JP2703795B2 - Modified ethylene / α-olefin copolymer and method for producing the same - Google Patents

Description

Description: TECHNICAL FIELD OF THE INVENTION The present invention relates to a modified ethylene / α-olefin copolymer, and more specifically, to the impact resistance of a polymer copolymerized with a polycyclic (meth) acrylate as a graft component. The present invention relates to a modified ethylene / α-olefin copolymer useful as a property improver and a method for producing the same.

(Prior art)

The cyclic olefin random copolymer is excellent in heat resistance, solvent resistance, chemical resistance, heat aging resistance, dielectric properties, and rigidity, and has already been disclosed in JP-A-61-98780 and JP-A-61-115.
No. 912, JP-A-61-115916, JP-A-61-12081
No. 6, JP-A-60-168708, and the like, it is desired to improve impact resistance.

[Object of the invention]

An object of the present invention is to provide a modified ethylene / α-olefin copolymer as an impact resistance improver capable of significantly improving the impact resistance of the cyclic olefin copolymer.

Another object of the present invention is to provide a modified ethylene / α-olefin copolymer which improves the impact resistance of the resin to be compounded and hardly lowers its flexural modulus.

It is a further object of the present invention to provide a method for graft polymerization of the modified ethylene / α-olefin copolymer.

[Summary of the Invention]

The modified ethylene / α-olefin copolymer according to the present invention has a general formula [I] or 40 to 98 parts by weight of an ethylene / α-olefin copolymer (a) having an ethylene content of 50 to 95 mol%. (II) Wherein, N and M are both integers of 0, 1, 2 or 3, L is the 3 or 4, R ₀ ^1, one of R ₀ ² is an (meth) acryloyl oxyl group And the other is a hydrogen atom, and X ¹ and X ² are each a direct bond, or a lower alkylene group selected from a methylene group, an ethylene group, a propylene group and a butylene group, or an X ¹ and X ² group selected from an oxyethylene group and an oxypropylene group. An oxygen lower alkylene group, R ^{1 to} R ⁸ are a hydrogen atom, or a lower alkyl group selected from a methyl group, an ethyl group, a propyl group, and a butyl group, or a halogen group; R ⁹ and R ¹⁰ are a hydrogen atom; Or methyl group, ethyl group, propyl group, lower alkyl group selected from butyl group, or ethylidene group, propylidene group,
Or a halogen group]. (B) 2
To 60 parts by weight by graft polymerization (where (a) +
(B) is selected to be 100 parts by weight. ).

According to the present invention, there is also provided a method for producing the modified ethylene / α-olefin copolymer.

[Action]

The present invention relates to an ethylene / α-olefin copolymer (a)
Is graft polymerized with a polycyclic (meth) acrylate monomer (b), and the resulting modified ethylene / α-olefin copolymer is blended with a cyclic olefin copolymer as a resin to be compounded. Is based on the finding that the impact resistance of the resin is remarkably improved, and the bending elastic modulus of the resin is hardly reduced.

In order to improve the impact resistance of the cyclic olefin copolymer, ethylene / α-olefin copolymers under various component conditions can be blended to improve the impact resistance. Therefore, the present invention is a modified product obtained by graft-polymerizing the ethylene / α-olefin copolymer (a) with a polycyclic (meth) acrylate monomer (b).
When this modified product is used as an impact resistance improver, it has a sufficient compatibility with the resin to be compounded and a dispersing action. Also, the effect of further improving impact resistance is exhibited.
In addition, since the modified product has good compatibility with the resin to be compounded, a decrease in the flexural modulus of the resin to be compounded is small and a decrease in heat resistance is small.

In the case of graft polymerization in the production of such a modified ethylene / α-olefin copolymer, an emulsion polymerization method, a melting method, and a solution method are appropriately selected and used, and a polycyclic (meth) acrylate monomer is used. The graft ratio of (b) can be appropriately adjusted.

(Preferred embodiment of the invention)

Hereinafter, preferred embodiments according to the present invention will be described in detail.

