Examples of the multifunctional monomers include those described above. The polyfunctional monomer is usually used in an amount of 0.1 to 20 parts by weight, preferably 0.3 to 5 parts by weight, per 100 parts by weight of the unsaturated copolymer (A).

The organic peroxide crosslinking may be carried out at atmospheric pressure or under pressure, but the crosslinking conditions are set so that the content of the hot toluene insoluble matter as a solid component is 30% by weight, preferably 50% by weight or more, more preferably 60% by weight or more. good. Specifically, the heating period is preferably adjusted to 5 to 7 times the half life. The content of the high temperature toluene insoluble matter in the solid component indicates the degree of crosslinking, and when the content of the high temperature toluene insoluble matter is in the above range, the impact resistance is improved when the crosslinked copolymer latex composition is used as the resin modifier.

As for the average particle diameter of the solid component of the crosslinked copolymer latex composition obtained above, the range of 0.1-3.0 micrometers is preferable. The crosslinked copolymer latex composition of the present invention is excellent in storage stability, and when the latex composition is used as a resin modifier, the impact resistance and surface glossiness of the resin are improved.

To the copolymer latex composition of the present invention, various known additives such as pigments, thickening agents, plasticizers, preservatives, antifoaming agents, pH adjusting agents, antioxidants and anti-aging agents can be added in known amounts depending on the application. . These additives may be added to the copolymer latex composition prior to crosslinking.

The (crosslinked) copolymer latex composition of the present invention can be used as a modifier for thermoplastic resins such as acrylonitrile / styrene copolymer (AS resin) and modified polyphenylene oxide (modified PPO resin). In this case the (crosslinked) copolymer latex composition is used after drying. The reaction product obtained by graft polymerization of acrylonitrile or the like in the presence of a (crosslinked) copolymer latex composition can be used as a resin modifier.

AS resin and modified PPO resin modified with the (crosslinked) copolymer latex composition of the present invention are excellent in weather resistance, solvent resistance, impact resistance, surface gloss, etc. It is used as a vehicle exterior ornament.

The crosslinked product of the present invention, particularly the organic peroxide crosslinked product, is useful for a film or sheet having a good balance between transparency, scratch resistance, heat resistance and flexibility. When the crosslinked product is used as a film, a copolymer obtained by copolymerizing at least one component selected from ethylene, an unconjugated diene, and optionally an α-olefin having 3 or more carbon atoms and an aromatic vinyl compound is preferable. This copolymer is the same as the copolymer mentioned above. From the viewpoint of heat resistance, the melting point is preferably 40 ° C. or higher, preferably 70 ° C. or higher as measured by DSC.

The film or sheet may be used as a decorative film, tablecloth, book cover, or the like. The thickness of the film or sheet is not particularly limited, but is usually in the range of 1 μm to 110 mm. In the case of using a film or sheet, the haze value of the crosslinked product is 0 to 50%, more preferably 0 to 30% (thickness 1 mm).

In particular, the unsaturated copolymer used in the crosslinked product of the present invention is a third unsaturated copolymer containing an aromatic vinyl compound, and the crosslinked product is in the form of a film or sheet, such as a frozen bag, a decorative film, a tablecloth, a book cover, and a tube. It is good to use as medical apparatus. The crosslinked product is preferably used for the same use as 'soft vinyl chloride resin' such as food containers, stationery, daily sundries (ie, cleaner bumpers, cutting mats, bath covers, and transfusion sets) and automobile interior ornaments.

Example

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Physical property tests were carried out under the following conditions.

Ozone test

The ozone resistance test is a static test performed in an ozone test bath under test conditions of 80 ppm of ozone concentration, 80% elongation rate, temperature 40 ° C, and test time of 96 hours. The ozone resistance was evaluated based on the standards of JIS K 6301 for the surface deterioration state. The evaluation criteria of the surface were as follows, and the surface state was graded as 'C-5', for example.

Cracks

A… There are a few cracks

B… There are many cracks

C… There are a myriad of cracks

Crack size and depth

One … Cracks can be seen with a 10x magnifier but not visible to the naked eye.

2 … The cracks can be observed with the naked eye.

3…. Deep and relatively large cracks (1 mm or less).

4 … Deep and large cracks (1 mm or more and 3 mm or less).

5... More than 3mm of crack exists and breakage occurs.

Tear test

The tear test inserted a 20 mm wide Teflon sheet between two unvulcanized rubber sheets and press vulcanized. Thereafter, the portion where the Teflon sheet was inserted was pulled with a chuck to measure peel strength.

Oil proof test

The oil resistance test was done in accordance with the immersion test specified in JIS K 6301, and the volume change (ΔV%) of the test piece was measured. JIS NO. 3 oils were used as test oils and tested at 100 ° C. for 72 hours.

Tensile test

Tensile strength (TB), elongation at break (EB), and permanent elongation (PS) were measured according to JIS K 6301.

Hardness test

JIS A hardness (HS) was measured according to JIS K 6301.

Compression permanent deformation

Compression set (CS) (compression conditions; 150 ° C, 22 hours), which is an index of the crosslinking density, was measured by the method shown in JIS K 6301.

Rubber properties

Rubber properties were evaluated by the following test method. In other words, the stiffness was evaluated by the tensile strength (TB), the wear resistance was evaluated by the Lanburn method, the braking property of the wet furnace surface (wet skid) was evaluated by tan δ at 0 ° C, and the rolling resistance by the spectrometer. It evaluated with tan delta at 50 degreeC.

Melting Point (Tm) and Glass Transition Temperature (Tg)

The endothermic curve was measured by DSC, and the temperature at the maximum peak position was taken as the melting point (Tm).

The measurement was performed by the following method. The sample was placed in an aluminum pan and heated to 200 ° C. at a rate of 10 ° C./min and held at 200 ° C. for 5 minutes. Then, it cooled to -150 degreeC at the speed of 20 degree-C / min. Then, Tm was calculated | required by the endothermic curve at the time of heating at the speed of 10 degree-C / min.

From the endothermic peak measured by the DSC, the heat of fusion per unit weight was measured, and this was divided by the heat of fusion of crystalline polyethylene by 70 cal / g to obtain a degree of crystallization (%).

