JPS59217709A - Modified propylene polymer having low molecular weight and its production - Google Patents

Abstract

PURPOSE:To obtain the titled polymer having a specific physical property and low content of gelatinous modified polymer, and giving a coating film having excellent heat resistance, hardness and adhesivity, by grafting an unsaturated carboxylic acid derivative to a linear propylene oligomer. CONSTITUTION:A linear propylene oligomer is made to react with an unsaturated carboxylic acid derivative selected from unsaturated carboxylic acid, its anhydride and its ester, under heating, to obtain the objective polymer wherein the propylene oligomer has a propylene content of 60-100wt% and other 2-20C alpha-olefin content of 0-40wt%, an intrinsic viscosity [eta] of 0.03-0.8dl/g measured in decalin at 135 deg.C, a molecular weight distribution (represented by Mw/Mn) of 1-8, a melting point of 120-165 deg.C, a softening point of 50-160 deg.C, and a crystallinity of 20-65%. The ratio of the grafted unsaturated carboxylic acid component is 0.01-20g, the content of the gelatinous modified polymer is <=0.05g, and the amount of the terminal vinyl group is <=0.005mol per 100g of the propylene oligomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel graft copolymerization modifications of low molecular weight propylene polymers with unsaturated carbo/acid derivatives.

More specifically, the present invention relates to a modified low molecular weight propylene polymer having a significantly low content of a gel-like modified polymer.

Conventionally, low-molecular-weight ethylene polymers containing ethylene as a main component have been produced by polymerizing α-olefins containing ethylene as a main component in the presence of a transition metal catalyst containing titanium or vanadium as a main component using a medium-low pressure method. It is industrially produced by direct production, by high-pressure method, or by lowering the molecular weight of a high-molecular-weight ethylene polymer polymerized by medium-low pressure method by thermal degradation method or radical degradation method. Modified ethylene polymers are also produced by graft copolymerizing these low molecular weight ethylene polymers with unsaturated carboxylic acid derivative components such as maleic acid and maleic anhydride, and are widely used for various purposes. However, these modified ethylene low molecular weight polymers
The melting point and the softening point of II-/Z are also low, and they cannot be used for applications requiring heat resistance.

On the other hand, unlike low molecular weight ethylene polymers, stereoregular and crystalline propylene low molecular weight polymers that are mainly composed of propylene components, α-olefins that are mainly composed of propylene components are used as transition metal catalysts. It was not possible to produce it directly by polymerization in the presence of However, when producing a stereoregular and crystalline propylene polymer by polymerizing an α-olefin whose main component is propylene in the presence of the transition metal catalyst using a medium-low pressure method, it can be obtained by extraction. Atactic propylene low molecular weight polymers are inferior and have low melting and softening points, so even if they are modified, they cannot be used for applications that require heat resistance.

Conventionally, as a method for producing a stereoregular and crystalline low molecular weight propylene polymer containing a propylene component as a main component, a stereoregular and crystalline high molecular weight polymer polymerized by the above-mentioned medium-low pressure method has been used. A method has been adopted in which the molecular weight of a propylene polymer is lowered by thermal degradation or 6-radical degradation. The low-molecular-weight propylene polymer obtained by this method contains a considerable amount of vinyl-type carbon-carbon unsaturated bonds at the end of its molecular chain. Even if graft copolymerization was carried out, only a modified low molecular weight propylene polymer having a significantly high content of gel-like modified polymer could be obtained. Even if a modified low molecular weight propylene polymer containing a large amount of such a gel-like modified polymer is used as a raw material for manufacturing paints, coatings, ink additives, etc., it is impossible to demonstrate excellent performance. Ta.

By employing a specific polymerization process using a specific transition metal catalyst, the applicant has directly produced a low content of vinyl-type carbon-carbon unsaturated bonds from a propylene-based α-olefin. It was discovered and proposed that a low molecular weight propylene polymer having stereoregularity and crystallinity can be obtained.

The present inventors have discovered that when an unsaturated carboxylic acid derivative is graft copolymerized to such a novel low molecular weight propylene polymer,
It has been discovered that a low molecular weight modified propylene polymer having a significantly low content of gel-like modified polymer can be easily obtained, and the present invention has been achieved.

