JP2002371112A - (METH)ACRYLOYL GROUP-MODIFIED ETHYLENE-alpha-OLEFIN COPOLYMER, METHOD FOR PRODUCING THE SAME, AND RUBBER COMPOSITION - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crosslinkable modified ethylene-α-olefin copolymer excellent in processability, mechanical strength and abrasion resistance and suitably usable as rubber for automotive parts, mechanical parts, electronic parts, civil engineering construction materials, fuel cell packings, by introducing a specific functional group onto the side chain, and to provide a rubber composition including the copolymer. SOLUTION: This (meth)acryloyl group-modified ethylene-α-olefin copolymer has the (meth)acryloyl group on the side chain of the ethylene-α-olefin copolymer and has an intrinsic viscosity [η] determined in 135 deg.C decalin of 0.01-10 dl/g, the alternative rubber composition is obtained by compounding the copolymer with a vulcanizing agent and/or crossliking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a modified ethylene / α-olefin copolymer obtained by modifying an ethylene / α-olefin copolymer with a (meth) acryloyl group. More specifically, the present invention relates to a modified ethylene / α-olefin copolymer having improved crosslinking efficiency by introducing a specific functional group ((meth) acryloyl group). Furthermore, the present invention relates to the modified ethylene α
-Contains an olefin-based copolymer, has excellent workability, mechanical strength and wear resistance, and is suitable for cross-linking, which is suitably used as a rubber material for automobile parts, mechanical parts, electronic parts, civil engineering construction materials, packing for fuel cells, etc. The present invention relates to a rubber composition containing a modified ethylene / α-olefin copolymer.

[0002]

2. Description of the Related Art Ethylene / α-olefin copolymers and ethylene / α-olefin / non-conjugated polyene copolymers (hereinafter abbreviated as “ethylene / α-olefin copolymers”) are known for their heat resistance, weather resistance and the like. Excellent in various fields. However, these conventional ethylene α-
Olefin-based copolymers have lower crosslinking speeds than diene-based rubbers such as natural rubber, styrene-butadiene rubber, isoprene rubber, butadiene rubber, and nitrile rubber.
It is difficult to produce a crosslinked rubber with high productivity. In order to increase the crosslinking rate of the ethylene / α-olefin-based copolymer, a large amount of the crosslinking agent may be used. However, if the crosslinking is attempted with a large amount of the crosslinking agent, the crosslinking agent blooms on the surface of the obtained crosslinked rubber. It may be unpleasant for hygiene. In addition, Japanese Patent Application Laid-Open Nos.
Japanese Patent No. 128427 discloses that the use of a non-conjugated polyene represented by 7-methyl-1,6-octadiene increases the crosslinking speed, but is not sufficient.

On the other hand, regarding the production of a modified olefin copolymer, a method of grafting maleic anhydride or the like with an extruder, a method of chemically modifying an unsaturated bond introduced into a side chain by copolymerization, a method of high temperature -A method of copolymerizing by radical polymerization under high pressure or a method of copolymerizing a functional group-containing monomer with an olefin by masking a specific functional group is known. With respect to olefin copolymers obtained by introducing an unsaturated group into a side chain by a chemical reaction using these modified olefin copolymers, ethylene, a monoolefin having 3 to 20 carbon atoms, ethylene organosilane and the like are copolymerized. A method is known in which after polymerization, an unsaturated alcohol such as allyl alcohol is substituted for a hydrolyzable group bonded to a silicon atom (Japanese Patent Publication No. 58-38).
443). Also, Japanese Patent Application Laid-Open No. 62-121715
In Japanese Patent Application Laid-Open No. H10-157, a modified olefin copolymer is known in which an addition reaction product obtained by grafting a carboxylic acid compound to an olefin copolymer is further reacted with a monovalent unsaturated amine and / or an unsaturated alcohol. However, there is no description of a (meth) acryloyl group. As for polyolefins having a (meth) acryloyl group, terminal-modified polyolefins are known (Japanese Patent No. 3164).
No. 632). However, this polymer is a polymer having a (meth) acryloyl group only at a terminal, and an olefin copolymer having a (meth) acryloyl group in a side chain at random is not known. Further, there is no mention of improving the crosslinking rate of a modified olefin copolymer having a (meth) acryloyl group.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and is directed to an automobile having excellent workability, mechanical strength and abrasion resistance by introducing a specific functional group into a side chain. It is an object of the present invention to provide a crosslinkable modified ethylene / α-olefin-based copolymer suitably used as a rubber material for components, mechanical components, electronic components, civil engineering materials, packing for fuel cells, and the like, and a rubber composition thereof. .

[0005]

SUMMARY OF THE INVENTION The present invention provides an ethylene / α
The olefin-based copolymer has a (meth) acryloyl group in a side chain thereof, and has an intrinsic viscosity [η] of 0.01 to 10 dl / g measured in decalin at 135 ° C. ( The present invention relates to a (meth) acryloyl group-modified ethylene / α-olefin copolymer. The (meth) acryloyl group-modified ethylene / α-olefin copolymer of the present invention preferably has 0.1 to 500 mmol of (meth) acryloyl group per 100 g of the copolymer. Acryloyl group-modified ethylene / α-olefin copolymers include silyl group, hydroxyl group, alkoxy group, amino group, carboxyl group, ester group, epoxy group, amide group, sulfone group, imide group, isocyanate group, vinyl group, vinylene Ethylene / α having at least one functional group selected from the group consisting of a group and an acid anhydride
-It is obtained by reacting a (meth) acryloyl group-containing compound with an olefin-based copolymer. Examples of the (meth) acryloyl group-containing compound include compounds represented by the following general formula (1).

[0006]

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[In the general formula (1), R ¹ is a hydrogen atom or a methyl group, A is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a single bond, and X ¹ is a silyl group. Group, hydroxyl group, amino group, carboxyl group, epoxy group, amide group, sulfone group, imide group, isocyanate group, mercapto group, or halogen atom, and q is 1
Represents an integer of 1 to 3. The modified ethylene / α-olefin copolymer is obtained by copolymerizing a compound represented by the following general formula (2), ethylene, an α-olefin having 3 to 10 carbon atoms and, if necessary, a non-conjugated polyene. Copolymer obtained by the above method.