Intrinsic viscosity (η)

Intrinsic viscosity was measured in 135 degreeC decalin.

Mw / Mn

Mw / Mn was measured using GPC (gel permeation chromatography) in an Olso-dichlorobenzene solvent at 140 ° C.

Test Methods

(1) Tensile strength (TB) was measured in accordance with JIS K 6301.

(2) Ranburn wear was measured with a Ranburn wear tester (manufactured by Iwamoto Seisakusho Kabushiki Kaisha) under the following conditions.

Measuring conditions

Load: 3 kg

Sample circumferential speed: 150 m / min.

Main speed of grinder: 100m / min.

(3) tan δ was measured under the following conditions using a dynamic spectrometer (manufactured by Rheometrics Corporation).

Measuring conditions

Shear strain: 0.5%

Frequency: 15 Hz

Example A1

(Preliminary activation of the catalyst)

In a glass vessel completely substituted with nitrogen, 5.5 mg of (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium synthesized by a known method was weighed, and 0.75 mmol of aluminum atoms An equivalent amount of 0.75 ml of 1.0 mmol / ml triisobutylaluminum (hereinafter simply referred to as TIBA) was added together to the vessel. Thereafter, the mixture was irradiated with ultrasonic waves at 23 ° C. for 15 minutes to prepare a catalyst solution.

(Synthesis of Ethylene / Butadiene Copolymer)

288 ml of toluene and 0.075 ml of the catalyst solution prepared in the preliminary activation process of the catalyst were added to a 2 liter autoclave dried under reduced pressure and replaced with nitrogen at room temperature, and ethylene was supplied under stirring to give a pressure of 6 kg / cm ² G. Raised. The autoclave was then depressurized and the pressurization and pressure relief procedures were repeated three times.

Then 7 g of 1,3-butadiene gas were introduced at atmospheric pressure in the presence of ethylene and the temperature of the autoclave was raised to 50 ° C. The system was then pressurized to 6 kg / cm ² G with ethylene. 1.5 ml of triphenyl carbenium tetra (pentafluorophenyl) borate toluene solution (0.002 mM / ml) was added to start copolymerization of ethylene and 1,3-butadiene. In the above copolymerization, the catalyst concentration is 0.005 mmol / liter of (dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane) dichloride titanium per electric field, and triphenylcarbenium tetra (pentafluorophenyl Borate was 0.01 mmol / liter. Ethylene was continuously fed during the polymerization to maintain an internal pressure of 6 kg / cm ² G. After 5 minutes the polymerization reaction was stopped by adding methyl alcohol.

After the pressure was released, the polymer solution was taken out, and 5 ml of concentrated hydrochloric acid was added to 1 liter of water, and washed with an equivalent amount of an aqueous solution prepared to transfer the catalyst residue to an aqueous phase.

The contact mixed solution was allowed to stand and the aqueous phase was separated off. In addition, the polymerization liquid was washed twice with distilled water, and the oil and water were separated. Subsequently, the oil-separated polymerization liquid was stirred vigorously with three times the amount of acetone to precipitate a polymer. The polymer was washed thoroughly with acetone and filtered to collect the solid phase (copolymer). The copolymer was dried in 130 ° C., 350 mmHg, nitrogen stream for 12 hours.

The yield of the ethylene / butadiene copolymer thus prepared was 13 g, the intrinsic viscosity (η) measured in 135 ° C decalin was 3.5 dl / g, the glass transition temperature (Tg) was -39 ° C, and the oxo number was 31 g / 100 g. , Ethylene content is 96mol%, 5-membered ring structure is 2.4mol%, 3-membered ring structure is 0.1mol%, 1,2-addition structure is 0.4mol%, 1,4-addition structure is 1.1mol% and activity is 104kg / mmolZr · hr.

The results are shown in Table 4.

Example A2

The procedure of Example A1 was repeated except that the amount of 1,3-butadiene was changed to 10 g. The yield of the produced ethylene / butadiene copolymer was 14 g, measured in decalin at 135 ° C., the ultimate viscosity (η) was 4.0 dl / g, the glass transition temperature (Tg) was -38 ° C., the oxo value was 40 g / 100 g, and the ethylene content was 91 mol%, 5-membered ring structure is 6.8mol%, cyclopropane ring structure is 0.1mol%, 1,2-addition structure is 0.6mol%, 1,4-addition structure is 1.5mol% and activity is 112kg / mmolZr.hr It was.

The results are shown in Table 4.

Example A3

The procedure of Example A1 was repeated except that 1,3-butadiene was changed to 4 g. The yield of the resulting ethylene / butadiene copolymer was 15 g, measured in 135 ° C decalin, the ultimate viscosity (η) was 4.2 dl / g, the glass transition temperature (Tg) was -40 ° C, the oxo value was 21 g / 100 g, and the ethylene content was 97 mol. %, 5-membered ring structure is 1.9mol%, cyclopropane ring structure is 0.1mol%, 1,2-addition structure is 0.4mol%, 1,4-addition structure is 0.6mol% and activity is 120kg / mmolZr.hr It was.

The results are shown in Table 4.

Example A4

Example A1 was repeated except that 5,500 ml (25 degreeC and 1 atmosphere) of propylene were further introduced, the 1, 3- butadiene was changed to 4 g, and the reaction temperature was changed to 20 degreeC. The yield of the resulting ethylene / propylene / butadiene copolymer is 1.7 g, the intrinsic viscosity (η) measured in 135 ° C decalin is 1.7 dl / g, the glass transition temperature (Tg) is -45 ° C, and the oxo value is 18.1 g / 100 g, 67.5 mol% of ethylene, 24.9 mol% of propylene, 5.0 mol% of 5-membered ring structure, 0.1 mol% of cyclopropane ring structure, 0.5 mol% of 1,2-addition structure, 1,4 -The addition structure was 2.0 mol%, and the activity was 13 kg / mmolZr hr.

The results are shown in Table 4.