According to the present invention, since the uninvented modified low molecular weight polymers have a small content of gel-like modified polymers, modified propylene low molecular weight polymers obtained by directly or further halogenated these modified propylene low molecular weight polymers can be obtained. When used as a lubricant, paint, coating film, ink additive, etc., it has the characteristic that a film with excellent heat resistance, surface hardness, adhesion, etc. can be obtained.

To summarize the present invention, the present invention relates to modified propylene obtained by graft-copolymerizing an unsaturated carboxylic acid derivative component unit consisting of an unsaturated carboxylic acid, an acid anhydride thereof, or an ester thereof to a substantially linear low molecular weight propylene polymer. A low molecular weight polymer, wherein the propylene low molecular weight polymer contains an α-olefin component unit (a) containing 60 to 10,000% by weight of the propylene component unit (a) and having a carbon atom number other than propylene in the range of 2 to 20. b) is in the range of 0 to 40% by weight [where the sum of (a) and (b) is 100]. ], provided that the intrinsic viscosity [η
] is in the range of 0.03 to 0.8 d 1 / g, (C) the molecular weight distribution expressed by weight average molecular weight / number average molecular weight is in the range of 1 to 8, and (C) is measured with a differential scanning calorimeter. G) has a softening point measured by constant force penetration method (TMA method) of 5.
V) the degree of crystallinity measured by X-ray diffraction is in the range of 20 to 65 φ, and G) the grafting ratio of the unsaturated carboxylic acid derivative component unit (C) is in the range of 0 to 160°C, The amount is in the range of 0.01 to 20 parts by weight per 100 parts by weight of the modified low molecular weight polymer; ．．
0.004 mol or less, and the content of the gel-like modified polymer in the modified low molecular weight polymer is 0.05 g per 100 g of the modified low molecular weight polymer.
The gist of the material invention is a modified propylene low molecular weight polymer characterized by being in the following range, and further satisfying the above requirements (Al or A substantially linear low molecular weight propylene polymer having a content of 0.005 mol or less and 0 parts by weight per 100 parts by weight of the low molecular weight propylene polymer.
．． The above-mentioned ((
The gist of the invention is a method for producing a modified low molecular weight propylene polymer that satisfies the requirements of A) or Yama.

The composition of the propylene component unit (a) in the propylene low molecular weight polymer constituting the modified propylene low molecular weight polymer of the present invention needs to be in the range of 60 to 100% by weight, and more preferably 70 to 100% by weight. It is preferable that it be within the range of Further, the composition of α-olefin component units (bl) of constituent components other than propylene must be in the range of 0 to 40 weight units, and more preferably in the range of 0 to 30 weight units.

Here, in either case, the sum of (a) and the surface is 10
It is 0.

The α-olefin component unit (b) other than propylene in the propylene low molecular weight polymer constituting the modified propylene low molecular weight polymer of the present invention has an α-olefin component unit (b) having 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. It is an olefin component unit. Specifically, as the α-olefin component unit,
Ethylene, 1-butene, imbutene, 1-pentene, 2
-Methyl-1-butene, 3-methyl-1-butene, 1-
hexene, 3-methyl-1-pentene, 2-methyl-1
Component units such as -pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-icosene can be mentioned.

The component units of α-olefins other than propylene in the propylene low molecular weight polymer constituting the modified propylene low molecular weight polymer of the present invention are values measured by ISO-NMR spectroscopy.

The unsaturated carboxylic acid derivative component unit (C) constituting the modified propylene low molecular weight polymer of the present invention has a carbon atom number of 6.
to 20, preferably 4 to 10 unsaturated carboxylic acids, their acid anhydrides, or their esters. Specifically, unsaturated cyclomonocarboxylic acids such as acrylic acid and methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, allylsuccinic acid, mesaconic acid, glutaconic acid, endocis-bicyclo(2,2,1)hept -2-
ene-5,6-dicarboxylic acid (nadic acid ■), methylendocys-bicyclo (2゜2.1]hept-2-ene-5,6-dicarboxylic acid (methylnadic acid ■), tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as methylhexahydrophthalic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, allylconohlic anhydride, glutaconic anhydride, nadic anhydride, methylnadic anhydride,
Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride, methyl acrylate, ethyl methacrylate, monomethyl maleate, dimethyl maleate, diethyl fumarate, dimethyl itaconate, diisopropyl citraconate, glutacone Examples include lower alkyl esters of the unsaturated carboxylic acids such as dibutyl acid, monomethyl nadic acid, dimethyl nadic acid, monomethyl methyl nadic acid, dimethyl methyl nadic acid, diethyl tetrahydrofucurate, and mixtures of two or more of these components. Even if it is, there is no problem.