The modified ethylene / α-olefin copolymer of the present invention is
The poly (meth) acrylate monomer (b) is graft-polymerized to the ethylene / α-olefin copolymer (a). Examples of the graft polymerization method include emulsion polymerization in which the ethylene / α-olefin copolymer (a) is dispersed in water, solution polymerization in which the ethylene / α-olefin copolymer (a) is dissolved in an organic solvent, and melt polymerization in which the mixture is heated and kneaded.

Such a modified ethylene / α-olefin copolymer of the present invention is blended with another polymer, for example, a cyclic olefin-based copolymer described below, and is used to enhance the physical properties of the polymer, especially impact resistance. You. That is, the modified ethylene / α-olefin copolymer of the present invention can be used as an excellent impact resistance imparting agent.

 Hereinafter, each component will be described in detail.

Ethylene / α-olefin copolymer (a) In the ethylene / α-olefin copolymer of the present invention, the ethylene content is in the range of 50 to 95 mol%, particularly in the range of 60 to 85 mol%. preferable.

The α-olefin is a linear or branched one such as propylene, 1-butene,
-Methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1
Α-olefins having 3 to 20 carbon atoms, such as -hexadecene, 1-octadecene and 1-eicosene. Of these, α-olefins having 3 to 15, especially 3 to 10 carbon atoms are preferred.

The ethylene / α-olefin copolymer preferably has a melt flow rate at 230 ° C. [MFR, a value measured under a load of 2160 g (method according to ASTM D 1238E)] in the range of 0.1 to 50 g / 10 min. More preferably, it is in the range of 0.5 to 10 g / 10 minutes. When an ethylene / α-olefin copolymer having such an MFR is used as a raw material, a modified product thereof, that is, the modified ethylene / α-olefin of the present invention is used.
The olefin copolymer has a sufficient dispersing effect on the resin to be blended, for example, ethylene / cyclic olefin copolymer, etc., and exhibits an effect as an impact modifier of the resin to be blended.

The density of the ethylene / α-olefin copolymer is 0.90 g /
It is preferably in the cm ³ or less in the range, more preferably 0.8
It is in the range of 6 to 0.89 g / cm ³ . Further, the ethylene / α-olefin copolymer is low in crystallinity or amorphous, and its crystallinity is usually in the range of 0 to 50%, preferably in the range of 0 to 30%.

The ethylene / α-olefin copolymer usually contains mainly an ethylene component and an α-olefin component, but may contain a diene component in a range of 3.0 mol% or less depending on the case. As the diene component, 1,4-hexadiene,
1,6-octadiene, 2-methyl-1,5-hexadiene,
Linear non-conjugated dienes such as 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene, 5-ethylidene-2-
Norbornene, 5-methylene-2-norbornene, 5-
Cyclic non-conjugated dienes such as isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, and also 2-ethylidene-3-isopropylidene -5-norbornene, 2-propenyl-2,2-norbornadiene and the like.

Such an ethylene / α-olefin copolymer (a)
Graft polymerization of the polycyclic (meth) acrylate monomer (b) by the modification method described below.
A crosslinking aid such as a peroxide and, if necessary, a polyfunctional vinyl monomer exemplified by divinylbenzene may be added thereto, followed by heat treatment to crosslink the copolymer (a) to have a higher molecular weight and then use the resulting copolymer for modification.

Polycyclic (meth) acrylate monomer (b) The polycyclic (meth) acrylate monomer (b) constituting the poly (meth) acrylate polymer of the present invention has the general formula [I] or [II] ] Wherein, N and M are both integers of 0, 1, 2 or 3, L is the 3 or 4, R ₀ ^1, one of R ₀ ² is an (meth) acryloyl oxyl group And the other is a hydrogen atom, and X ¹ and X ² are each a direct bond, or a lower alkylene group selected from a methylene group, an ethylene group, a propylene group and a butylene group, or an X ¹ and X ² group selected from an oxyethylene group and an oxypropylene group. An oxygen lower alkylene group, R ^{1 to} R ⁸ are a hydrogen atom, or a lower alkyl group selected from a methyl group, an ethyl group, a propyl group, and a butyl group, or a halogen group; R ⁹ and R ¹⁰ are a hydrogen atom; Or methyl group, ethyl group, propyl group, lower alkyl group selected from butyl group, or ethylidene group, propylidene group,
Or a halogen group] is a polycyclic (meth) acrylate monomer (b) represented by the following formula:

In the general formulas (I) and (II), for example, R ^{1 to} R
^{The ten} groups may be different, partly different, or all the same. In particular, R ⁹ and R ^{10 in} the formula [II] can be combined to form an alkylidene group such as an ethylidene group or a propylidene group.