Example A1 A2 A3 A4 Unit (mol%) E / BD E / BD E / BD E / P / BD 1,2-addition 0.4 0.6 0.4 0.5 3,4-addition 1,4-addition 1.1 1.5 0.6 2.0 5-membered ring (cyclopentane ring) 2.4 6.8 1.9 5.0 3-membered ring (cyclopropane ring) 0.1 0.1 0.1 0.1 Ethylene Unit 96 91 97 67.5 Propylene unit 24.9 Styrene Unit Tg (℃) -39 -38 -40 -45 Tm (℃) 95 70 100 - Intrinsic viscosity (η) (dl / g) 3.5 4.0 4.2 1.7 Oxoga IV (g / 100g) 31 40 21 18 Catalyst Activity (kg / mmolZr · hr) 104 112 120 13 Mw / Mn 2.3 2.4 2.3 2.4 E: ethylene, BD: 1,3-butadiene, P: propylene

Example A5

38 ml of toluene and 6 g of ethylene / propylene / 1,3-butadiene copolymer prepared in Example A4 were introduced into a 200 ml glass autoclave completely substituted with nitrogen, and the temperature was raised to 140 ° C. while stirring the mixture. In another vessel, a solution was prepared by dissolving 1.06 g of maleic anhydride and 0.18 g of dicumyl peroxide in 8 ml of toluene. The solution was added dropwise to the autoclave at a constant rate over 3.5 hours, followed by stirring for 30 minutes. During the dropping, the temperature was slowly raised to 160 ° C. After the reaction was completed, the reaction solution was cooled to 70 ° C. and added to 200 ml of methanol to precipitate a polymer. The precipitated polymer was further washed with 200 ml of acetone and vacuum dried at 130 ° C. for 12 hours to prepare a graft modified ethylene / propylene / 1,3-butadiene copolymer. In the resulting modified polymer, it was modified with 3.5% by weight maleic anhydride. The intrinsic viscosity (η) of the modified polymer measured in 135 ° C decalin was 1.8 dl / g.

Example A6

(Manufacture of Vulcanized Rubber)

The copolymer prepared in Example A4, zincized, stearic acid, HAF carbon black (HAF Asahi # 70TM, manufactured by Asahi Carbon Co., Ltd.), and dicumyl peroxide (DCP-40C) were added in the following amounts, followed by an open roll (shear). Roll / back end roll: kneaded at 50/60 ° C., 16/18 rpm) to prepare unvulcanized rubber.

(Composition composition)

Copolymer prepared in Example A4: 100 parts by weight

Zinc: 5 parts by weight

Stearic acid: 1 part by weight

HAF Carbon Black: 50 parts by weight

Dicumyl peroxide (DCP-40): 7 parts by weight

The unvulcanized blended rubber thus prepared was heated in a press heated at 170 ° C. for 15 minutes to prepare a vulcanized sheet. Thereafter, the production sheet was subjected to tensile, hardness and compression set tests under the above conditions.

The tensile strength TB (MPa) was 18, the elongation EB (%) was 200, the hardness was HS (JIS A), 72. The compression set was 13 (CS).

The results are shown in Table 5.

Comparative Example A1

Ethylene / propylene / 5-ethylidene-2-norbornene copolymer rubber (ethylene: propylene = 73: 27 (molar ratio), oxo number = 18 g without using the copolymer prepared in Example A4 (4 in Table 4)) / 100g, [η] = 1.85) was repeated, except that the procedure of Example A6 was repeated.

Tensile strength TB (MPa) was 18, elongation EP (%) was 230, hardness HS (JIS A) was 69, and compression set was CS (%) 20.

The results are shown in Table 5.

Example A6 Comparative Example A1 Vulcanization property TB (MPa) 18 18 EB (%) 200 230 HS (JIS A) 72 69 CS (%) 13 20

Example A7

4400 ml (25 ° C., 1 atm) of propylene was further introduced, except that the amount of 1,3-butadiene, the amount of the catalyst solution, the reaction time, and the reaction temperature were changed to 7 g, 0.045 ml, 15 minutes, and 20 ° C., respectively. The procedure of A1 was repeated. The yield of the produced ethylene / propylene / butadiene copolymer was 2.9 g, the limiting viscosity (η) in 135 ° C decalin was 2.5 dl / g, the glass transition temperature (Tg) was -43 ° C, and the oxo value (IV) was 25.1 g. / 100g, ethylene content is 71.4mol%, propylene content is 20.1mol%, the 5-membered ring structure is 5.3mol%, cyclopropane ring structure is 0.2mol%, 1,2-addition structure is 0.7mol%, 1,4- The addition structure was 2.3 mol% and the activity was 13 kg / mmolZr hr.

Example A8

(Manufacture of Vulcanized Rubber)

The copolymer prepared in Example A7, zincated, stearic acid, HAF carbon black (HAF Asahi # 70TM, manufactured by Asahi Carbon Co., Ltd.) and dicumylperoxide (DCP-40C) were added in the following amounts, followed by an open roll (shear roll / Post-roll: 50/60 ° C., 16/18 rpm), and kneaded to prepare an unvulcanized blended rubber.

(Composition composition)

Copolymer: 100 parts by weight

Zinc: 5 parts by weight

Stearic acid: 1 part by weight

HAF Carbon Black: 50 parts by weight

DCP-40C: 7 parts by weight

The unvulcanized blended rubber thus prepared was heated in a press heated at 170 ° C. for 15 minutes to prepare a vulcanized sheet. After that I did the next test.

The results are shown in Table 6.

The sheet is suitable for use as a glass run channel.

Furthermore, the roll nip was adjusted to 1 mm, the unvulcanized rubber was separated and taken out, and it crosslinked for 10 minutes in the oven heated at 220 degreeC. Thereafter, surface adhesion was observed.

The results are shown in Table 6.

Properties TB (MPa) 22 EB (%) 210 HS (JIS A) 75 CS (%) 11 Surface Adhesion radish

Example A9

70 parts by weight of the unsaturated copolymer prepared in Example A4 and 30 parts by weight of polypropylene (PP, J700 ^™ , manufactured by Mitsui Chemicals, Inc.) were kneaded for 5 minutes at 180 ° C. with a Banbury mixer in a nitrogen atmosphere. Thereafter, the kneaded material was passed through a roll to prepare a sheet. Subsequently, it cut out with the sheet cutter and manufactured the square pellet.