Among these unsaturated carboxylic acid derivative component units,
Maleic acid, maleic anhydride, -13-, ^ nadic acid or nadic acid anhydride are preferred.

The grafting ratio of the unsaturated carboxylic acid derivative component unit (C) constituting the modified low molecular weight propylene polymer of the present invention is in the range of 0.01 to 20 parts by weight based on 100 parts by weight of the base low molecular weight propylene polymer. It is preferably in the range of 0.05 to 15 parts by weight, and particularly preferably in the range of 0.1 to 10 parts by weight. When the grafting ratio of the graft modification component (C) is less than 0.01 parts by weight or more than 20 parts by weight, the modified propylene low molecular weight polymer obtained by graft copolymerizing the unsaturated carboxylic acid derivative component units is used as a lubricant. The adhesion of the composition containing the modified product to a different substrate, the printing properties of a molded article made of the composition, the adhesion properties of Lamicoat, and the coating film properties of the chlorinated product are reduced.

The content of terminal vinyl unsaturated bonds in the modified low molecular weight propylene polymer of the present invention must be in the range of 0.004 mol or less per 100 1 of the modified low molecular weight propylene polymer, and is 0.00
It is preferably in the range of 3 moles or less. Further, the content of the gel-like modified polymer in the modified propylene low molecular weight polymer must be 0.05.9 or less per 100 g, and more preferably 0.02,! It is preferably in the range of 9 or less. If the content of terminal vinyl unsaturated bonds in the modified low molecular weight propylene polymer or the content of the gel-like modified polymer exceeds the above range, the lubricant effect, adhesiveness, printing properties, and lamicoat may deteriorate in any case. Both the adhesion properties of chlorinated substances and the coating properties of chlorinated substances appear to deteriorate. The content of terminal vinyl unsaturated bonds and the content of the gel-like modified polymer in the modified low molecular weight propylene polymer were measured by the following method.

[Amount of terminal vinyl unsaturated bond gold]

Using orthodichlorobenzene as a solvent, JIS
- It was measured by the method according to -0070.

[Gel-like modified polymer content]

10 g of the modified propylene low molecular weight polymer was dissolved in 100 ml of paraxylene at 140°C, and this solution was heated to 140 ml.
The gel is filtered using a filter device kept at ℃ and the gelled material is separated. The collected gelled product is heated and vacuum-dried to remove loose xylene, and the weight of the gelled product is measured.

The modified propylene low molecular weight polymer of the present invention has an excellent lubricant effect, a composition containing it has a welding property on different substrates, a printing property of a molded article made of the composition, an adhesion property of Lamicort, and a chlorinated product. In order to exhibit excellent performance in coating film properties, the intrinsic viscosity [η] (value measured at 135°C in decalin solvent) must be 0.03 to 0.8.
It is necessary to be in the range of d1/9, and further 0.0
5 to 0.7 (fll#', especially 0.06 to Q
, 6 dl/9. Intrinsic viscosity [
As η] increases, the lubricant effect of the modified product, the adhesion of the composition containing the modified product to different types of substrates, the printing properties of molded articles made of the composition, and the adhesion properties of Lamicoat all decrease. Furthermore, the properties of the coating film made of the chlorinated modified product also deteriorate. Furthermore, even if the intrinsic viscosity [η] is too small, the aforementioned lubricant effect,
The adhesion of the composition, the printing properties of the molded body, the adhesion properties of Lamicoat, and the coating film properties become poor.