[0008]

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[In the general formula (2), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y ² , Y ³ , Y ⁴
Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a functional group such as a silyl group, a hydroxyl group, an alkoxy group, an amino group, a carboxyl group, or an amide group, and Y ² , Y ³ , at least one of Y ⁴ is a functional group, also, Y ^2, Y ^3, when two or more of Y ⁴ is a functional group, they acid anhydride formed by connecting to each other [- O- (CO) -O-] or an imide group (-CO-
NH-CO-). o is an integer of 0 to 2, p
Represents an integer of 0 to 5. Y ² , Y ³ , Y ⁴ in the compound represented by the general formula (2)
At least one of them is —SiR ³ _m Z _3-m (provided that
R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, Z represents a chlorine atom, a bromine atom, or a halogen atom among iodine atoms;
m represents an integer of 0 to 2).
The modified ethylene / α-olefin copolymer includes a compound represented by the following general formula (3), ethylene, an α-olefin having 3 to 10 carbon atoms, and if necessary, a non-conjugated polyene. It may be a copolymer obtained by polymerization. CH ₂ ＣＨCH— (CH ₂ ) _n —Y ¹ (3) [In the general formula (3), Y ¹ is a functional group of a silyl group, a hydroxyl group, an alkoxy group, an amino group, a carboxyl group, or an amide group. And n represents an integer of 0 to 6. Here, Y in the compound represented by the above general formula (3)
_{^{1, -SiR 3 m Z 3-m}} ( provided that, R ³ represents a hydrogen atom or a hydrocarbon group which may having 1 to 20 carbon atoms include a hetero atom,, Z is a chlorine atom, a bromine atom, an iodine atom Among them, a functional group represented by any one of halogen atoms and m represents an integer of 0 to 2) is preferable. As the (meth) acryloyl group-modified ethylene / α-olefin copolymer of the present invention, (a-1) 0.01 to 30 mol% of the structural unit derived from the general formula (2); ) 5 to 90 mol% of structural units derived from ethylene, and (a-3) 5 to 6 structural units derived from α-olefin having 3 to 10 carbon atoms.
0 mol%, and 0 to 12 mol% of the structural unit derived from the (a-4) non-conjugated polyene compound, and the intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 d.
Those obtained by reacting a compound represented by the above general formula (1) with a 1 / g modified ethylene / α-olefin copolymer are preferred. Further, as the (meth) acryloyl group-modified ethylene / α-olefin copolymer of the present invention, (a-1) 0.01 to 30 mol% of a structural unit derived from the above general formula (3); -2) 5 to 90 mol% of a structural unit derived from ethylene, and (a-3) 3 to 3 carbon atoms.
5 to 60 mol% of the structural unit derived from the α-olefin of 10 and 0 to 12 mol% of the structural unit derived from the (a-4) non-conjugated polyene-based compound were measured in decalin at 135 ° C. Intrinsic viscosity [η] is 0.01 to 10 dl /
g of the modified ethylene / α-olefin-based copolymer,
Those obtained by reacting the compound represented by the general formula (1) are also preferable. Next, the present invention is characterized by comprising (A) the (meth) acryloyl group-modified ethylene / α-olefin-based copolymer and (B) a vulcanizing agent and / or a crosslinking agent. , (Meth) acryloyl group-modified ethylene / α-olefin copolymer-containing rubber composition (hereinafter also referred to as “rubber composition of the present invention”). Further, the rubber composition of the present invention may further contain (C) an olefin copolymer rubber other than the component (A).

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below. The ethylene / α-olefin-based copolymer having a (meth) acryloyl group in the side chain of the present invention (hereinafter, referred to as “the copolymer”)
In the production of “(A) olefin copolymer”), first, an ethylene / α-olefin copolymer in which a functional group is introduced into a normal ethylene / α-olefin copolymer is produced. The ethylene / α-olefin-based copolymer system into which a functional group has been introduced is produced by a known technique. For example, U.S. Pat. No. 3,236,917 describes a method based on a graft reaction between an ethylene / propylene copolymer and maleic anhydride. Also,
JP-A-64-9221 describes a method for grafting glycidyl methacrylate to an ethylene / propylene copolymer. JP-A-6-212938 discloses that a reactive unsaturated group of an olefin copolymer having a reactive unsaturated group obtained by copolymerizing an α-olefin and a non-conjugated diene includes a hydroxyl group, a carboxyl group, A method for introducing a functional group such as an epoxy group, a halogen group, a nitro group, an amino group, and a sulfone group is described. An olefin copolymer obtained by copolymerizing an olefin monomer having a functional group such as a carboxyl group or an amino group is also known (JP-B-49-43275, JP-A-HEI 4-43275).
No. 503963). The functional group of the functional group-containing ethylene / α-olefin copolymer thus obtained is reacted with the compound represented by the general formula (1) to convert the (meth) acryloyl group to an ethylene / α-olefin. It can be introduced into a system copolymer. This introduction method is not particularly limited, and may be performed in a solution state, a molten state, or a solid state, or a known catalyst may be added to promote the reaction.

As the olefin copolymer (A) of the present invention, a compound in which at least one of Y ² , Y ³ and Y ^{4 in} the above general formula (2) is a functional group, or the above general formula (3) )), An unsaturated silane compound in which the functional group Y ¹ is —SiR ³ _m Z _3-m , ethylene, α-olefin,
A method of introducing a (meth) acryloyl group into an ethylene / α-olefin copolymer by reacting a compound represented by the general formula (1) after copolymerizing a non-conjugated polyene as required, After copolymerization, a (meth) acryloyl group can be introduced without taking out the copolymer, which is preferable.

Specific examples of the compound represented by the general formula (1) include aminoethyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxybutyl acrylate, and acrylic acid. 4-hydroxyphenyl, glycidyl methacrylate, aminoethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 4-hydroxyphenyl methacrylate, 4-hydroxyphenylethyl methacrylate, pentaerythritol Examples include triacrylate, pentaerythritol trimethacrylate, acrylic acid, acrylamide, acrylic acid chloride, methacrylic acid, methacrylamide, methacrylic acid chloride, and the like. Among these, 2-hydroxyethyl methacrylate, hydroxybutyl methacrylate, 4-hydroxyphenyl methacrylate, and 4-hydroxyphenylethyl methacrylate are preferred from the viewpoint of the stability of the modified copolymer. These compounds can be used alone or in combination of two or more.

In the above general formula (2), Y ² , Y ³ , Y
At least one functional group of the ^4, -SiR _{³ m} Z _^3-m
Specific examples of the unsaturated silane represented by are 5-trichlorosilyl-2-norbornene, 5-methyldichlorosilyl-2-norbornene, 5-dimethylchlorosilyl-2-
Norbornene, 5- {2- (dimethylchlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene, 5-
{2- (methyldichlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene, 5- {2- (trichlorosilyl) ethyl} bicyclo [2.2.1] hept-
2-ene, 5- {2- (methylphenoxychlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene, 5- {2- (methylmethoxychlorosilyl) ethyl} bicyclo [2.2. 1] Hept-2-ene, 5-
{3- (dimethylchlorosilyl) propyl} bicyclo [2.2.1] hept-2-ene, 5- {4- (dimethylchlorosilyl) butyl} bicyclo [2.2.1] hept-2-ene and the like Is mentioned.