0.1 part by weight of divinylbenzene (hereinafter referred to as DVS) and 0.15 part by weight of 2,5-dimethyl-2,5- (tert-butylperoxy) hexane (hereinafter referred to as POX) are mixed into 100 parts by weight of the tetrahedral pellets, Stir with a Henschel mixer.

Subsequently, the mixture was kneaded with raboplastomill (model 20R200, manufactured by Toyo Seiki Seisakyuso Co., Ltd.) at 200 rpm for 5 minutes at 100 rpm in a nitrogen atmosphere.

The resulting olefin thermoplastic elastomer composition was molded in a press heated to 200 ° C. to produce a 2 × 80 × 80 mm square plate.

(Oil resistance test)

A 2 × 10 × 10 mm test piece was punched out from the prepared square plate, and the initial volume (VO) of the test piece was measured using a water immersion volume measuring device.

The test piece was immersed in JIS NO.1 oil heated to 70 ° C. for 3 days, and after recovering the temperature to room temperature, the volume (V) of the test piece after expansion was measured by the same method. From these values, the degree of expansion (ΔV) was measured using the following equation.

ΔV (%) = {(V-VO) / VO} × 100

In this result, the degree of expansion (ΔV) was 98%.

Comparative Example 2

ENB-EPT copolymer (ethylene) having a composition ratio of ethylene / propylene / ENB (ethylidene norbornene) of 68.3 / 29.3 / 2.4 (mole), an intrinsic viscosity (η) of 1.8 dl / g, and an oxo value of 18 g / 100 g / Propylene / ethylidene norbornene terpolymer) was repeated in Example A9.

In this result, the degree of expansion (ΔV) was 121 (%).

Example B1

(Preliminary activation of the catalyst)

In a glass vessel completely substituted with nitrogen, 16.0 mg of isopropylidene bisindenyl zirconium dichloride synthesized by a known method was weighed, and an equivalent amount of 22.57 mmol of aluminum atom and 1.484 mmol / ml of methylaluminoxane (hereinafter referred to as MAO) 15.2 ml of toluene solution) were added together to the vessel. Thereafter, the mixture was ultrasonically irradiated at 23 ° C. for 15 minutes to prepare a catalyst solution.

(Synthesis of Ethylene / Isoprene Copolymer)

177.2 ml of toluene and 117.5 ml of isoprene were added to a 2-liter autoclave dried under reduced pressure and nitrogen at room temperature. Thereafter, 0.3 ml of a toluene solution of 1.0 mmol / ml triisobutyl aluminum (hereinafter referred to as MAO) was added, and ethylene was supplied with stirring to raise the pressure to 6 kg / cm ² G. The autoclave was then depressurized and the pressurization and pressure relief procedures were repeated three times. The temperature was then set to 30 ° C. in the presence of ethylene at atmospheric pressure. The system was pressurized with 6 kg / cm ² G with ethylene and 1.52 ml of the catalyst solution prepared in preactivation of the catalyst was added to initiate copolymerization of ethylene and isoprene.

The catalyst concentration of isopropylidene bisindenylzirconium dichloride in the copolymerization is 0.0123 mmol / liter, and the catalyst concentration of MAO is 7.5 mmol / liter. The internal pressure during the polymerization was maintained at 6 kg / cm ² G by continuously feeding ethylene. After 30 minutes, methyl alcohol was added to identify the polymerization.

After the pressure was released, the polymer solution was taken out and washed with an equivalent aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water to transfer the catalyst residue to an aqueous phase. The contact mixed solution was allowed to stand and the aqueous phase was separated off. In addition, the polymerization liquid was washed twice with distilled water, and the oil and water were separated.

Subsequently, the oil-separated polymerization liquid was stirred vigorously with three times the amount of acetone to precipitate a polymer. The polymer was washed thoroughly with acetone and filtered to collect the solid phase (copolymer). The copolymer was dried in a stream of nitrogen at 130 ° C., 350 mmHg, for 12 hours. The yield of the ethylene / isoprene copolymer thus prepared was 47 g, the intrinsic viscosity (η) measured in 135 ° C decalin was 1.5 dl / g, the glass transition temperature (Tg) was -30 ° C., and the oxo number was 27 g / 100 g. , Ethylene content is 97mol%, ring structure is 1.5mol%, 1,2-addition structure is 0.04mol%, 3,4-addition structure is 0.96mol%, 1,4-addition structure is 0.5mol% and activity is 26 kg / mmolZr hr.

The results are shown in Table 7.

Example B2

5500 ml of propylene (25 DEG C, 1 atm) were further introduced, and the procedure of Example B1 was repeated except that the amount of isoprene was changed to 60 ml and the reaction temperature was changed to 20 deg. The yield of the produced ethylene / propylene / isoprene copolymer was 18.8 g, the intrinsic viscosity (η) was measured in 135 ° C decalin, 1.4 dl / g, the glass transition temperature (Tg) was -40 ° C., the oxo value was 15 g / 100 g, and the ethylene content. 68.8 mol% silver, propylene content 25.7mol%, ring structure 3.5mol%, 1,2-addition structure 0.05mol%, 3,4-addition structure 1.25mol%, 1,4-addition structure 0.7mol % And activity was 10 kg / mmolZr hr.

The results are shown in Table 7.

Example B3

38 ml of toluene and 6 g of the ethylene / propylene / isoprene copolymer prepared in Example B2 were introduced into a 200 ml glass autoclave completely substituted with nitrogen, and the temperature was raised to 140 ° C. while stirring the mixture. In another vessel, a solution was prepared by dissolving 1.06 g of maleic anhydride and 0.18 g of dicumyl peroxide in 8 ml of toluene. The solution was added dropwise to the autoclave at a constant rate over 3.5 hours, followed by stirring for 30 minutes. During the dropping, the temperature was slowly raised to 160 ° C. After the reaction was completed, the reaction solution was cooled to 70 ° C and added to 200 ml of methanol to precipitate a polymer. The precipitated polymer was further washed with 200 ml of acetone, and vacuum dried at 130 ° C. for 12 hours to prepare a graft modified ethylene / propylene / isoprene copolymer. In the resulting modified polymer, it was modified with 3.5% by weight maleic anhydride. The intrinsic viscosity (η) of the modified polymer measured in 135 ° C decalin was 1.4 dl / g.