Molecular weight distribution (MW/Mn) expressed as weight average molecular weight/number average molecular weight of the modified propylene low molecular weight polymer of the present invention
is gel permeation chromatography (CPC)
It is measured by The molecular weight distribution of the modified propylene low molecular weight polymer is in the range of 1 to 8, preferably 1 to 7. (Measurement of molecular weight distribution by PC was carried out according to the long method. That is, using 0-dichlorobenzene as a solvent, 0.0 parts by weight of polymer per 100 parts by weight of solvent.
4. 2.6-+tert-butyl p- as l stabilizer
0.0 cresol per 100 parts by weight of polymer! Add M) to form a solution, and then pass through a 1μ filter to remove insoluble matter such as dust. After that, column temperature 1
35°C, flow rate 1. It was measured using a GPC measuring machine set at OmJ/min, and the numerical ratio was converted on a polystyrene basis.

The melting point of the modified propylene low molecular weight polymer of the present invention measured by differential scanning calorimetry, (D S C) is 120
The temperature range is from 130 to 165°C, preferably from 130 to 165°C. Note that the melting point here is measured as follows. That is, the sample is subjected to a differential scanning calorimeter (du pout
990 model), the temperature was raised from room temperature at a rate of 20°C/min, and when it reached 250°C, the temperature was raised at a rate of 20°C/min, once lowered to 25°C, and then raised again to 20°C/min.
The temperature is raised at a rate of min. min, and the melting point is read from the melting peak at this time (in many cases, multiple melting peaks appear, so in this case, the value on the lower melting point side was adopted).

The softening point of the modified propylene low molecular weight polymer of the present invention, as measured by constant force penetration method (TMA method), is in the range of 50 to 160°C, preferably 60 to 160°C. Even if the softening point of the low molecular weight polymer becomes too low or too high, the lubricant properties of the modified low molecular weight polymer, the printing properties of the molded product containing the modified product, and the Lamicor
The adhesion properties of 1- begin to deteriorate. Softening point is measured by the following method. In other words, the sample was compressed to a thickness of 1w.
A plate-like sheet of l1 was prepared, and this small piece sheet) (3wrn
Terminal M made by du pout
Pour into the mechanical analizer and set the needle weight to 49. The temperature was raised from room temperature at a rate of 5° C./min using F, and the temperature was read when the needle was 0.1 needle in size.

The crystallinity of the modified propylene low molecular weight polymer of the present invention as measured by X-ray diffraction is in the range of 20 to 5 cm,
Preferably it is in the range of 60 to 65%. Even if the crystallinity of the low molecular weight polymer becomes too low or too high, the lubricant properties of the modified low molecular weight polymer,
The printing properties of the molded article containing the modified product and the adhesion properties of LamiCoat begin to deteriorate. Crystallinity was measured by the following method. X-ray diffraction device (manufactured by Rigaku Denki Co., Ltd., RU-1
00PL), measure the X-ray diffraction pattern from 204° to 60°, separate the crystalline part and the amorphous part by the drawing method,
The degree of crystallinity was determined from the ratio of the total X-ray intensity to the X-ray intensity of the crystalline part.

The modified propylene low molecular weight polymer of the present invention has a substantially linear structure. Here, "substantially linear" means a linear structure having a short branch of an alkyl group such as a methyl group or a chain structure having a necessary branch chain and not having a three-dimensional crosslinked structure. can be confirmed by the fact that it is soluble in an organic solvent, such as varaxylene, and that no gel-like substance is present.

The propylene low molecular weight polymer used in the production of the modified propylene low molecular weight polymer of the present invention is a novel propylene low molecular weight polymer that is substantially linear, stereoregular, and crystalline and has propylene component units as its main component. It is a polymer, and its roughness and physical properties are specified by the following. (1) Its composition is that the propylene component unit (a) is 60
or 10,000% by weight or 70 or 10,000% by weight
% by weight and the number of carbon atoms other than propylene is 2 to 20,
Preferably, the α-olefin component unit (b) is in the range of 2 to 18, in an amount of 0 to 40% by weight, preferably in the range of 0 to 30% by weight, and the structure thereof is substantially linear.