[0014] Specific examples of the unsaturated silane compound functional group Y ¹ in the general formula (3) is a -SiR ³ _m Z _3-m, vinyl trichlorosilane, vinyl methyl dichlorosilane, vinyl dimethylchlorosilane , Vinylethyldichlorosilane, vinyloctyldichlorosilane,
Examples thereof include allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allylhexyldichlorosilane, butenylmethyldichlorosilane, 5-hexenyldimethylchlorosilane, 5-hexenyldimethylchlorosilane, and 7-octenyldimethylchlorosilane. Of these, 5-hexenyldimethylchlorosilane, 7-octenyldimethylchlorosilane, 5-dimethylchlorosilyl-2-norbornene,
-{2- (dimethylchlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene and the like are particularly preferred.
These compounds can be used alone or in combination of two or more.

In the olefin copolymer (A) of the present invention, the content of the (meth) acryloyl group is 0.1 to 500 mmol per 100 g of the olefin copolymer (A).
It is preferably contained in the range of 0.5 to 200 mmol, more preferably 1 to 10 mmol.
0 mmol. If the amount is less than 0.1 mmol, the obtained copolymer may have a reduced effect on crosslinking. On the other hand, it is difficult to contain more than 500 mmol.

In the olefin copolymer (A) of the present invention, (a-1) the structural unit derived from the general formula (2) or the general formula (3) is in the range of 0.01 to 30 mol%. Is preferably contained, more preferably 0.05 to 10 mol%, particularly preferably 0.1 to 5 mol%. When the content ratio is less than 0.01 mol%,
The content of the (meth) acryloyl group in the obtained copolymer may decrease, and the effect on crosslinking may decrease. on the other hand,
If the content exceeds 30 mol%, copolymerization with a monomer other than the olefin-based monomer may be difficult, and the elasticity of the obtained copolymer may be insufficient.

In the olefin copolymer (A) of the present invention, the structural unit derived from ethylene (a-2) is preferably contained in the range of 5 to 90 mol% of all the structural units. , 10 to 85 mol%, more preferably, 15 to 80 mol%. If the content is less than 5 mol%, the mechanical strength and abrasion resistance of the obtained copolymer may decrease. On the other hand, if the content exceeds 90 mol%, the elasticity of the obtained copolymer may be insufficient.

In the olefin copolymer (A) of the present invention, the α-olefin having 3 to 10 carbon atoms includes propylene, 1-butene, 1-pentene, 4-methyl-pentene-1, 1-hexene , 1-heptene, 1-octene, 1-decene, styrene, p-methylstyrene and the like. Among them, propylene, 1-butene, 1-hexene, 1-octene are preferably used,
Further, propylene and 1-butene are most preferably used. These compounds can be used alone or in combination of two or more. Α- having 10 or less carbon atoms
When an olefin is used, the copolymerizability of the α-olefin with other monomers is improved.

(A-3) The structural unit derived from the α-olefin is preferably contained in the range of 5 to 60 mol%, more preferably 10 to 50 mol%, of all the structural units.
Mol%, particularly preferably 15 to 40 mol%. If the content ratio is less than 5 mol%, the elasticity of the obtained copolymer may be insufficient. On the other hand, if the content ratio exceeds 50 mol%, the mechanical strength and abrasion resistance of the obtained copolymer may decrease.

In the olefin copolymer (A) of the present invention, the non-conjugated polyene is contained in the copolymer as required. Specific examples of the non-conjugated polyene include 1,4-hexadiene, 1,6-hexadiene,
1,5-hexadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,
7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 7-methyl-1,6-octadiene, dihydromyrcene, 4-ethylidene-1,6
-Octadiene, 7-methyl-4-ethylidene-1,6
-Octadiene, 7-methyl-4-ethylidene-1,6
-Nonadiene, 6,7-dimethyl-4-ethylidene-
1,6-octadiene, 7-methyl-4-ethylidene,
-1,6-decadiene, tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, bicyclo- (2,2,1) -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2- Examples thereof include norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene. These compounds are 1
Species can be used alone or in combination of two or more. Preferred examples of the non-conjugated polyene include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.

In the olefin copolymer (A) of the present invention, the structural unit derived from (a-4) a non-conjugated polyene comprises:
It is preferably contained in a proportion of 0 to 12 mol% in all the structural units, more preferably 0 to 8 mol%, particularly preferably 0 to 5 mol%. When the content ratio of the non-conjugated polyene exceeds 12 mol%, the catalytic activity is remarkably reduced, which is not preferable in terms of cost.

The (A) (meth) acryloyl group-modified ethylene / α-olefin copolymer used in the present invention comprises:
The intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, preferably 0.05 to 7 dl / g, more preferably 0.1 to 10 dl / g.
５5 dl / g. This intrinsic viscosity [η] is 0.01d
If it is less than 1 / g, kneading when blending with another olefin-based copolymer rubber is difficult. On the other hand, when the intrinsic viscosity [η] exceeds 10 dl / g, the moldability of the copolymer decreases.

The (A) olefin-based copolymer having a (meth) acryloyl group of the present invention can be obtained by a gel permeation chromatography method using an o-dichlorobenzene solvent at 135 ° C. in terms of polystyrene equivalent weight average molecular weight M.
w is preferably from 1,000 to 3,000,000, more preferably from 3,000 to 1,000,000.
0, particularly preferably 5,000 to 700,000, and the number average molecular weight Mn in terms of polystyrene is 500 to 1,
00000, more preferably 1,000 to 500,000, particularly preferably 2,000.
00 to 300,000.

The (A) olefin copolymer having a (meth) acryloyl group of the present invention preferably has a glass transition temperature of -90 to 50 ° C, more preferably
−70 to 10 ° C. Thereby, a copolymer having sufficient elasticity can be obtained. Here, (A) the glass transition temperature of the olefin-based copolymer can be measured by a differential scanning calorimeter (DSC).

The structure of the olefin copolymer (A) having a (meth) acryloyl group in the side chain of the copolymer of the present invention is as follows:
The infrared absorption spectrum can be confirmed by an absorption derived from carbonyl around 1,725 cm ^{-1 and} an absorption derived from alkene around 1,640 cm ^-1 . Further, 6.1 ppm by nuclear magnetic resonance spectra ^{(1 H-NMR), 5} .
The structure can be confirmed from the peak of the alkene proton at 6 ppm.