Example B1 B2 Constituent units (mol%) E / IP E / P / IP 1,2-addition 0.04 0.05 3,4-addition 0.96 1.25 1,4-addition 0.5 0.7 5-membered ring (cyclopentane ring) 1.5 3.5 Ethylene Unit 97 68.8 Propylene unit 25.7 Tg (℃) -30 -40 Tm (℃) 100 - Intrinsic viscosity [η]) (dl / g) 1.5 1.4 Oxo (IV) (g / 100g) 27 15 Catalyst Activity (kg / mmolZr · hr) 26 10 E: ethylene, BD: 1,3-butadiene, P: propylene, IP: isoprene

Example B4

(Manufacture of Vulcanized Rubber)

Copolymer prepared in Example B2, zincated, stearic acid, HAF carbon black (HAF Asahi # 70TM, manufactured by Asahi Carbon Co., Ltd.), vulcanization accelerator MBT (Sanseller MBT ^TM , Sanshin Chemical Co., Ltd.), vulcanization accelerator TMTD ( Sanseller TT ^™ , manufactured by Sanshin Chemical Co., Ltd.) and sulfur were added in the following amounts. These were kneaded in an open roll (front roll / back roll: 50/60 ° C., 16/18 rpm) to prepare unvulcanized rubber compound.

(Composition composition)

Copolymer prepared in Example B2: 100 parts by weight

Zinc: 5 parts by weight

Stearic acid: 1 part by weight

HAF Carbon Black: 50 parts by weight

Vulcanization accelerator MBT: 0.5 parts by weight

Vulcanization accelerator TMTD: 1.0 parts by weight

Sulfur: 1.5 parts by weight

The vulcanized blended rubber was heated for 20 minutes in a press heated to 160 ° C. to prepare a vulcanized sheet. Then, the tensile strength, hardness, and compression set test of the sheet were carried out under the above conditions.

Tensile strength TB (MPa) was 20, elongation EB (%) was 270, and hardness HS (JIS A) was 76.

The results are shown in Table 8.

Comparative Example B1

Ethylene / propylene / 5-vinyl-2-norbornene copolymer rubber (ethylene: propylene = 71: 29 (molar ratio), oxo number = 9 g / 100 g, [η] =) without using the copolymer prepared in Example B2 Example B4 was repeated except that 2.12 dl / g) was used.

It could not be vulcanized and no physical properties were measured.

This result is shown in Table 8.

Example B4 Comparative Example B1 Vulcanization property TB (MPa) 20 Unvulcanized EB (%) 270 HS (JIS A) CS (%) 76

Example B5

The procedure of Example A9 was repeated except that the rubber prepared in Example B2 was used, and oil resistance was evaluated. In this result, ΔV (%) was 102%.

Comparative Example B2

ENB-EPT copolymer (ethylene / propylene / ethylidene norbornene with an ethylene / propylene / ENB component ratio of 70.2 / 27.9 / 1.9 (molar ratio), an intrinsic viscosity (η) of 1.5 dl / g and an oxo value of 15 g / 100 g Copolymer) procedure was repeated with Example B5.

As a result, ΔV (%) was 125 (%).

Example B6

40 g of the ethylene / isoprene copolymer prepared in Example B1 were collected. 2,5-dimethyl-2,5-ditertbutylperoxyhexane was mixed with the copolymer, kneaded for 3 minutes at 200 ° C. at 100 rpm in laboplasmomill, and crosslinked.

The haze of the crosslinked polymer was 12%, the heat resistance index temperature was 115 ° C, the Young's modulus was 98 MPa, and the martensity hardness was 10.6 mm ^-1 .

The haze of the ethylene / isoprene copolymer before crosslinking was 10%, the heat resistance index temperature was 112 ° C, the Young's modulus was 94 MPa, and the martensite hardness was 9.6 mm ⁻¹ .

These physical properties were measured by the following method.

Haze (%):

A sheet having a thickness of 1.0 mm was molded and measured with a digital turbidimeter DH-20D manufactured by Nippon Denshoku Kogyo Co., Ltd.

Martens Hardness (/ mm):

The test piece was broken by the Martens scratch hardness tester, and the reciprocal of the breaking width was measured.

Heat test

A load of 2 kg / cm ² was applied to the sample having a thickness of 2 mm in accordance with JIS K 7196, and the temperature was raised to 5 ° C / min. The permeation temperature was obtained from the TMA (thermomechanical analysis) curve and the temperature was taken as heat index.

Young's modulus (YM) (MPa):

JIS 3 dumbbells were sandwiched between chucks at 30 mm intervals, and YM was measured at a tensile rate of 30 mm / min at room temperature (23 ° C).

Synthesis Example C1

(Preliminary activation of catalyst)

13.5 mg of (dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane) dichloride titanium synthesized by a known method was weighed into a glass vessel completely substituted with nitrogen. 22.86 mmol of an aluminum atom and 22.86 ml of an equivalent amount of 0.808 mmol / ml methyl aluminoxane (hereinafter referred to as MAO) were added together to the vessel. Thereafter, the mixture was irradiated with ultrasonic waves at 23 ° C. for 15 minutes to prepare a catalyst solution.

(Synthesis of ethylene / butadiene / styrene copolymer)

440.6 ml of toluene and 30 ml of styrene were added to a 2 liter autoclave dried under reduced pressure and replaced with nitrogen at room temperature, and ethylene was supplied with stirring to raise the pressure to 6 kg / cm ² G. The autoclave was then depressurized. The procedure of pressurizing and depressurizing was repeated three times.

