JPH01168705A - Preparation of hydroxylated olefin copolymer - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a method for producing a hydroxy group-containing olefin copolymer.

[Prior Art] It is well known that ethylene is copolymerized with functional group-containing polymers such as vinyl acetate and acrylic monomers by radical polymerization. However, α-olefins such as propylene and l-butene cannot be polymerized at all by radical polymerization, or even if they can be polymerized, only low molecular weight polymers are produced. A so-called Ziegler polymerization catalyst formed from a transition metal compound such as a Ti compound or a V compound and a typical metal compound such as an organoaluminum compound exhibits excellent polymerization activity for olefins consisting of carbon and hydrogen. However, since olefins with functional groups containing elements such as oxygen and nitrogen inactivate the Ziegler polymerization catalyst, it is not preferable to use olefins with such functional groups. Use is not recommended.

On the other hand, copolymers of ethylene and α-olefins or copolymers of ethylene, α-olefins and non-conjugated dienes are used as materials for automobiles and electric wires due to their good weather resistance, ozone resistance, and heat resistance. It is widely used as a building material, industrial material, and plastic blending material. However, since this polymer does not have functional groups as expected from its chemical structure, it has very poor adhesion and compatibility with other materials such as metals, resins other than polyolefins, and elastomers. The problem is that it is inferior.

[Problems to be Solved by the Invention] The present invention provides a hydroxy group-containing olefin that has improved properties such as adhesion and compatibility with other materials other than metals and polyolefins, such as resins and elastomers, and has reactivity. The purpose of the present invention is to provide a method for efficiently producing a copolymer.

[Means for Solving the Problems] The above object is, according to the present invention, to produce ethylene, ethylene, carbon atoms of 3 to 18 α-orphine and the following general formula [I] CHz=CH-R'40H) [I] [wherein,
a is an integer from 1 to 3; , n is 0 to 2
m + n is not 0, R2 is a direct bond or an aliphatic hydrocarbon group having 1 or more carbon atoms, and R3 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms] In a method for producing a hydroxy group-containing olefin copolymer by copolymerizing at least one hydroxy group-containing monomer selected from the group consisting of saturated monomers, 0.7 to 2 hydroxy groups are added per mole of the hydroxy group. This is achieved by a method for producing a hydroxy group-containing olefin copolymer, which is characterized in that copolymerization is carried out continuously in the presence of a molar amount of a halogen-containing metal compound other than a halogenated organic aluminum compound.

The present invention will be explained in detail below.

In the method of the present invention, the soluble vanadium compound component used as a catalyst component is a vanadium compound component soluble in the hydrocarbon medium of the polymerization reaction system, and specifically has the general formula VO(OR)aXb or V C0R)cXd (
However, R is a hydrocarbon group, 0≦a≦3.0≦b≦3.2≦a
+b≦3.0≦C≦4.0≦d≦4.3≦c+d≦4)
Typical examples include vanadium compounds represented by or electron donor adducts thereof. More specifically, VOCI 3 , VO(QC,R5)CI
2, VO(OC2Hs)ic I s VO(0-i
s o C5Ht) CI,, VO(〇-n -C4Hs
) CI 2 , VO(OC2Hs)s , VOB
rx, VC+4, VOCI2, VO(0-n-C
4Hs)s, etc. can be exemplified.

Electron donors that may be used in the preparation of the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, and acid anhydrides. , an oxygen-containing electron donor such as alkoxysilane, and a nitrogen-containing electron donor such as ammonia, amine, nitrile, isocyanate, etc. can be used. More specifically, methanol, ethanol, propatool, pentanol, hexanol, octatool, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, amyl alcohol, isopropylbenzyl alcohol, etc. Alcohols having 1 to 18 carbon atoms phenol, cresonol xylenol, ethylphenol, propylphenol, nonylphenol,
Phenols having 6 to 20 carbon atoms which may have a lower alkyl group such as cumylphenol and naphthol; Ketones having 3 to 15 carbon atoms such as acetone, methyl ethyl ketone butyl ketone, acetophenone, benzophenone and benzoquinone; acetaldehyde, propionaldehyde , octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde and other aldehydes having 2 to 15 carbon atoms; methyl formate, methyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methinovalerate butyrate , methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, ethyl benzoate, butyl benzoate, octyl benzoate, cyclohexino benzoate, phenyl benzoate, benzino benzoate, methino toluate, ethyl toluate, amyl toluate, ethyl toluate Ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropylene tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate , di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate, etc. with 2 to 3 carbon atoms
0 organic acid esters; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluyl chloride, anisyl chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran, anisole, Ethers having 2 to 20 carbon atoms such as diphenyl ether; Acid amides such as acetamide, benzoic acid amide and toluic acid amide: methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetra Examples include amines such as methylene diamine; nitriles such as acetonitrile, benzonitrile, and tolnitrile; and alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Two or more types of these electron donors can be used.