The olefin copolymer (A) of the present invention comprises:
Although it is possible to use it alone, it is also possible to use a normal (C) olefin copolymer other than the component (A) [a normal ethylene / α-olefin (non-conjugated polyene) copolymer] (hereinafter referred to as “(C) Olefin-based copolymer "). When the olefin copolymer (A) of the present invention is used by blending with an ordinary olefin copolymer (C), the weight ratio of the component (A) to the component (C) is usually from 1/99 to 99/1, preferably 3/97 to 97/3, more preferably 5/95 to 95
/ 5.

The olefin copolymer (A) as described above can be produced as follows. That is, a compound represented by the general formula (2) or a compound represented by the general formula (3), ethylene, and a compound having 3 to 1 carbon atoms.
After copolymerizing an α-olefin of 0 and a non-conjugated polyene as required, a compound represented by the general formula (1) is added to stop the polymerization reaction, and the silyl group introduced into the copolymer is added. To introduce a (meth) acryloyl group. To promote the reaction, a base such as triethylamine, pyridine, N, N-dimethylaniline may be used. When the compound represented by the general formula (1) does not react with all functional groups such as silyl groups, methanol, ethanol, isopropyl alcohol, n-butanol and the like can be added. Thereafter, the unreacted monomer, the solvent, and the like are removed to obtain an ethylene / α-olefin copolymer having a (meth) acryloyl group in a side chain.

In this polymerization, a catalyst comprising a transition metal compound, preferably a compound of a metal selected from Groups 4 and 5 of the periodic table, and an organoaluminum compound is used. It is preferable to use a catalyst that gives a relatively random monomer arrangement in the copolymerization reaction of ethylene and α-olefin (and non-conjugated polyene). Specific examples of the catalyst system include the following. (1) A catalyst system comprising a vanadium compound soluble in a hydrocarbon compound and an organoaluminum compound, wherein the vanadium compound or the organoaluminum compound contains at least one chlorine atom. In this catalyst system, an oxygen- or nitrogen-containing electron donor such as an ester of an organic or inorganic acid, an ether, an amine, a ketone, or an alkoxysilane may be added to the vanadium compound and the organoaluminum compound. it can.

(2) A catalyst system comprising a titanium or zirconium halide supported on silica or magnesium chloride and an organic aluminum. Here, as the titanium halide, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, or the like can be used. As the organic aluminum compound, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylalumoxane, or the like can be used. In this catalyst system, dioctyl phthalate, tetraalkoxysilane, diphenyldimethoxysilane, and the like can be further added to the above compound.

(3) Titanium, zirconium, hafnium having one or two cyclopentadienyl, indenyl or fluorenyl groups having a substituent selected from hydrogen, an alkyl group and an allyl group as ligands A catalyst system comprising a transition metal compound of a metal selected from the group consisting of: and an organoaluminum compound containing at least 50 molar equivalents of methylalumoxane. (4) A metallocene catalyst comprising bisalkyl-substituted or N-alkyl-substituted saltyl aldimine, titanium, zirconium or hafnium dichloride, and methylalumoxane (MAO).

The polymerization reaction is preferably carried out in the presence of a suitable solvent or diluent. As such a solvent or diluent, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof can be used. Specifically, butane, pentane, hexane, heptane, 2-butene, 2-methyl-2
-Butene, cyclopentane, methylcyclopentane, cyclohexane, isooctane, benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane and the like. These solvents or diluents can remove 20p of water by distillation or adsorption.
pm or less.

The polymerization reaction is carried out at 0 to 150 ° C., particularly at 10 to 1
It is preferably performed at a temperature of 00 ° C. In the polymerization reaction, a molecular weight modifier can be used as necessary, and specific examples thereof include hydrogen, diethylzinc, diisobutylaluminum hydride and the like. Further, the reactor for performing the polymerization reaction may be any of a batch type and a continuous type. As the continuous reactor, a tube reactor, a tower reactor, a tank reactor, or the like can be used.

The reaction with the compound represented by the general formula (1) is preferably performed at a temperature of 0 to 150 ° C., particularly preferably 10 to 100 ° C. The compound represented by the general formula (1) is
It may be dissolved or diluted with a solvent or diluent before use.
As such a solvent or diluent, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof can be used. Specific examples include butane, pentane, hexane, heptane, 2-butene, 2-methyl-2-butene, cyclopentane, methylcyclopentane, cyclohexane, isooctane, benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane, and the like. be able to.

The copolymer solution containing the olefin copolymer (A) thus obtained is passed through an adsorption column filled with silica, alumina, diatomaceous earth or the like, or It is preferable that a large amount of water, alcohol, or the like is added to the resultant, followed by washing to remove residual polymerization catalyst and the like.

For the purpose of improving the stability of (A) the olefin-based copolymer, a known phenol-based, phosphorus-based, sulfur-based antioxidant can be added.

The olefin copolymer (A) of the present invention comprises:
Depending on its use, performance based on it, a known compounding agent,
For example, a vulcanizing agent, a vulcanizing aid, a rubber reinforcing agent, a pigment, a filler, a softener, an anti-scorch agent, an anti-aging agent, a processing aid, and the like can be added.

As the method for crosslinking the olefin copolymer (A) of the present invention, a known crosslinking method can be employed, and usually, crosslinking with sulfur or a sulfur-based compound, resin crosslinking, quinoid crosslinking, organic peroxides, etc. Crosslinking methods such as product crosslinking, electron beam irradiation crosslinking, ultraviolet irradiation crosslinking, and radiation crosslinking can be employed.

The (A) olefin copolymer of the present invention comprises:
It has a high crosslinking speed, is excellent in processability, mechanical strength and abrasion resistance, and is suitably used as a rubber material for automobile parts, mechanical parts, electronic parts, civil engineering materials, fuel cell packings and the like.

The vulcanizing agent of the above-mentioned component (B) used in the present invention is not particularly limited. For example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, and insoluble sulfur;
Inorganic vulcanizing agents such as sulfur chloride, selenium and tellurium; and sulfur-containing organic compounds such as morpholine disulfide, alkylphenol disulfides, thiuram disulfides and dithiocarbamates. These vulcanizing agents can be used alone or in combination of two or more. (B) The mixing ratio of the vulcanizing agent is 10% for the rubber component (component (A) or component (A) and component (C))
The amount is usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight with respect to 0 parts by weight.