(11) Intrinsic viscosity [η] measured in decalin solvent is 0
．． Must be in the range of 03 to 0,8 (11#I).

(iii) Melting point measured by differential scanning calorimeter is 120
The temperature should be in the range of 130 to 165°C, preferably 130 to 165°C.

(1v) Softening point measured by constant force penetration method (TMA method) is 50 to 160°C, preferably 60 to 165°C
be within the range of

(v) crystallinity of 20 to 65 as measured by X-ray diffraction method;
%, preferably in the range of 60 to 65%.

(The content of terminal vinyl unsaturated bonds present in 1, A 100.9 is 0.005 mol or less, preferably 0.005 mol or less, preferably 0.
Must be within the range of 0.003 moles or less.

Propylene low molecular weight polymer -21- specified by
".

Therefore, even if a propylene low molecular weight polymer whose composition and physical properties are outside the above ranges is used, it will be difficult to obtain the above-mentioned modified propylene low molecular weight polymer of the present invention. As a result, the lubricant effect of the modified propylene low molecular weight polymer,
The printing properties of the molded article of the composition, the adhesion of Lamicoat, and the performance of the coating film made of the chlorinated product of the modified product become insufficient.

In addition, physical properties of the propylene low molecular weight polymer other than those described above include the following.

(vii) Isotafticity (stereoregularity) is usually in the range of 80 to 99%, preferably 85 to 99%.

Here, the composition value or physical property value of the above-mentioned (1) or vil of the low molecular weight propylene polymer was measured by the same method as for the modified low molecular weight propylene polymer described above.

Furthermore, the isotafticity (stereoregularity) of the propylene low molecular weight polymer is the triadtacticity determined by 13C-NMR using the signal of the carbon atom of the methyl group. However, the methyl group of polypropylene adjacent to ethylene was excluded.

The stereoregular and crystalline propylene low molecular weight polymer used as a raw material for producing the modified low molecular weight propylene polymer of the present invention can be manufactured by the following method.

In other words, the propylene low molecular weight polymer is produced by hydrogen/α-olefin (
In the coexistence of hydrogen such that the partial pressure ratio (partial pressure ratio) is 1 or more, an α-olefin mixture containing O to 40 weight φ of propylene and an α-olefin having a carbon number of 2 to 20 other than propylene is polymerized. can get. The highly active T1 catalyst used at that time is formed from a highly active titanium catalyst component containing magnesium, titanium, nitrogen, and an electron donor as essential components, an organoaluminum compound catalyst component, and an organosilicon compound catalyst component. It is a catalyst. The present applicant filed a patent application on May 11, 1980, under the title of "Polyolefin wax and method for producing the same" regarding the low molecular weight propylene polymer and its production method. In detail, it can be manufactured by the method proposed in the specification of the patent application.

The modified propylene low molecular weight polymer of the present invention can be produced by the following method. The graft copolymerization reaction occurs by reacting the low molecular weight propylene polymer and the unsaturated carboxylic acid derivative under heating. The graft copolymerization reaction can be carried out in the presence of a solvent in a solution state or in a molten state. It is particularly preferred to carry out the modification reaction in the presence of a radical initiator. The proportion of the radical initiator used is usually 0.00 parts by weight per 100 parts by weight of the low molecular weight propylene polymer.
It is necessary that it is within the range of 01, 0, and OO parts by weight,
More preferably, the amount is in the range of 0.1 to 200 parts by weight.

When carrying out the modification reaction in a solution state, the proportion of the solvent used is usually 100 to 100,000 parts by weight, preferably 60 parts by weight, based on 100 parts by weight of the low molecular weight propylene polymer.
It ranges from 0 to 10,000 parts by weight. The temperature during the modification reaction is usually in the range of 50 to 250°C, preferably 60 to 200°C, and the reaction time is usually in the range of 15 to 250°C.
It ranges from 60 minutes to 480 minutes, preferably from 60 minutes to 420 minutes. Solvents used in the modification reaction include hexane,
Heflin, octane, decane, dodecane, tetradecane, aliphatic hydrocarbons such as kerosene, cycloaliphatic hydrocarbons such as methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, cyclododecane, benzene, toluene, xylene, ethylbenzene, Aromatic hydrocarbons, such as cumene, ethyltoluene, trimethylbenzene, cymene, diisopropylbenzene.