Said polycyclic (meth) acrylate monomer (b) is, for example, of the corresponding general formula [III] or [IV] Wherein all of N, M, L, R ¹ to R ¹⁰ are the same as described above, and reacting formic acid with the polycyclic olefin represented by the formula By reacting an alkylene oxide such as propylene oxide, the following general formula [V] or [VI] Wherein either one of X ₀ ¹ and X ₀ ² is hydroxyl and the other is hydrogen atom, N, M, L, X 1, X 2, R 1, to R
¹⁰ are the same as described above), and further obtains a polycyclic alcohol represented by the formula:
It can be adjusted by reacting (meth) acrylic acids such as methacrylic acid or (meth) acrylic halides such as acrylic halide and methacrylic halide.

Among the polycyclic (meth) acrylate monomers (b), as the monomer represented by the general formula [I], specifically, the compounds described in Table 1 can be exemplified. Examples of the monomer represented by the formula [II] include the compounds described in Table 2.

Graft Polymer and Graft Polymerization Method The polycyclic (meth) acrylate monomer (b) is graft-polymerized to the ethylene / α-olefin copolymer (a), and the graft ratio thereof is set to the ethylene / α-olefin copolymer ( a) is in the range of 2 to 60 parts by weight of the polycyclic (meth) acrylate monomer (b) with respect to 40 to 98 polymer parts,
The total of the components (a) and (b) is 100 parts by weight.
Further, the amount of the polycyclic (meth) acrylate monomer (b) is preferably in the range of 5 to 30 parts by weight.

The modified ethylene / α-olefin copolymer of the present invention based on the above range has excellent compatibility with the resin to be compounded, for example, the ethylene / cyclic olefin copolymer, and has a large effect of improving impact resistance. Further, the melt flow rate of the modified ethylene / α-olefin copolymer [MFR, ASTM D1238 condition L
20 g / 10 min or less, preferably 10 g / 10 min.
Minute range.

Various methods can be used to graft-polymerize the polycyclic (meth) acrylate monomer (b) to the ethylene / α-olefin copolymer (a). A solution method in which the radical generator and the monomer (b) are heated while the union (a) is dissolved in an appropriate solvent,
A melting method in which the copolymer (a) is heated and kneaded with a radical generator and the monomer (b) in a molten state, and an aqueous dispersion of the copolymer (a) is mixed with the monomer (b). An emulsification method or the like in which an initiator is added can be employed.

In the solution method, as a solvent, for example, benzene, toluene, aromatic hydrocarbon solvents such as xylene, n-hexane, cyclohexane, aliphatic hydrocarbon solvents such as n-heptane, dichloromethane, chloroform, carbon tetrachloride,
Halogenated aliphatic hydrocarbon solvents such as 1,1,1-trichloroethane, tetrachloroethylene, trichloroethylene and 1-chlorobutane can be used. The grafting reaction is carried out using the above-mentioned solvent, and is preferably carried out under strong stirring while adjusting the concentration of the copolymer (a) to be 10 to 500 g /. The reaction temperature may be any temperature that is higher than the temperature at which the copolymer (a) dissolves in the above solvent, and is actually 50 to
A range of 200 ° C, especially 100 to 180 ° C, is preferred. The time temperature is usually 0.5 to 24 hours.