A vulcanization accelerator can be used together with the vulcanizing agent. Examples of such a vulcanization accelerator include aldehyde ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine, di (o-tolyl) guanidine and o-tolylpiguanide; thiocarbanilide, di (o-tolyl) thiourea; N,
N′-diethylthiourea, tetramethylthiourea,
Thioureas such as trimethylthiourea and dilaurylthiourea; mercaptobenzothiazole, dibenzothiazole disulfide, 2- (4-morpholinothio)
Benzothiazole, 2- (2,4-dinitrophenyl)
Thiazoles such as -mercaptobenzothiazole, (N, N'-diethylthiocarbamoylthio) benzothiazole; Nt-butyl-2-benzothiazylsulfenamide, N, N'-dicyclohexyl-2- Benzothiazylsulfenamide, N, N'-diisopropyl-
Sulfenamides such as 2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram disulfide;
Thiurams such as tetraethylthiuram disulfide, tetra-n-butylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide; zinc dimethylthiocarbamate, zinc diethylthiocarbamate, zinc di-n-butylthiocarbamate And carbamates such as zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium dimethylthiocarbamate and iron dimethylthiocarbamate; and xanthates such as zinc butylthioxanthate. These vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerator is usually 0.1 to 20 parts by weight, preferably 0.2 to 100 parts by weight based on 100 parts by weight of the rubber component [component (A) or components (A) and (C)]. To 10 parts by weight.

In addition to the above vulcanizing agents and vulcanization accelerators, vulcanization accelerating auxiliaries can be added as required. Examples of such vulcanization accelerating aids include metal oxides such as magnesium oxide, zinc white, litharge, leadtan, and lead white; organic acids (salts) such as stearic acid, oleic acid, and zinc stearate. Of these,
Particularly preferred are zinc white and stearic acid. The vulcanization accelerators can be used alone or in combination of two or more. The amount of the vulcanization accelerating aid is usually 0.5 to 20 parts by weight based on 100 parts by weight of the rubber component [component (A) or components (A) and (C)].

Next, as the crosslinking agent in the component (B), for example, 1,1-di-tert-butylperoxy-3,
3,5-trimethylcyclohexane, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 1,3-bis (t Organic peroxides such as -butylperoxyisopropyl) benzene. These crosslinking agents can be used alone or
A mixture of more than one species can be used. The compounding amount of the crosslinking agent is usually 0.1 to 1 with respect to 100 parts by weight of the rubber component (component (A) or component (A) and component (C)).
It is 5 parts by weight, preferably 0.5 to 10 parts by weight.

A crosslinking aid may be used in combination with the crosslinking agent. As such a crosslinking aid, for example,
Sulfur or sulfur compounds such as sulfur and dipentamethylenethiuram tetrasulfide; ethylene di (meth) acrylate, polyethylene di (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, metaphenylene bismaleimide, toluylene bismaleimide, etc. Polyfunctional monomers; oxime compounds such as p-quinone oxime and p, p'-benzoylquinone oxime. These crosslinking assistants can be used alone or in combination of two or more.
The compounding amount of the crosslinking aid is usually 0.5 to 20 parts by weight based on 100 parts by weight of the rubber component [component (A) or components (A) and (C)].

Further, the rubber composition of the present invention may contain a filler or a softener. Examples of the filler include SRF, FEF, HAF, ISAF,
Examples include carbon black such as SAF, FT, and MT, and inorganic fillers such as white carbon, fine particle magnesium silicate, calcium carbonate, magnesium carbonate, clay, and talc. These fillers can be used alone or in combination of two or more. The amount of the filler is usually 10 to 20 parts by weight per 100 parts by weight of the rubber component [(A) component or (A) component and (C) component].
0 parts by weight, preferably 10 to 100 parts by weight.

Examples of the softener include aromatic oils, naphthenic oils, and the like which are commonly used for rubber.
Examples include process oils such as paraffin oil, vegetable oils such as coconut oil, and synthetic oils such as alkylbenzene oil. Of these, process oils are preferable, and paraffin oil is particularly preferable. The above softeners can be used alone or in combination of two or more. The amount of the softener is usually 10 to 13 parts by weight per 100 parts by weight of the rubber component [(A) component or (A) component and (C) component].
0 parts by weight, preferably 20 to 100 parts by weight.

The (meth) acryloyl group-modified ethylene / α-olefin copolymer of the present invention has excellent crosslinking efficiency because the (meth) acryloyl group is introduced into the side chain of the polymer. Further, the crosslinkable rubber composition containing the (meth) acryloyl group-modified ethylene / α-olefin copolymer is excellent in processability, mechanical strength and abrasion resistance, and is used for automobile parts, machine parts, electronic parts, It is suitably used as a rubber material for civil engineering building materials, packing for fuel cells, and the like.

[0047]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

Example 1 Toluene 1 was placed in a 2 L separable flask purged with nitrogen.
000 mL and add 5- ｛2- (dimethylchlorosilyl
L) Ethyl bicyclo [2.2.1] hept-2-ene
5 mmol and 2 ml of 5-ethylidene-2-norbornene
And ethylene (supply rate: 5 L / min) / propylene
(Supply amount: 5 L / min) / hydrogen (supply amount: 3.5 L
/ Min) While continuously supplying the mixed gas, the polymerization catalyst
As Al_Two(C_TwoH_Five)_ThreeCl_Three0.81 mol / L
6.2 ml of hexane solution [Al_Two(C _TwoH_Five)_ThreeCl_Three5m
mol] and then VCl_Four0.10mol of
/ L hexane solution 5mL (VCl_Four0.5 mmol)
Ethylene and propylene at 25 ° C for 10 minutes.
Len, 2- (5-norbornenyl) ethyldimethylchloro
Silane and 5-ethylidene-2-norbornene
A polymerization reaction was performed. Then, triethylamine 25mm
ol and 25 mmol of 2-hydroxyethyl methacrylate
And stirred for 30 minutes, then n-butanol 10 ml
Was added and stirred for 10 minutes. Next, water 5 was added to the copolymer solution.
After adding 00 ml and stirring for 10 minutes, the copolymer solution
(Organic layer) only, and the copolymer solution was
After washing twice with ml, pour into a large amount of methanol.
Precipitating polymer and drying by heating roll
As a result, 20 g of an olefin-based copolymer (A1) was obtained.
Was. The olefin copolymer (A1) has an infrared absorption
When analyzed by the yield spectrum method, 1,640 cm^-1Attached
Since a peak was observed nearby, the methacryloyl group
I confirmed the introduction. further,¹Analyze by H-NMR measurement
As a result, the content ratio of structural units derived from ethylene was
71.5 mol%, containing structural units derived from propylene
The ratio is 26.3 mol%, and the content of the methacryloyl group is
13.1 (mmol / 100 g polymer)
5-ethylidene-2-norbornene determined by elementary titration
The content of structural units derived from olefins was 1.8 mol%.
Was. Intrinsic viscosity measured in 135 ° C decalin
[Η] was 1.3. Olefii obtained in Example 1
The IR chart of the copolymer (A1) is shown in FIG.