Examples include chlorobenzene, bromobenzene, 0-dichlorobenzene, carbon tetrachloride, trichloroethane, 1-IJ chloroethylene, tetrachloroethane, and 10genated hydrocarbons such as tetrachloroethylene. Among these, alkyl aromatic hydrocarbons are particularly preferred.

When such a solvent is used, the solvent is often added to the reaction product, and the amount thereof is particularly large when an alkyl aromatic hydrocarbon is used. Furthermore, when carrying out the Kraft modification reaction in a molten state, the modification is carried out by melt-kneading a mixture consisting of the propylene low molecular weight polymer, the unsaturated carboxylic acid derivative, and the radical initiator using an extruder or the like. It is also possible to cause a reaction.

Typical radical initiators used in the graft modification reaction are organic peroxides, and
Specifically, there are alkyl peroxides, aryl peroxides, acyl peroxides, aroyl peroxides, ketone penoxides, peroxycarbonates, peroxycarboxylates, hydroperoxides, and the like. Examples of alkyl peroxides include diinopropyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di-tert-butylperoxyhexine-3, etc., as a+) -/l/h/L/oxide. are dicumyl peroxide, etc.; acyl peroxides include dilauroyl peroxide; aroyl peroxides include dibenzoyl peroxide; ketone peroxides include methyl ethyl ketone hydroperoxide and cyclohexanone peroxide; hydroperoxides include tert-butyl hydroperoxide and cumene hydroperoxide. etc. can be mentioned. Among these, di-tert-phthylperoxide, 2,5-dimethyl-2,5-tert-phthylberoxy-hexyne-6, dicumyl peroxide, dibenzoyl peroxide and the like are preferred.

The unsaturated carboxylic acid derivative graft copolymer-modified low molecular weight propylene polymer of the present invention provides an excellent lubricant effect during extrusion molding when blended with a propylene polymer, and also improves the adhesion of the composition to different types of substrates. The surface of a molded article obtained from the composition has excellent printing properties, and furthermore, the lamicoat formed from the composition has excellent adhesion properties to a substrate.

In order to use it as a lubricant during extrusion molding of a propylene polymer, the proportion of the modified low molecular weight propylene polymer is usually 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the propylene polymer. It ranges from 5 to 5 parts by weight.

The composition containing the modified propylene low molecular weight polymer is applied to a different substrate, such as metals such as steel, aluminum, copper, stainless steel, and lead, or nylon, saponified ethylene/vinyl acetate copolymers, epoxy resins, urethane resins, and melamine resins. In order to adhere to any polar plastic or paper, the proportion of the modified low molecular weight propylene polymer is in the range of 0.1 to 50 parts by weight per 100 parts by weight of the propylene polymer.

In addition, the modified propylene low molecular weight polymer is extremely useful as a binder when adding an inorganic filler or glass fiber to the propylene polymer, and in this case, the blending ratio of the modified propylene low molecular weight polymer is The amount ranges from 0.1 to 50 parts by weight per 100 parts by weight of the propylene polymer.

Furthermore, if the composition containing the modified propylene low molecular weight polymer is to be used as a laminate, the blending ratio of the modified propylene low molecular weight polymer is usually 1 to 50 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the propylene polymer. ranges from 2 to 40 parts by weight.

Furthermore, the halides of the modified low molecular weight propylene polymer of the present invention have significantly improved solubility in various organic solvents compared to unmodified propylene polymers,
The coating film obtained by using the chloride as a film-forming element is characterized by excellent coating properties such as adhesion, coating strength, and heat resistance.

When the halide is a chlorinated product, the chlorination ratio when preparing the chlorinated product of the modified product is such that the chlorine content of the chlorinated product after chlorination is usually 5 to 80% by weight,
Preferably, it is carried out to reach a range of 10 to 70% by weight.