Then 18 ml of 1,3-butadiene (25 ° C., 1 atmosphere) was added in the presence of ethylene at atmospheric pressure, and the temperature of the autoclave was raised to 30 ° C. The system was then pressurized with 6 kg / cm ² G with ethylene, 3.11 ml of the catalyst solution prepared in preliminary activation of the catalyst was added and copolymerization of ethylene, styrene and 1,3-butadiene was initiated. In this copolymerization, the catalyst concentration of (dimethyl (t-butyl amide) tetramethyl-η ⁵ -cyclopentadienyl) dichloride titanium per electric field in the copolymer was 0.01 mmol / liter, and the catalyst concentration of MAO was 6.0 mmol / liter. The internal pressure was maintained at 6 kg / cm ² G by feeding ethylene continuously during the polymerization. After 15 minutes, methyl alcohol was added to terminate the polymerization reaction. After the pressure was released, the polymer solution was taken out, washed with an equivalent aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 liter of water, and the catalyst residue was transferred to an aqueous phase.

The contact mixed solution was allowed to stand and the aqueous phase was separated and removed. Further, the polymerization liquid phase was washed twice with distilled water, and then the oil and water were separated, and the polymerized liquid phase was contacted with vigorous stirring with three times the amount of acetone. The polymer was washed thoroughly with acetone and filtered to collect the solid phase (copolymer). The copolymer was dried at 130 ° C. and 350 mm Hg for 12 hours in a nitrogen stream.

The ethylene / styrene / 1,3-butadiene copolymer yield thus prepared was 13 g, the intrinsic viscosity (η) was measured in 135 ° C decalin, 2.0 dl / g, the glass transition temperature (Tg) was -30 ° C., and the oxo value was 22 g /. 100 g, ethylene content of 86.7 mol%, styrene content of 4.0 mol%, 5-membered ring structure of 5.9 mol%, cyclopropane ring structure of 0.2mol%, 1,2-addition structure of 0.7mol%, 1,4- Additional structure was 2.5 mol%, and activity was 10.4 kg / mmolZr hr.

The results are shown in Table 9.

Example C2

The procedure of Example C1 was followed except that 4400 ml (25 ° C., 1 atm) of propylene was further introduced, the amount of 1,3-butadiene was changed to 13 ml, the amount of styrene was changed to 50 ml, and the reaction temperature was changed to 20 ° C. Repeated. The yield of the produced ethylene / propylene / styrene / 1,3-butadiene copolymer was 9 g, the intrinsic viscosity (η) measured in 135 ° C decalin, 2.1 dl / g, the glass transition temperature (Tg) was -44 ° C, and oxo value 17.5g / 100g, ethylene content 63.6mol%, propylene content 23.7mol%, styrene content 5.4mol%, 5-membered ring structure 4.8mol%, cyclopropane ring structure 0.1mol%, 1,2-addition structure 0.5 mol%, 1,4-addition structure was 1.9 mol%, and activity was 7.2 kg / mmolZr hr.

The results are shown in Table 9.

Example C3

38 ml of toluene and 6 g of ethylene / propylene / styrene / 1,3-butadiene copolymer prepared in Example C2 were introduced into a 200 ml glass autoclave completely substituted with nitrogen, and the temperature was raised to 140 ° C. while stirring the mixture. . In another vessel, a solution was prepared by dissolving 1.06 g of maleic anhydride and 0.18 g of dicumyl peroxide in 8 ml of toluene. The solution was added dropwise to the autoclave at a constant rate over 3.5 hours, followed by stirring for 30 minutes. During the dropping, the temperature was slowly raised to 160 ° C. After the reaction was completed, the reaction solution was cooled to 70 ° C. and added to 200 ml of methanol to precipitate a polymer. The precipitated polymer was further washed with 200 ml of acetone and vacuum dried at 130 ° C. for 12 hours to prepare a graft modified ethylene / propylene / styrene / 1,3-butadiene copolymer. In the resulting modified polymer, it was modified with 3.5% by weight maleic anhydride. The intrinsic viscosity of the modified polymer measured in 135 ° C decalin was 2.0 dl / g.

Example C1 C2 Constituent units (mol%) E / S / BD E / P / S / BD 1,2-addition 0.7 0.5 3,4-addition 1,4-addition 2.5 1.9 5-membered ring (cyclopentane ring) 5.9 4.8 3-membered ring (cyclopropane ring) 0.2 0.1 Ethylene Unit 86.7 63.6 Propylene unit 23.7 Styrene units 4.0 5.4 Tg (℃) -30 -44 Tm (℃) 52 - Intrinsic viscosity [η] (dl / g) 2.0 2.1 Oxo (IV) (g / 100g) 22 17.5 Catalyst Activity (kg / mmolZr · hr) 10.4 7.2 Mw / Mn 2.5 2.5 E: ethylene, BD: 1,3-butadiene, P: propylene, S: styrene

Example C4

(Manufacture of Vulcanized Rubber)

Examples C2 copolymer, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70 ^TM, syaje between Asahi Carbon whether or sikki) and dicumyl peroxide (DCP-40C) was manufactured by adding the following amounts. These were kneaded with an open roll (front roll / back roll: 50/60 ° C., 16/18 rpm) to produce an unvulcanized blended rubber.

(Composition composition)

Copolymer prepared in Example C2: 100 parts by weight

Zinc: 5 parts by weight

Stearic acid: 1 part by weight

HAF Carbon Black: 50 parts by weight

Dicumyl peroxide (DCP-40C): 7 parts by weight

The unvulcanized blended rubber thus prepared was heated in a press heated at 170 ° C. for 15 minutes to prepare a vulcanized sheet. Then, the tensile strength, hardness, and compression set of the vulcanized sheet were tested under the above conditions.

Tensile strength TB (MPa) was 21, elongation EB (%) was 210, hardness was HS (JISA) was 72, and compression set (CS) (%) was 14.

The results are shown in Table 10.

Comparative Example C1

Ethylene / propylene / styrene / 5-ethylidene-2-norbornene copolymer rubber (ethylene: propylene = 74: 26 (molar ratio), styrene content = 4.6 mol%, oxo without using the copolymer prepared in Example C2) The procedure of Example C4 was repeated except that == 18 g / 100 g, [η] = 1.45).

Tensile strength TB (MPa) was 20, elongation EP (%) was 260, hardness (HS (JIS A)) was 70, and compression set was CS (%).

The results are shown in Table 10.