As the organoaluminum compound catalyst component used in the present invention, compounds having at least one AI-carbon bond in the molecule can be used, such as (i) general formula R
'． ．． A I (O R'), H, X.

(Here, R1 and R2 are the number of carbon atoms, usually 1 to 15
, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is Oh
m≦3, n is 0≦n<3, p is 0≦n<3, q
is a number such that 0≦q<3, and m + n +
p + q = 3); (ii) general formula M'A I R';

(Here, Ml is Li, Na, or Ni, and R1 is the same as above.) Complex alkylated products of Group 1 metals and aluminum, etc., can be mentioned.

Examples of the organoaluminum compounds belonging to (i) above include the following.

General formula R'', AI(OR, -1 (where R1 and R2 are the same as above; m is preferably a number of 1.5≦m≦3).

General formula R', A 13-+++ (where R1 is the same as above, X is halogen, and m is preferably 0 < m < 3).

General formula R', A I H3-+++ (Here, R1 is the same as above. m is preferably 2≦m<3
).

General formula R', AI(OR"), X.

(Here R1 and R1 are the same as before. X is halogen, 0
<m≦3.0≦n <3.0≦q<3, m+n+q
= 3).

Among the aluminum compounds belonging to (i), more specifically, trialkenylaluminums such as trialkylaluminum nitriisoprenylaluminum such as triethylaluminum and tributylaluminium; dialkylaluminum alkoxides such as diethylaluminium ethoxide and diptylaluminum butoxide; In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, R'0. IAI(ORtsu.

, S etc.; dialkylaluminum halides such as diethylaluminum chloride, diptylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum sesquichloride, Partially halogenated a) Rekylaluminum: Diethylaluminium Partially hydrogenated alkylaluminums such as hydride, dialkyl aluminum hydride such as diptylaluminum hydride, alkyl aluminum halide such as ethyl aluminum dicdolide, probyl aluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride , partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxypromide. Moreover, as a compound similar to (i), an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom may be used.

Examples of such compounds include (C!HI)! AI
0 A 1 (C!HS)! , (CaH*)zA 1
()A I (CaHI)! , (CxHs)zA
An example is INAI(CxHs)x. Compounds belonging to the above (■) include LIA
I (C2H4)4, L I A I (C2H1@
)4 can be exemplified.

Among these, it is particularly preferable to use alkylaluminum halides, alkylaluminum cibarides, or mixtures thereof.

In the method of the present invention, the halogen-containing metal compound other than the halogenated organoaluminum compound used in a ratio of 0.7 to 2 moles per 1 mole of hydroxyl group-containing aluminum is specifically a halogen-containing organosilicon. Compounds, halogen-containing silicon compounds, halogen-containing tin compounds, halogen-containing boron compounds, halogen-containing titanium compounds, halogen-containing vanadium compounds, halogen-containing zirconium compounds, halogen-containing tungsten compounds, halogen-containing niobium compounds, halogen-containing hafnium compounds, halogen-containing tantalum Examples include compounds.

More specifically, the halogen-containing metal compound is, for example, R1SiH,X.

(Here, R1 is a hydrocarbon group containing usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and may be the same or different, X is a halogen, and m is O<m<
3, n is a number of 0≦n<3, p is a number from 0 to 4, and m+p-4). More specifically,
cH, 5tcl, , CHsSiHcll, CHsCH
2S 1c11 , (CHs)zsi C1z , CH
3CH! S i HC1z , (CHs)xsiHc1
% CHlCHICHas i C13, (CHs) (
CH3CHriS i C+! , CHs(CHx)*
S iCl, , CHs-CHCH*S i C
1s, CH.