-29-, C. The modified low molecular weight propylene polymer of the present invention has good solubility in some solvents, and therefore, solutions dissolved in such solvents can be used for various substrates, such as gold scraps, polyolefins, It can be used for coating materials such as glass, inorganic fillers, surface treatment agents for glass fibers, adhesives, paints, etc. Suitable solvents used for this purpose include halogenated hydrocarbons such as carbon tetrachloride, tricrene, chloroform, and chlorobenzene, and hydrocarbons such as cyclohexane and cyclohexene.

The modified low molecular weight propylene polymer of the present invention can still be formed into films, sheets, hollow bottles, tubes, and various molded products by extrusion molding, injection molding, blow molding, vacuum forming, etc. in the same way as ordinary propylene polymers or copolymers. and can be used.

In these various uses, stabilizers, antioxidants,
Ultraviolet absorbers, pigments, dyes, various fillers, etc. can be blended as appropriate.

The modified low molecular weight propylene polymer of the present invention can also be used as a modifier for other resins and rubbers by being blended with many resins and rubbers. For example, it can be used in a blend with polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene/propylene copolymer, ethylene/1-butene copolymer, or the like.

It is also possible to improve the solvent paintability, adhesion, printability, etc. of various molded products such as films, sheets, tubes, pipes, and hollow pins of the composition obtained by conventional molding methods. Generally, similar effects are observed when amorphous copolymer rubber is blended, but in this case, there are drawbacks such as a decrease in mechanical strength and hardness of the blended composition, but the modified propylene of the present invention Compositions blended with low molecular weight polymers do not have this drawback because they still have crystallinity.

Next, the modified propylene low molecular weight polymer of the present invention will be specifically explained with reference to Examples.

Example 1 Low molecular weight propylene polymer (intrinsic viscosity [η] 0.2
7dl1g, Mw/Mn, 2,3, melting point 151°C, softening point 160°C, crystallinity 56%, content of terminal vinyl unsaturated bonds 1.5 × 10-' mol/100. ! 7. Stereoregularity 94%) 500. ! 17 was charged into a 1.5 t glass reactor and melted at 170°C. Then, maleic anhydride 26.3f1 and tert=butyl peroxide (hereinafter abbreviated as DTBP○) 2.63. ! i
After adding and reacting by heating for 5 hours, the molten state of 1! Volatile components were removed by degassing in a 15 mm H7 vacuum for 1 hour, followed by cooling. The obtained maleic anhydride graft modified propylene low molecular weight polymer had a maleic anhydride graft amount of 2.69 [η
) [], 17cH/ji Mw/Mn2゜0, melting point 14
No terminal vinyl unsaturated bond was detected at 7°C, softening point 126°C, crystallinity 55%.

01- Examples 2 to 9 and Comparative Examples 1 to 5 Using the propylene low molecular weight polymer shown in Table 1, the type and amount of unsaturated carboxylic acid or its acid anhydride, and the type and amount of peroxide are changed. Other than that, various modified propylene low molecular weight polymers were prepared by carrying out the reaction in the same manner as in Example 1.

The results are shown in Table 1.

[Print suitability evaluation method]

Propylene homopolymer ([η) 2.0 d1/9)
Then, a water-based ink [manufactured by Toyo Ink Mfg. KK, trade name: Aqua King] was applied to an injection molded plate made from a composition prepared by blending 5 parts by weight of the graft copolymerized modified propylene low molecular weight polymer prepared by the above method. 1ml 1l
) was applied. Affinity of the ink on the molded plate when water-based ink is applied (as an evaluation criterion for whether or not ink repellency occurs, if repellency occurs)
The adhesion of the coating film after drying was examined by a substrate test. The results are shown in Table 1.

32- For comparison, when the modified low-molecular-weight propylene polymer was not added, the repelling phenomenon was significant and printing was impossible.

[Evaluation method of Lamicort properties]

Propylene polymer ([η): 1.25 cll/,!
i+) and 10% by weight of the graft-modified propylene low molecular weight polymer prepared by the above method was melted and applied to an At plate with a thickness of 100 μm using a bar coater.
Adhesion was measured using a substrate test.

In addition, the shape performance and blocking properties of the coated film were also investigated. The evaluation method is shown below. For comparison, when the modified propylene low molecular weight polymer was not blended, the adhesion was 5/100.