The reaction operation may be a batch type or a continuous type, but a batch type is preferable for uniform grafting. The grafting reaction is preferably carried out by simultaneously and sequentially adding the monomer (b) and the radical initiator to the copolymer (a) solution. Further, in order to control the graft chain length as needed, thiols exemplified by laurylmercaptan, p-toluenethiol, etc., halogenated hydrocarbons exemplified by carbon tetrabromide, etc., and trinitrotoluene are exemplified. Substituted aromatic hydrocarbons, acrolein exemplified by acrolein oxime, etc., iron chloride,
Chain transfer agents such as metal halides exemplified by copper chloride and the like and organic metals exemplified by diethyl zinc and the like can be added to the polymerization system.

The addition amount of the monomer (b) and the radical initiator can be appropriately changed depending on the type of the copolymer (a), the type of the solvent, the reaction temperature, the desired graft amount, and the like.

Next, when performing a graft copolymerization reaction by a melting method,
This is performed by heating the copolymer (a) to a temperature not lower than its melting point, for example, an extruder, a Banbury mixer, a co-kneader,
A kneading device such as a roll can be used. It is preferable that the monomer (b) and the radical initiator are previously blended with the copolymer (a). However, when an extruder is used, the monomer (b) and the radical initiator are used. It may be side-fed to the extruder. The addition amount of the monomer (b) and the radical initiator can be appropriately changed as in the case of the solution method.

As the above radical initiator, organic peroxides,
Organic peresters such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-
2,5-di (peroxybenzoate) hexyne-3,1,4
-Bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl acetate, 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexin-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, tert-butylper-sec- Examples include ectoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate, and other azo compounds such as azobis-isobutylnitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, etc. Are preferred.

When performing a graft copolymerization reaction by the emulsification method, ethylene
The α-olefin copolymer (a) is in an aqueous dispersion state,
It can be obtained by emulsion graft polymerization of a polycyclic (meth) acrylate monomer (b) as a monomer.

Before performing the graft polymerization operation, the aqueous dispersion is added with a crosslinking aid such as the above-mentioned peroxide and, if necessary, a polyfunctional vinyl monomer exemplified by divinylbenzene, and heat-treated to obtain an ethylene / α-olefin copolymer. (A) may be made high molecular weight by crosslinking. By such an operation for increasing the molecular weight, an excellent impact modifier can be obtained.

The aqueous dispersion of the copolymer (a) is described in, for example, JP-A-51-62.
It can be obtained by the method disclosed in JP-A-890. When grafting, a persulfate or an organic peroxide is usually used as a polymerization initiator. Examples of the initiator include ammonium persulfate, potassium persulfate, benzoyl peroxide-dimethylaniline and the like. Further, in the emulsion graft-modified polymerization, it is preferable to use a surfactant to stabilize the reaction system, for example, sodium laurate, sodium dodecylbenzenesulfonate,
Sodium oleate and the like can be used. The reaction temperature can be appropriately selected within a range of 0 ° C to 150 ° C.

Method for Using Modified Ethylene / α-Olefin Copolymer By appropriately using the various graft polymerization methods described above, a modified ethylene / α-olefin copolymer having a desired graft ratio can be obtained. The modified ethylene / α-olefin copolymer thus obtained can be used as an impact modifier, and when blended with the resin to be blended, the impact resistance of the resin to be blended is improved.
In addition, the resin to be blended has improved impact resistance and is less likely to lower the flexural modulus (FM). Further, the heat resistance is hardly reduced.

Examples of the resin to be blended include a cyclic olefin-based random copolymer and a cyclic olefin ring-opening copolymer. These have excellent heat resistance, solvent resistance, chemical resistance, heat aging resistance, dielectric properties, and rigidity.
JP-A-98780, JP-A-61-115912, JP-A-61-1
No. 15716, JP-A-61-120816 and JP-A-60
-168708 and the like.

Also, if necessary, to control the graft chain length,
Thiols exemplified by laurylmercaptan, p-toluenethiol, etc., halogenated hydrocarbons exemplified by carbon tetrabromide, etc., substituted aromatic hydrocarbons exemplified by trinitrotoluene, etc., exemplified by acrolein oxime, etc. Chain transfer agents such as acrolein, metal halides exemplified by iron chloride, copper chloride and the like, and organic metals exemplified by diethylzinc and the like can be added to the polymerization system.