(CH, CH,), S i C1,, (CH, CH, C
H,)(CH3)S i C11, (CHsCHx)1
3 iHc 1°CHs (halogen-containing organosilicon compounds such as CH 4 S i C1s, 5iC1,,5i
Br, , H5iC1s, HsSiClx, HsSiCl
Silicon compounds such as 5nC1,, tin compounds such as 5nBra, B C1m , B B r s s B
Boron compounds such as F s, T i C14, T i
Titanium compounds such as B r 4, Tj I4, VC'
l, vanadium compounds such as V OCl s, ZrC
1,, M OC1s , W C ] @ , N b C1
Examples include metal compounds such as a, HfCla, and TaCI. Among these, silicon compounds and halogen-containing organosilicon compounds are preferred.

The hydroxy group-containing monomer used as a polymerization raw material in the method of the present invention has the following general formula:
or the following aliphatic hydrocarbon group] and the following general formula rl
] [wherein p is O or l, m, n are O to 2
m+n is not O, R1 is a direct bond or an aliphatic hydrocarbon group having 1 or more carbon atoms, and Rs is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms] A monomer containing a hydroxyl group selected from the group consisting of monomers.

In the general formula [1F, a is preferably l, and the general formula [1[
], and m+n is preferably l.

In the case of 42-1 as the hydroxy group-containing monomer represented by the above formula [1], specifically, 4-penten-1-ol, 5-hexen-1-ol, 6-hebuten-1-ol, 7 -Omega-alkenyl alcohols such as octen-1-ol, 8-nonen-1-ol, 9-zocen-1-ol, 10-undecen-1-ol, ll-dodecen-1-ol, 5-hexene-2 -ol, 6-hebuten-2-ol, 7-octyne-2-
ol, 8-nonen-2-ol, 9-decen-2-ol, lO-undecen-2-ol, 6-hebuten-
3-ol, 7-octyn-3-ol, 8-nonene-
3-ol, 9-decen-3-ol, 10-undecen-3-ol, ll-dodecen-3-ol, 7-octin-4-ol, 8-nonen-4-ol, 9-decen-4-ol All, 10-undecen-4-ol, 8
-Nonen-5-ol, 9-decen-5-ol, lO
-Alcohols with a linear hydrocarbon moiety such as undecen-5-ol, 2-ethyl-5-hexene-1-
ol, 3-methyl-6-hebuten-1-ol, 3-
Methyl-7-octen-1-ol, 4-methyl-8-
nonen-1-ol, 3-ethyl-9-decen-1-ol, 2-methyl-10-undecen-2-ol, 2
, 2-dimethyl-7-octen-1-ol, 3-ethyl-2-methyl-8-nonen-1-ol, 2°2.3
-Trimethyl-9-decene-1-oat 2.3.3.
Examples include alcohols in which the hydrocarbon moiety is branched, such as 4-tetramethyl-IO-undecen-2-ol. In addition, in the case of Q-2, 7-octene-
1,2-diol, 8-nonene-1,2-diol, 9
-decene-1,2-diol, 10-dodecene-1,2
-diol, alcohols such as 11-undecene-1,2-diol, in the case of Q-3, 9-decene-1,2,
Examples include 3-triol, lO-dodecene-1°2,3-triol, and the like.

Further, specific examples of the hydroxy group-containing monomer represented by the general formula [1[] include propylene, l- Butene, l-pentene, l-hexene, l-heptene, l-:t-butene, l-decene, ■-dodecene,
■-tetradecene, l-hexadecene, 1-octadecene, l-eicosene, 3-methyl-1-pentene, 3-
Methyl-1-butene, 4-methyl-1-pentene, 4-
Examples include methyl-1-hexene and 5-methyl-1-hexene.

In the method of the present invention, ethylene, the a-olefin, and the hydroxyl group-containing polymer are copolymerized, but in addition to the three essential components, as necessary, as long as the object of the present invention is not impaired. Other copolymerizable unsaturated monomer components can also be copolymerized. Specifically, the copolymerizable unsaturated monomer includes, for example, 1,4-hexadiene, 4-methyl-1,4-in a mole less than equimolar to the ethylene component unit in the random copolymer to be produced. hexadiene, 5-
Examples include non-conjugated dienes such as methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylene-2-norbornene, and 5-vinyl-2-norbornene. can.

The copolymerization reaction according to the method of the invention is carried out in a hydrocarbon medium. Hydrocarbon media include, for example, aliphatic hydrocarbons such as hexane, heptane, octane, and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Examples include sexually unsaturated monomers, and a mixed medium of two or more of these may be used.