Example C4 Comparative Example C1 Vulcanization property TB (MPa) 21 20 EB (%) 210 260 HS (JIS A) CS (%) 72 70 CS (%) 14 22

Example C5

(Synthesis of ethylene / propylene / styrene / 1,3-butadiene)

3900 ml (25 degreeC, 1 atmosphere) of propylene were further introduce | transduced, the procedure of Example C1 was repeated except changing the amount of catalysts to 1.56 ml, and changing reaction temperature to 20 degreeC. The yield of the produced ethylene / propylene / styrene / 1,3-butadiene copolymer was 4.2 g, the intrinsic viscosity (η) was measured in 135 ° C decalin, 2.5 dl / g, the glass transition temperature (Tg) was -42 ° C., and the oxo value was 21 g / 100 g, 67.8 mol% ethylene, 18.9 mol% propylene, 5.4 mol% styrene, 4.8 mol% for 5-membered ring structure, 0.1 mol% for cyclopropane ring structure, 0.5 mol for 1,2-addition structure mol%, 1,4-addition structure was 1.9mol% and activity was 7.2kg / mmolZr · hr.

(Manufacture of Vulcanized Rubber)

Thus prepared ethylene / propylene / styrene / 1,3-butadiene copolymers, zinc white, stearic acid, HAF carbon black (HAF Asahi # 70 ^TM, between whether or Asahi carbon sikki syaje) and the amount of dicumyl peroxide (DCP-40C) and then Added. These were kneaded with an open roll (front roll / back roll: 50/60 ° C., 16/18 rpm) to produce an unvulcanized blended rubber.

(Composition composition)

Ethylene / propylene / styrene / 1,3-butadiene copolymer: 100 parts by weight

Zinc: 5 parts by weight

Stearic acid: 1 part by weight

HAF Carbon Black: 50 parts by weight

DCP-40C: 7 parts by weight

The unvulcanized blended rubber thus prepared was heated in a press heated at 170 ° C. for 15 minutes to prepare a vulcanized sheet. Tensile strength TB (MPa) of the vulcanized sheet was 23, elongation EB (%) was 230, hardness HS (JIS A) was 76, compressive permanent deformation (CS) (%) was 12, and no surface adhesion was observed.

The sheet is suitable for use as a glass run channel.

Further, the roll nip was adjusted to 1 mm, the unvulcanized rubber was separated, taken out, and crosslinked for 10 minutes in an oven heated to 220 deg. Thereafter, surface adhesion was observed.

The results are shown in Table 11.

Vulcanization Properties Example C5 TB (MPa) 23 EB (%) 230 HS (JIS A) 76 CS (%) 12 Surface Adhesion radish

Example C6

The procedure of Example C1 was repeated except that the catalyst was changed to isopropylidene bis (indenyl) zirconium dichloride synthesized by known methods.

The yield of the resulting ethylene / styrene / butadiene copolymer was 2.5 g, the intrinsic viscosity (η) was measured in 135 ° C decalin, 1.1 dl / g, the glass transition temperature (Tg) was -25 ° C, the oxo value was 15 g / 100 g, and the ethylene content. 88.0 mol% of silver, 4.5 mol% of styrene, 4.8 mol% of 5-membered ring structure, 0.2 mol% of cyclopropane ring structure, 0.6 mol% of 1,2-addition structure, 1.9 mol% of 1,4-addition structure And activity was 2 kg / mmolZr hr.

Example C7

The procedure of Example A9 was repeated except that the rubber prepared in Example C2 was used, and oil resistance was evaluated. As a result, ΔV (%) was 91%.

Comparative Example C2

ENB-EPT copolymer (ethylene / propylene / ethyl) having an ethylene / propylene / styrene / ENB component ratio of 65.7 / 26.7 / 5.3 / 2.3 (molar ratio), an intrinsic viscosity (η) of 2.0 dl / g, and an oxovalent 18 g / 100 g Example C7 was repeated except for using a lidene norbornene copolymer). Then oil resistance was evaluated. As a result, ΔV (%) was 112%.

According to the present invention, it has excellent weather resistance, heat resistance, oil resistance, etc., has an economical advantage, has a low glass transition temperature, has excellent low temperature resistance, has excellent crosslinking efficiency, particularly organic peroxide crosslinking efficiency, and sulfur. There is provided an unsaturated copolymer which can be crosslinked and which can be produced at low cost and economically.

According to the present invention, there is also provided a method capable of producing an unsaturated copolymer having the above excellent physical properties.

Claims (26)