The cyclic olefin copolymer is mainly an α-olefin copolymer such as ethylene or propylene, but a copolymer containing at least 30 parts by weight of a cyclic olefin component is preferable.

Specific examples of the cyclic olefin include the compounds of Tables 3 to 6 and 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene. -Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,
8a-octahydronaphthalene, 2-propyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,
5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,1,
4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Fluoro-1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-cyclohexyl-1,4,5, 8-dimethano-1,2,3,
4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-
Ethylidene-1,4,5,8-Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-ethylidene-3-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-3-ethyl- 1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-3-isopropyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethylidene-3-butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-
n-propylidene-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-n-propylidene-3-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a
-Octahydronaphthalene, 2-n-propylidene-3
-Ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-propylidene-3-isopropyl-1,4,5,8 -Dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene, 2-n-propylidene-3-
Butyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isopropylidene-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isopropylidene-3-methyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isopropylidene-3-ethyl-1,4,5,8-dimethano-1,2,3,4,4a , 5,8,8a-Octahydronaphthalene, 2-isopropylidene-3-isopropyl-1,4,5,
8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isopropylidene-3-butyl-1,4,5,8-
Octahydronaphthalenes such as dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene can be exemplified.

The modified ethylene / α-olefin copolymer of the present invention is slightly different depending on the graft ratio,
It is preferred to use from 1 to 70 parts by weight per part by weight.

[Effects of the Invention] As described above, the modified ethylene / α-olefin copolymer of the present invention has excellent resistance to resistance by using the polycyclic (meth) acrylate monomer (b) as the modified monomer. It can be used as an impact modifier. In addition, when the modified ethylene / α-olefin copolymer is used as an impact modifier, the resin to be blended has a very small decrease in the flexural modulus, and the heat resistance is maintained as well as in the past. You.

〔Example〕

Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to these embodiments. Test methods and evaluation methods for various physical property values in the present invention are shown below.

(1) Thermal deformation temperature (TMA): TMA10 (Th
This was measured by the thermal deformation behavior of a 1 mm thick sheet using an electromechanical analyzer. That is, a quartz needle was placed on the sheet, a load of 50 g was applied, the temperature was raised at 5 ° C./min, and the temperature at which the needle penetrated 0.1 mm was defined as TMA.

(2) Impact strength: Using a Toyo Seiki Izod impact tester, press a 2mm thick pressed sheet to a length of 63.8mm and a width of 12.
A 7 mm sample was punched out, a notch of 0.25 mmR was inserted, and the measurement was performed at 23 ° C.

(3) Rigidity (flexural modulus): Using an Instron tensile tester, a press sheet having a thickness of 2 mm, a length of 63.8 mm and a width of 1
Punch 2.7mm sample, compression speed 5mm / min, distance between supports 3
The measurement was performed at 2 mm and 23 ° C.

Izod impact test and bending test are performed after press forming.
After a day passed.

Example 1 An ethylene-propylene-ethylidene norbornene (ENB) terpolymer having an ethylene content of 80.8 mol%, a propylene content of 17.7 mol%, and an iodine value of 12, 70% of which is divinylbenzene and a peroxide initiator 0.001 part by weight of a surfactant (sodium lauryl sulfate) is added to 200 parts by weight of the aqueous dispersion (solid content concentration: 10% by weight) of the resin crosslinked and insolubilized. Heated to the emulsified solution 60 ° C., with stirring, methacrylic acid-3-tetracyclo [4,4,0,1 ^2,5, 1
^[7,10 ] 8 parts by weight of dodecyl (hereinafter abbreviated as MTCD) and 0.2 parts by weight of a polymerization initiator (potassium persulfate) were added dropwise over 4 hours to carry out emulsion polymerization. After completion of the dropwise addition, a post-reaction was carried out at 60 ° C. for further 30 minutes with stirring. After completion of the reaction, MTCD
Was confirmed to be 100% reacted by gas chromatography.