Example 2 Except that 10 mmol of 5- {2- (dimethylchlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene, 30 mmol of triethylamine and 30 mmol of 2-hydroxyethyl methacrylate were used. The same operation as in Example 1 was performed to obtain an olefin-based copolymer (A2) 20
g was obtained. When this olefin-based copolymer (A2) was analyzed by infrared absorption spectroscopy, 1,640 c
The introduction of a methacryloyl group was confirmed from the fact that a peak was observed near m ^-1 . Further, when analyzed by ¹ H-NMR measurement, the content of structural units derived from ethylene was 70.0 mol%, the content of structural units derived from propylene was 27.5 mol%, and the content of methacryloyl groups was The amount is 24.1 (mmol / 100 g polymer),
The content of structural units derived from 5-ethylidene-2-norbornene determined by iodine titration was 1.7 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.4.

EXAMPLE 3 Hexane was used in place of toluene, the supply rate of hydrogen was 0.5 L / min, and 5-ethylidene-2-norbornene was not used.
The same operation as in Example 1 was performed except that 100 mmol of 2-hydroxyethyl methacrylate was used, to obtain 30 g of an olefin-based copolymer (A3). When this modified olefin-based copolymer (A3) was analyzed by an infrared absorption spectroscopy, a peak was observed at around 1,640 cm ^-1 , confirming the introduction of a methacryloyl group. Further, when analyzed by ¹ H-NMR measurement, the content of the structural unit derived from ethylene was 68.1 mol%, and the content of the structural unit derived from propylene was 31.
5 mol%, methacryloyl group content is 10.8 (m
mol / 100 g polymer). 135 ° C
The intrinsic viscosity [η] measured in decalin was 2.3.

Example 4 Hexane 2,2 was placed in a 3 L separable flask purged with nitrogen.
000 mL and 5-methyl-5-carboxy-bicyclo
[2.2.1] 0.5 mol / L of hept-2-ene
70 mL of a xane solution (5-methyl-5-carboxyl-
Bicyclo [2.2.1] -2-heptene 35 mmol)
Was put. Then, while stirring the system, Al (iso)
-Bu)_ThreeBy adding 42 mmol of
5-methyl-5-carboxy-bicyclo [2.2.
1] Maski of carboxyl group in hept-2-ene
Was performed. Then, 5-ethylidene-
2 ml of 2-norbornene was added, and ethylene (supply amount: 5
L / min) / propylene (supply amount: 5 L / min) /
Hydrogen (supply rate: 0.5 L / min) mixed gas continuously
While supplying, as a polymerization catalyst, Al_Two(C_TwoH_Five)_ThreeCl
_Three104 mL of a 0.81 mol / L hexane solution of [Al_Two
(C _TwoH_Five)_ThreeCl_Three84 mmol] and then V
Cl_Four24 mL of a 0.10 mol / L hexane solution (V
Cl_Four2.4 mmol) was added and the reaction was carried out at 5 ° C. for 10 minutes.
, Ethylene, propylene, 5-methyl-5-carbo
Xy-bicyclo [2.2.1] hept-2-ene and
A copolymerization reaction of 5-ethylidene-2-norbornene was performed.
Was. 630 mmol of lactic acid was added to the obtained copolymer solution.
Add the butanol solution and stir for 10 minutes.
, A demasking treatment was performed. Then, copolymerization
After adding 1 L of water to the body solution and stirring for 10 minutes,
Collect only the coalescing solution (organic layer) and transfer the copolymer solution.
The remaining lactic acid is obtained by washing three times with 1 L of water.
And other removal processes. Then, the copolymer solution is steamed.
The solvent was removed by blowing air. So
After that, the solid content is separated from the obtained slurry and added.
Drying with a hot roll gives a solid
30 g of a olefin copolymer (X4) was obtained. This oref
Dissolve 5 g of vinyl copolymer (X4) in 25 ml of toluene
And 2 g of glycidyl methacrylate and triphenylphosphine
Then, the mixture was heated under reflux for 5 hours. This anti
After filtering the reaction solution through an 80 mesh wire mesh, 500 ml
Pour the polymer into methanol and heat the roll.
Methacryloyl base by drying
4.6 g of a decorated olefin copolymer (A4) was obtained. this
Infrared absorption spectrum of olefin copolymer (A4)
When analyzed by the Tor method, 1,640 cm^-1Nearby
Methacryloyl group was confirmed
I accepted. further,¹H-NMR analysis
Of course, the content of the structural unit derived from ethylene was 72.7.
Mol%, the content of structural units derived from propylene is 2
5.3 mol%, methacryloyl group content is 17.6
(Mmol / 100g polymer), iodine value titration
Derived from 5-ethylidene-2-norbornene
The content ratio of the structural unit was 1.4 mol%. Ma
The intrinsic viscosity [η] measured in decalin at 135 ° C. is
1.2.

Example 5 Polymerization was carried out in the same manner as in Example 4 except that 5-ethylidene-2-norbornene was not used, to obtain 33 g of an olefin-based copolymer (X5). Using 5 g of this olefin copolymer (X5), a methacryloyl group introduction reaction was carried out in the same manner as in Example 1 to obtain an olefin copolymer (A5).
4.5 g were obtained. When this olefin-based copolymer (A5) was analyzed by infrared absorption spectroscopy, 1,6
Since a peak was observed at around 40 cm ^−1, the introduction of a methacryloyl group was confirmed. Further, ¹ H-NMR
When analyzed by a measuring method, the content of the structural unit derived from ethylene was 69.7 mol%, the content of the structural unit derived from propylene was 29.7 mol%, and the content of the methacryloyl group was 17.3 ( mmol / 100g polymer)
Met. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.4.

Example 6 5 g of the olefin copolymer (X5) obtained in Example 5
Was dissolved in 30 ml of toluene, 2 g of 2-hydroxyethyl methacrylate and 0.4 g of boron trifluoride diethyl ether complex were added, and the mixture was heated under reflux for 15 hours. The reaction solution was filtered through an 80 mesh wire mesh, poured into 500 ml of methanol to precipitate a polymer, and dried by a heating roll to obtain 4.6 g of an olefin-based copolymer (A6). The olefin copolymer (A6) was analyzed by infrared absorption spectrum method for confirmed the introduction of methacryloyl group since the peak near 1,640Cm ^-1 were observed. In addition, ¹ H
As a result of analysis by an NMR measurement method, the content of the structural unit derived from ethylene was 69.5 mol%, the content of the structural unit derived from propylene was 29.9 mol%, and the content of the methacryloyl group was 17. 3 (mmol / 100 g polymer). The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.4.