It is an unsaturated copolymer which is a copolymer of the C2-C12 alpha-olefin and the conjugated diene monomer represented with the following general formula (I-b), The physical property is: (a) In the copolymer, 1,2-added units (including 3,4-addition units) derived from conjugated diene monomers (Ib) form double bonds in the side chains of the copolymer, and conjugated diene monomers (Ib) 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of heavy to heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of main chains derived from 1,4-addition units) is in the range of 5/95 to 99/1. Unsaturated copolymer. Wherein R ¹ is an alkyl or aryl group having 1 to 8 carbon atoms It is an unsaturated copolymer which is a copolymer of the C2-C12 alpha-olefin and the conjugated diene monomer represented with the said general formula (I-b), The physical property is: (a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (Ib) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (Ib) 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of the ratio of heavy bonds (double bonds of the side chains derived from 1,2-addition units / double bonds of the main chain derived from 1,4-addition units) is in the range of 5/95 to 99/1; (b) a 5-membered ring is present in the main chain of the copolymer, (c) the ratio of the amount of the double bonds derived from the total addition units to the five-membered rings (total / 5-membered rings of the double bonds derived from the total addition units) is in the range of 20/80 to 90/10. Unsaturated copolymer. The unsaturated copolymer of claim 1 or 2, wherein the conjugated diene monomer is isoprene. The α-olefin is a combination of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms, and in the combination, the molar ratio of ethylene to an α-olefin having 3 to 12 carbon atoms is used. Unsaturated copolymer, it is the range of 99/1-40/60. The unsaturated copolymer according to claim 1 or 2, wherein the copolymer contains 0.01 to 30 mol% of the total amount of the structural units derived from the conjugated diene monomer. 3. The glass according to claim 1, wherein the unsaturated copolymer has an oxo value of 1 to 50 g / 100 g, an intrinsic viscosity (η) measured at 135 ° C. and decalin, and 0.01 to 10 dl / g. Unsaturated copolymer, characterized in that the transition temperature (Tg) is 25 ℃ or less. (a) the unsaturated copolymer of claim 1 or 2, (b) an unsaturated copolymer-containing elastomer composition, comprising a crosslinking agent and / or a filler. A method for producing the unsaturated copolymer of claim 1 or 2, wherein the C 2-12 alpha-olefin and at least one conjugated diene monomer represented by the above general formula (Ib) are copolymerized in the presence of a catalyst. A method for producing an unsaturated copolymer, characterized by using the following component (a) and at least one catalyst system of at least one compound selected from the following components (b), (c) and (d). (a) the transition metal complex represented by the following general formula (II) or (III): Wherein M is Ti, Zr, Hf, Rn, Nd, Sm or Ru; Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof π-bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms (b) a compound which reacts with the transition metal (M) of component (a) to form an ionic complex, (c) an organoaluminum compound, and (d) aluminoxanes. It is an unsaturated copolymer which is a copolymer of a C2-C12 alpha-olefin, an aromatic vinyl compound, and the conjugated diene monomer represented by following General formula (I), The physical property is: (a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (I 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of heavy to heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of main chains derived from 1,4-addition units) is in the range of 5/95 to 99/1. Unsaturated copolymers. In formula, R <^1> and R <^2> is respectively independently a hydrogen atom, a C1-C8 alkyl group, or an aryl group, and at least ^one of R <^1> and R <^2> is a hydrogen atom It is an unsaturated copolymer which is a copolymer of a C2-C12 alpha-olefin, an aromatic vinyl compound, and the conjugated diene monomer represented by following General formula (I), The physical property is: (a) In the copolymer, 1,2-addition units (including 3,4-addition units) derived from the conjugated diene monomer (I) form a double bond in the side chain of the copolymer, and the conjugated diene monomer (I 1,4-addition unit derived from) forms a double bond in the main chain of the copolymer, and 2 of the main chain derived from the 1,4-addition unit of the double bond of the side chain derived from the 1,2-addition unit The ratio of heavy to heavy bonds (double bonds of side chains derived from 1,2-addition units / double bonds of backbones derived from 1,4-addition units) ranges from 10/90 to 99/1: (b) a 5-membered ring is present in the main chain of the copolymer, (c) the ratio of the amount of double bonds derived from the total addition units to the 5-membered rings (total / 5-membered rings of the double bonds derived from the total addition units) is in the range of 20/80 to 90/10; (d) Unsaturated copolymer characterized in that the structural unit derived from an aromatic vinyl compound is 0.1-60 mol%. The unsaturated copolymer according to claim 9 or 10, wherein the copolymer contains 0.01 to 30 mol% of the total amount of the structural units derived from the conjugated diene monomer. The unsaturated copolymer according to claim 9 or 10, wherein the conjugated diene monomer is 1,3-butadiene. The unsaturated copolymer according to claim 9 or 10, wherein the conjugated diene monomer is isoprene. The α-olefin according to claim 9 or 10 is a combination of ethylene or ethylene and an α-olefin having 3 to 12 carbon atoms, and in the combination, the molar ratio of ethylene to an α-olefin having 3 to 12 carbon atoms is 11. Unsaturated copolymer, it is the range of 99/1-40/60. The unsaturated copolymer according to claim 9 or 10, wherein the aromatic vinyl compound is styrene. The oxo number is 1-50 g / 100 g, the intrinsic viscosity (eta) measured by 135 degreeC and decalin is 0.01-10 dl / g, and glass transition temperature (Tg) is 25 degrees C or less of Claim 9 or 10. Unsaturated copolymer, characterized in that. The unsaturated copolymer according to claim 9 or 10, wherein the peak of the melting point (Tm) of the copolymer is 120 ° C or less as measured by DSC. A modified copolymer obtained by graft modification of the unsaturated copolymer of claim 9 or 10 with at least one compound selected from the group consisting of (i) an unsaturated carboxylic acid or a derivative thereof and (ii) an aromatic vinyl compound, wherein the unsaturated carboxylic acid or The graft ratio of the derivative | guide_body and the aromatic vinyl compound is 0.01-30 weight%, The modified copolymer characterized by the above-mentioned. (a) the unsaturated copolymer of claim 9 or 10 and (b) an unsaturated copolymer-containing elastomer composition, comprising a crosslinking agent and / or a filler. The method for producing an unsaturated copolymer according to claim 9 or 10, wherein a C2-C12 alpha-olefin, an aromatic vinyl compound, and at least one conjugated diene monomer represented by the general formula (I) are copolymerized in the presence of a catalyst. The method for producing an unsaturated copolymer according to claim 1, wherein at least one catalyst system comprising the following components (a) and at least one compound selected from the following components (b), (c) and (d) is used as a catalyst. (a) the transition metal complex represented by the following general formula (II) or (III): Wherein M is Ti, Zr, Hf, Rn, Nd, Sm or Ru; Cp1 and Cp2 are each a cyclopentadienyl group, an indenyl group, a fluorenyl group or a derivative thereof π-bonded to M; X ¹ and X ² are anionic ionic ligands or neutral Lewis base ligands, respectively; Y is a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom; Z is C, O, B, S, Ge, Si, Sn or a group containing any of these atoms (b) a compound which reacts with the transition metal (M) of component (a) to form an ionic complex, (c) an organoaluminum compound, and (d) aluminoxanes. The crosslinked product obtained by crosslinking the composition of Claim 7. The crosslinked product according to claim 21, wherein the crosslinking agent used for crosslinking the composition is an organic peroxide. 23. A film or sheet comprising the crosslinked product of claim 21 or 22. A crosslinked product obtained by crosslinking a composition according to claim 19. The crosslinked product according to claim 24, wherein the crosslinking agent used for crosslinking the composition is an organic peroxide. A film or sheet comprising the crosslinked product of claim 24 or 25.