In the method of the invention, the copolymerization reaction is carried out in a continuous manner. The concentration of the soluble vanadium compound supplied to the polymerization reaction system at that time is in the range of 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system, The ratio of aluminum atoms to vanadium atoms in the polymerization reaction system (AI/
V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. When the concentration of the soluble vanadium compound supplied to the copolymerization reaction system is higher than 10 times the concentration in the copolymerization reaction system, a copolymer with a uniform molecular weight distribution and a narrow composition distribution, which is the object of the present invention, cannot be obtained. do not have. Furthermore, if the ratio of aluminum atoms to vanadium atoms (Al/V) in the copolymerization reaction system is less than 2, the polymerization activity will be low and the copolymer targeted by the present invention will not be obtained.

The soluble vanadium compound and the organoaluminum compound are each normally supplied diluted with the hydrocarbon medium. Here, the soluble vanadium compound needs to be diluted to the above concentration range, but the organoaluminum compound may be prepared at an arbitrary concentration, for example, 50 times or less of the concentration in the polymerization reaction system, and then supplied to the polymerization reaction system. will be adopted.

In the method of the present invention, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0. O
It ranges from 1 to 18 gram atoms/Q, preferably from 0.05 to 5 gram atoms/Q.

Further, in the method of the present invention, the copolymerization reaction is carried out at a temperature of -50 to 100°C, preferably -30 to 80°C, more preferably -20 to 60°C. In the method of the invention, the copolymerization reaction is carried out in a continuous manner.

Ethylene as a polymerization raw material, an a-olefin having 3 to 18 carbon atoms, a hydroxy group-containing monomer, a soluble vanadium compound component, an organoaluminum compound component, and a halogen-containing metal compound as other catalyst components to be copolymerized as necessary. and a hydrocarbon medium are continuously fed into the polymerization reaction system, and the copolymerization reaction mixture is continuously withdrawn from the polymerization reaction system.

The average residence time during the copolymerization reaction varies depending on the type of polymerization raw material, the concentration of the catalyst component, and the temperature, but is usually in the range of 5 minutes to 5 hours, preferably 10 minutes to 3 hours. The pressure during the copolymerization reaction is usually over 0 and 50k.
g/Cm! , preferably exceeding 0 and maintained at 20 to 9/cm'', and optionally an inert gas such as nitrogen or argon may be present. Also, in order to adjust the molecular weight of the copolymer, as appropriate, Molecular weight modifiers such as hydrogen may also be present.

The proportion of heptamer fed may be varied, but the amount of σ-olefin is maintained at a level such that the σ-olefin constitutes 5 to 70 mole percent of the resulting copolymer, preferably 10 to 60 mole percent. It is desirable to do so. The hydroxy group-containing monomer is supplied in such an amount that it constitutes 0.1 to 20 mole percent of the product.

The amount of the halogen-containing metal compound supplied is at least 0.7 to 20 mol, preferably 0.8 to 1.5 mol, based on the amount of hydroxyl groups supplied.

The hydroxy group-containing olefin copolymer obtained by the method of the present invention consists of a repeating unit (a) essentially derived from ethylene, a repeating unit (b) originating from a d-olefin having 3 to 18 carbon atoms, and the hydroxy Consists of repeating units (C) derived from group-containing monomers.

The repeating unit (a) and repeating unit (b) in the olefin copolymer have a molar ratio of 99/l to 30/70, preferably 9515 to 40/60, more preferably 90/1.
0 to 45155, and repeating unit (c)/(repeating unit (a) ten repeating unit (b)) is 0.01/99
．． 99-30/70, preferably 0.1/99.99-
25/85, more preferably 0.2/99.8 to 20/
It is 80.

The [v] of the hydroxy group-containing olefin copolymer obtained by the method of the present invention was 0 when measured in toluene at 30°C.
．． 0f-10dll/g, preferably 0.03-6dQ
/y.

The copolymer obtained by the present invention has the heat resistance and weather resistance of polyolefins. Furthermore, because it contains a hydroxyl group, it can be used for metals, polyesters, polycarbonates,
By removing resins or elastomers other than polyolefins such as polyphenylene ether, polyMMA, nylon, and polyacetal, and blending them with polyolefins such as polyethylene and polypropylene, it is effective to improve adhesion and paintability.

Furthermore, by blending it with the above-mentioned engineering plastics and polyolefins, it has the effect of improving the impact resistance of these polymers.

The present invention can provide a method for efficiently producing such useful copolymers.