(11 Judgment Criteria for Film Formation Ability: A film of uniform thickness can be formed without cracking.

×...Cracks occur or a film of uniform thickness cannot be formed.

(2) Blocking property judgment criteria (judgment method)...The coated surfaces were placed together under a pressure of 1009/ctl and left at 40°C and 70°RH for 24 hours, and then the following judgment criteria were used: Blocking properties were evaluated.

5...I don't feel any resistance when peeling 4
・・・・・・・・・ Feeling some resistance 6
・・・・・・・・・Resistance is clearly felt 2・・・・・・・・・ Considerable force is required to peel 1 ・・・・・・・・・ When peeling, the coating The paint film peels off.

1 (continued) -59- 37- Applicant: Mitsui Petrochemical Industries, Ltd. Agent Kazu Yamaguchi 38-

Claims (2)

[Claims] (1) A modified low molecular weight propylene polymer in which an unsaturated carboxylic acid derivative component unit consisting of an unsaturated carboxylic acid, an acid anhydride thereof, or an ester thereof is graft-copolymerized onto a substantially linear low molecular weight propylene polymer, (A) The low molecular weight propylene polymer has α-
The olefin component unit (b) is in the range of 1 to 40% by weight [where the sum of (a) and (b) is 100]. ), and the intrinsic viscosity measured at 135°C in decalin solvent [
η] is in the range of 0.03 to 0.8 (11/, 9, (Gl weight average molecular weight/number average molecular weight is in the range of 1 to 8, ■) Differential scanning calorimeter (g) has a softening point measured by constant force penetration method (TMA method) in the range of 50 to 160°C, and (F) has a softening point measured by X-ray diffraction method. The measured crystallinity is in the range of 20 to 65 inches, and 0) The grafting ratio of the unsaturated carboxylic acid derivative component unit (C) is 0.01 to 20 parts by weight based on 100 parts by weight of the low molecular weight propylene polymer. The content of terminal vinyl unsaturated bonds in the modified low molecular weight polymer is within the range of 0.0 g per 100 g of the modified low molecular weight polymer.
．． 004 mol or less, σ) The content of the gel-like modified polymer in the modified low molecular weight polymer is 0.05 per ioo,y of the modified low molecular weight polymer.
, 9 or less. (2) Satisfies the requirements (A) to (g) below and 10
The content of terminal vinyl unsaturated bonds in 0.9 is 0.00
A substantially linear low molecular weight propylene polymer in the range of 5 mol or less, and an unsaturated carboxylic acid, its acid anhydride, or its acid anhydride in the range of 0.01 to 20 parts by weight per 100 parts by weight of the low molecular weight propylene polymer. A method for producing a modified propylene low weight polymer that satisfies the following requirements (A) to σ) by reacting an unsaturated carboxylic acid derivative consisting of an ester under heating. France) The low molecular weight propylene polymer contains 60 ft to 10,000 parts by weight of propylene component units (a) and 0 to 40 parts by weight of α-olefin component units other than propylene having a carbon atom number ranging from 2 to 20 (b). % range [
Here, the sum of (a) and (b) is 100. (B) The intrinsic viscosity [η] measured at 135°C in Delican solvent is in the range of 0.03 to 0.8 dl/9, expressed as 0 weight average molecular weight/number average molecular weight. The molecular weight distribution is in the range of 1 to 8; ■) The melting point measured by differential scanning calorimeter is in the range of 120 to 165°C; However, the softening point is measured by constant force penetration method (TMA method) is 5
(1) The degree of crystallinity measured by X-ray diffraction is in the range of 20 to 65°C; O) The grafting ratio of the unsaturated carboxylic acid derivative component unit (C) is in the range of 0 to 160°C; (2) The content of terminal vinyl-type unsaturated oro bonds in the modified low molecular weight polymer is in the range of 0.01 to 20 parts by weight based on 100 parts by weight of the low molecular weight propylene polymer; I DO,! σ) The content of the gel-like modified polymer in the modified low molecular weight polymer is 0.05 mol per 100 g of the modified low molecular weight polymer.
,! Must be in the range of 7 or less.