Comparative Example 1 5- {2- (dimethylchlorosilyl) ethyl} bicyclo [2.2.1] hept-2-ene, triethylamine,
Except not using 2-hydroxyethyl methacrylate, the same operation as in Example 1 was performed to obtain 20 g of an olefin-based copolymer (B1). When this olefin-based copolymer (B1) was analyzed by infrared absorption spectroscopy, no peak was observed near 1,640 cm ^-1 . Further, when analyzed by ¹ H-NMR measurement, the content of the structural unit derived from ethylene was 71.5 mol%, and the content of the structural unit derived from propylene was 27.
The content of structural units derived from 5-ethyl-2-norbornene determined by iodine titration was 1.3 mol%. The intrinsic viscosity [η] measured in decalin at 135 ° C. was 1.2.

[Preparation of Rubber Composition] Example 7 70 g of the modified copolymer (A4) obtained in Example 4, 3.5 g of zinc oxide and 0.7 g of stearic acid were kept at 50 ° C. for 6 inches. For 5 minutes. 1.4 g of organic peroxide [1,3-bis (t-butylperoxyisopropyl) benzene] was added to the obtained kneaded material, and the mixture was kneaded for 5 minutes by a 6-inch roll machine maintained at 50 ° C. By doing so, a rubber compound was obtained.

Example 8 A rubber compound was obtained in the same manner as in Example 7, except that the modified copolymer (A5) obtained in Example 5 was used instead of the modified copolymer (A4). Was.

Example 9 A rubber compound was obtained in the same manner as in Example 7, except that the modified copolymer (A1) obtained in Example 1 was used instead of the modified copolymer (A4). Was.

Example 10 A rubber compound was obtained in the same manner as in Example 7, except that the modified copolymer (A2) obtained in Example 2 was used instead of the modified copolymer (A4). Was.

Comparative Example 2 Instead of the modified copolymer (A4), the copolymer (B1) obtained in Comparative Example 1 was used, and an organic peroxide [1,3-bis (t-butylperoxy) was used. [Isopropyl) benzene] and a rubber compound were obtained in the same manner as in Example 7, except that 0.7 g of trimethylolpropane trimethacrylate was added simultaneously with 1.4 g of [isopropyl] benzene].

Comparative Example 3 A rubber compound was obtained by performing the same operation as in Comparative Example 2 except that 2.8 g of the organic peroxide [1,3-bis (t-butylperoxyisopropyl) benzene] was used. Was.

[Evaluation of Rubber Composition] For each of the rubber compounds obtained in Examples 7 to 10 and Comparative Example 2, 160
Press pressure 150kgf by hot press heated to ℃
/ Cm ² for 30 minutes to obtain a crosslinked sheet. Further, regarding the rubber compound obtained in Comparative Example 3, 1
Press pressure 150k by hot press heated to 60 ° C
Heating was performed for 90 minutes under a pressure of gf / cm ² to obtain a crosslinked sheet. The following evaluation was performed using this crosslinked sheet as a test piece. Table 1 shows the results.

(1) Curast characteristics: Using a Curastometer V type manufactured by JSR Corporation, a difference between a maximum torque value and a minimum torque value of 90 based on a crosslinking curve at 160 ° C. for 40 minutes.
% (T ₉₀ ) and 10% (t ₁₀ ), and the difference t′c (d80) t′c
(D80) = was evaluated by the t ₉₀ -t _10. The smaller the value,
This shows that the crosslinking rate is high. Further, the maximum torque value MH was obtained. (2) Mesh chain concentration: 1 g of the test piece was immersed in 50 ml of toluene at room temperature for 72 hours, and determined from the degree of swelling of the test piece. The measurement of the mesh chain concentration is performed by the following Flory-Rainer (Fluor)
y-Rehner). νe = −1 / V ｛[ln (1-νr) + νr + μ · νr
² ] / [νr ^1/3 -2 · νr / f]｝ νe: network chain concentration V: solvent molecular volume (molecular weight / density) (for toluene;
92.14 / 0.868 = 105) νr: volume fraction of rubber in the swelling sample where νr = (volume of pure rubber contained in the weight of vulcanized rubber before swelling) / (in the weight of vulcanized rubber before swelling) Volume of pure rubber contained + volume of solvent absorbed by swollen rubber) μ: interaction constant of solvent (for toluene; 0.4
9) f: Number of functional groups (f = 4) (3) Tensile test: Tensile strength T _B (MPa), elongation at break E _B (%) and 10 in accordance with JIS K6301
The 0% modulus was measured. (4) Hardness test: Hardness was measured according to JIS K6301 (durometer). (5) Compression set: 1 according to JIS K6301
It was measured under the conditions of 50 ° C. × 70 hours.

[0063]

[Table 1]

[0064]

According to the present invention, it is possible to provide a modified ethylene / α-olefin copolymer having improved crosslinking efficiency by introducing a specific functional group ((meth) acryloyl group). In addition, the present invention includes the modified ethylene / α-olefin-based copolymer, and has excellent workability, mechanical strength, and abrasion resistance, and is used for automobile parts, mechanical parts, electronic parts, civil engineering materials, fuel cell packing, and the like. It is possible to provide a rubber composition containing a crosslinkable (meth) acryloyl group-modified ethylene / α-olefin-based copolymer suitably used as a rubber material.

[Brief description of the drawings]

FIG. 1 shows an olefin copolymer (A) obtained in Example 1.
It is an IR chart of 1).

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Motoharu Higuchi 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Minoru Tanaka 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR In-house F term (reference) 4J002 BB201 DA046 EK036 EV076 EV086 EV136 EV166 FD146 4J100 AA01Q AA02P AA03Q AA04Q AR09R AR11R BA71R CA04 CA05 CA31 DA09 DA31 HA62 HC29

Claims (15)