[Effects of the Invention] The present invention is characterized by excellent weather resistance, ozone resistance, and heat resistance, as well as excellent adhesion and compatibility with other materials such as metals, resins other than polyolefins, and elastomers. Hydroxy group-containing olefin copolymers that can be used, for example, as modifiers, modifiers, compatibilizers, adhesives, lubricating oil additives, paint additives, and primers for resins or rubber-like polymers. A new method is provided that allows efficient production of coalescence.

[Example] Next, the method of the present invention will be specifically explained using Examples.

Example 1 Ethylene, propylene and 5-norbornene-2-methanol were continuously copolymerized using a 2a glass polymerization vessel equipped with a stirring blade. That is, from the top of the polymerization vessel, a hexane solution of 5-norbornene-2-methanol and a hexane solution of TiC1 were added at a rate of 0.5a/hour, each as a catalyst, so that the concentration of each in the polymerization vessel was 8°3 mmol/l. Polymerize a hexane solution of (OH!H8)C1* with a vanadium concentration of 0.5 mm in the polymerization vessel.
A hexane solution of ethylaluminum sesquichloride was added at 0.6 g per hour so that the aluminum concentration in the polymerization vessel was 5 mmo+/12.
412 is continuously fed into the polymerization vessel, and ethylene is supplied from the top of the polymerization vessel at a rate of 80a/hour.

Propylene was supplied at a rate of 120 ff/hr and nitrogen at a rate of 60 Q/hr, while the polymerization liquid was continuously drawn out from the lower part of the polymerization vessel so that the polymerization liquid in the polymerization vessel was always at IQ. The copolymerization reaction was carried out at 30° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization vessel. When the copolymerization reaction is carried out under the above conditions, a polymerization reaction mixture containing an ethylene/propylene/5-norbornene-2-methanol copolymer is obtained. A small amount of methanol was added to the polymerization solution taken out from the bottom of the polymerization vessel to stop the polymerization reaction, and after deashing with an aqueous hydrochloric acid solution, the solution was poured into a large amount of methanol to precipitate the produced copolymer. The obtained copolymer was dried under reduced pressure at 80°C all day and night. Copolymer was obtained at a rate of 209 m/h.

The ethylene component of the copolymer measured by l''c-NMR is 7
1.1 mol%, 5-norbornene-2-methanol component 0.42 mol%, measured in toluene at 30 °C [
V] was 1.30 dff/g.

Examples 2 to 5 Polymerization was carried out in the same manner as in Example 1, except that the halogen and halogen-containing metal compounds were changed. The results are shown in Table 1.

Example 6 20 parts of hydroxy group-containing EPR synthesized in Example 2 and polypropylene (MFRf1g/10mln, 1197%
, [v]-2, Od2/g) at 2200°C using a single-screw extruder, and then further heated at 200°C to form a press sheet of the blend.

After washing the press sheet with tetrachlorethylene vapor for 30 seconds, apply a two-component urethane paint (Nippon B Chemical Co., Ltd.: R
-271) and baked at 100°C for 30 minutes. 180° peel strength of coating film (tensile speed 50 mm/m1
n) was 810 g/cm.

Comparative Example 1 Instead of the hydroxy group-containing EPR synthesized in Example 2, EPR not containing hydroxy groups (ethyl/7 content 8
The peel strength was measured in the same manner as in Example 6 using 0 mo1% [v] -1,50 dQ/g), and the peel strength was 10 g/cm.

Claims (1)

[Claims] (1) In a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound, ethylene, an α-olefin having 3 to 18 carbon atoms, and the following general formula [I] CH_2= CH-R^1■OH)_l [I] [in the formula,
l is an integer from 1 to 3, R^1 is an aliphatic hydrocarbon group having 2 or more carbon atoms] and an unsaturated monomer represented by the following general formula [II] ▲ Numerical formula, chemical formula, table, etc. Yes▼[II] [In the formula, p is 0 or 1, and m and n are 0 to 2
is an integer, m+n is not 0, R^2 is a direct bond or an aliphatic hydrocarbon group having 1 or more carbon atoms, and R^3 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms. In the method for producing a hydroxy group-containing olefin copolymer, in which at least one hydroxy group-containing monomer selected from the group consisting of unsaturated monomers is copolymerized, 0.7 1. A method for producing a hydroxy group-containing olefin copolymer, which comprises continuously copolymerizing in the presence of 2 to 2 moles of a halogen-containing metal compound other than a halogenated organic aluminum compound.