[Claims] 1. An ethylene / α-olefin copolymer having a (meth) acryloyl group in a side chain and an intrinsic viscosity [η] of 0.01 to 1 measured in decalin at 135 ° C.
A (meth) acryloyl group-modified ethylene / α-olefin-based copolymer, which is 0 dl / g. 2. 0.1 to 500 per 100 g of the copolymer
The (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 1, which has mmol of (meth) acryloyl group. 3. A group selected from the group consisting of silyl, hydroxyl, alkoxy, amino, carboxyl, ester, epoxy, amide, sulfone, imide, isocyanate, vinyl, vinylene and acid anhydride. The (meth) according to claim 1 or 2, which is obtained by reacting a (meth) acryloyl group-containing compound with a modified ethylene / α-olefin-based copolymer having at least one kind of functional group.
An acryloyl group-modified ethylene / α-olefin copolymer. 4. The (meth) acryloyl group-modified ethylene / α-olefin-based compound according to claim 1, wherein the (meth) acryloyl group-containing compound is a compound represented by the following general formula (1). Copolymer. Embedded image [In the general formula (1), R ¹ is a hydrogen atom or a methyl group, A is a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, or a single bond, and X ¹ is a silyl group, a hydroxyl group. , An amino group, a carboxyl group, an epoxy group, an amide group, a sulfone group, an imide group, an isocyanate group, a mercapto group, or a halogen atom, and q represents an integer of 1 to 3. ] 5. A modified ethylene / α-olefin copolymer is obtained by copolymerizing a compound represented by the following general formula (2), ethylene, an α-olefin having 3 to 10 carbon atoms and, if necessary, a non-conjugated polyene. The (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 3 or 4, which is a copolymer obtained by the above method. Embedded image [In the general formula (2), R ⁴ represents a hydrogen atom or a carbon atom
And Y ² , Y ³ , and Y ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a silyl group, a hydroxyl group, an alkoxy group, an amino group, or a carboxyl group. Or a functional group of an amide group, and Y ² ,
At least one of Y ³ and Y ⁴ is a functional group,
When two or more of Y ² , Y ³ and Y ⁴ are functional groups,
They are linked to each other to form an acid anhydride [—O—
(CO) -O-] or an imide group (-CO-NH-CO
−). o represents an integer of 0 to 2, and p represents an integer of 0 to 5. ] 6. A compound represented by the general formula (2), wherein at least one of Y ² , Y ³ and Y ⁴ is —SiR ³ _m Z _3-m
(However, R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may contain a hetero atom, Z represents a halogen atom among chlorine, bromine and iodine, and m represents The (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 5, which is a functional group represented by the following formula: 7. A modified ethylene / α-olefin-based copolymer comprising a compound represented by the following general formula (3), ethylene, an α-olefin having 3 to 10 carbon atoms and, if necessary, a non-conjugated polyene. The (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 3 or 4, which is a copolymer obtained by polymerization. CH ₂ ＣＨCH— (CH ₂ ) _n —Y ¹ (3) [In the general formula (3), Y ¹ is a functional group of a silyl group, a hydroxyl group, an alkoxy group, an amino group, a carboxyl group, or an amide group. And n represents an integer of 0 to 6. ] 8. Y ¹ of the general formula compound represented by (3)
Any There -SiR ³ _m Z _^3-m (provided that, R ³ represents a hydrogen atom or a hydrocarbon group which may having 1 to 20 carbon atoms include a hetero atom,, Z is a chlorine atom, a bromine atom, among the iodine atoms The (meth) acryloyl group-modified ethylene / α-olefin-based copolymer according to claim 7, wherein the halogen atom is represented by the following formula, and m is an integer of 0 to 2). 9. (a-1) 0.01 to 30 mol% of a structural unit derived from the general formula (2), (a-2) 5 to 90 mol% of a structural unit derived from ethylene, -3) 5 structural units derived from an α-olefin having 3 to 10 carbon atoms
有 し 60 mol% and (a-4) 0 to 12 mol% of structural units derived from a non-conjugated polyene-based compound,
Of intrinsic viscosity [η] measured in decalin of 0.01 to 1
The (meth) acryloyl group according to any one of claims 1 to 6, which is obtained by reacting a compound represented by the general formula (1) with a modified ethylene / α-olefin-based copolymer having a weight ratio of 0 dl / g. Modified ethylene / α-olefin copolymer. 10. (a-1) 0.01 to 30 mol% of a structural unit derived from the general formula (3), (a-2) 5 to 90 mol% of a structural unit derived from ethylene, -3) having 5 to 60 mol% of structural units derived from an α-olefin having 3 to 10 carbon atoms, and (a-4) having 0 to 12 mol% of structural units derived from a non-conjugated polyene-based compound; 135
Intrinsic viscosity [η] measured in decalin at a temperature of 0.01 to
The (meth) acryloyl group-modified ethylene / α according to claim 7 or 8, which is obtained by reacting a compound represented by the general formula (1) with a modified ethylene / α-olefin copolymer having a weight of 10 dl / g. -An olefin-based copolymer. 11. A group selected from the group consisting of silyl group, hydroxyl group, alkoxy group, amino group, carboxyl group, ester group, epoxy group, amide group, sulfone group, imide group, isocyanate group, vinyl group, vinylene group and acid anhydride. (Meth) acryloyl group-modified ethylene / α-olefin copolymer characterized by reacting a (meth) acryloyl group-containing compound with the modified ethylene / α-olefin copolymer having at least one kind of functional group. Manufacturing method of coalescence. 12. The method for producing a (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 11, wherein the (meth) acryloyl group-containing compound is a compound represented by the following general formula (1). Embedded image [In the general formula (1), R ¹ is a hydrogen atom or a methyl group, A is a hydrocarbon group which may having 1 to 20 carbon atoms include a hetero atom or a single bond,, X ¹ is a silyl group, a hydroxyl group , An amino group, a carboxyl group, an epoxy group, an amide group, a sulfone group, an imide group, an isocyanate group, a mercapto group, or a halogen atom, and q represents an integer of 1 to 3. ] 13. A modified ethylene / α-olefin copolymer comprising a compound represented by the following general formula (2), ethylene,
The (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 11 or 12, which is a copolymer obtained by copolymerizing an α-olefin having 3 to 10 carbon atoms and, if necessary, a non-conjugated polyene. A method for producing a polymer. Embedded image [In the general formula (2), R ⁴ represents a hydrogen atom or a carbon atom
And Y ² , Y ³ , and Y ⁴ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a silyl group, a hydroxyl group, an alkoxy group, an amino group, or a carboxyl group. Or a functional group of an amide group, and Y ² ,
At least one of Y ³ and Y ⁴ is a functional group,
When two or more of Y ² , Y ³ and Y ⁴ are functional groups,
They are linked to each other to form an acid anhydride [—O—
(CO) -O-] or an imide group (-CO-NH-CO
−). o represents an integer of 0 to 2, and p represents an integer of 0 to 5. ] 14. A composition comprising (A) the (meth) acryloyl group-modified ethylene / α-olefin-based copolymer according to any one of claims 1 to 10, and (B) a vulcanizing agent and / or a crosslinking agent. A rubber composition containing a (meth) acryloyl group-modified ethylene / α-olefin-based copolymer, characterized in that: 15. The rubber composition containing a (meth) acryloyl group-modified ethylene / α-olefin copolymer according to claim 14, further comprising (C) an olefin copolymer rubber other than the component (A). object.