As a result, a milky white uniform aqueous dispersion having a solid content of 14% by weight was obtained. The polymer obtained by drying the aqueous dispersion was homo-MT with methyl ethyl ketone at reflux temperature.
When the graft amount of MCTD was calculated from the weight of the graft polymer after extracting the CD polymer for 6 hours, it was 20%.
(The amount of grafting is a value of the amount of the grafted polycyclic (meth) acrylate monomer (b) in the modified polymer expressed in% by weight.

On the other hand, the oxygen content of the extracted graft polymer was analyzed. As a result, the value of the obtained graft amount was 19.8%. Hereinafter, the graft ratio was defined as a value calculated from the oxygen content.

Next, when the resulting modified ethylene / α-olefin copolymer is blended with an ethylene / DMON copolymer (compound resin) having excellent flexural modulus, the impact strength of the compounded resin increases and the bending elasticity increases. The decrease in rate was examined. First, an ethylene / DMON copolymer was prepared.

Preparation of ethylene-DMON copolymer Ethylene and 1,4,5,8-dimethano-1,2,4,4a, 5,8,8a were continuously used in a two-glass polymerization vessel equipped with stirring blades. −
Octahydronaphthalene (structural formula; Hereinafter, it is abbreviated as DMON. ) Was carried out. That is, the DMON cyclohexane solution is continuously supplied from the upper part of the polymerization vessel so that the concentration in the polymerization vessel becomes 60 g /, and is continuously supplied so that the vanadium concentration in the polymerization vessel becomes 0.9 mmol /. VO (C ₂ H ₅ ) Cl ₂ in cyclohexane as a catalyst and ethyl aluminum sesquichloride (Al (C ₂ H ₅ )) continuously supplied so that the aluminum concentration in the polymerization vessel becomes 7.2 mmol / mol _1.5 C
with continuously supplying cyclohexane solution in each reactor l _1.5), a polymerization solution within the polymerization vessel from the polymerization vessel bottom extract always polymerization solution continuously so as to maintain the 1. From the top of the polymerization vessel, ethylene is supplied at a rate of 85 per hour, hydrogen is supplied at a rate of 0.2 per hour, and nitrogen is supplied at a rate of 45 per hour. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached outside the polymerization.

When copolymerization is performed under the above reaction conditions, a polymerization reaction mixture containing an ethylene / DMON copolymer is obtained. A small amount of isopropyl alcohol was added to the polymerization liquid extracted from the lower part of the polymerization vessel to stop the polymerization reaction. Thereafter, the polymerization liquid was introduced into a household mixer containing about three times the amount of acetone with respect to the polymerization liquid while rotating the mixer, to precipitate a produced copolymer. This copolymer was collected by filtration, dispersed in acetone so that the polymer concentration became about 50 g /, and the copolymer was treated at the boiling point of acetone for about 2 hours. After the treatment described above, the copolymer was collected by filtration at 120 ° C.
And dried under reduced pressure overnight.

¹³ C of ethylene-DMON copolymer obtained as above
-The ethylene composition in the copolymer measured by NMR analysis was 67 mol%, the intrinsic viscosity [η] measured in decalin at 135 ° C was 0.6%.
0 dl / g and softening temperature (TMA) was 111 ° C. This was used as a blend resin.

Next, with respect to 80 parts by weight of the obtained ethylene / DMON copolymer, 20 parts by weight of a modified ethylene / α-olefin copolymer produced as an impact resistance improver was dry blended, and tetrakis [ Methylene-3 (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate]
0.5 part by weight of methane, 0.3 part by weight of di-lauryl-thio-di-propionate were blended, kneaded at 190 ° C. using a Brabender plastograph, compression-molded at 240 ° C., and 1 m
Pressed sheets of m and 2 mm thickness were obtained. A test piece was punched out of the obtained sheet to perform a physical property test. Table 8 shows the results.
It was shown to.

(Examples 2 to 7) Copolymers obtained by changing the respective component ratios of the ethylene / α-olefin copolymer (a) as shown in Table 7 were used, and the polycyclic (meta) to be graft-polymerized was used. Graft polymerization was carried out in the same manner as in Example 1 except that the structure of the acrylate monomer (b) and the amount thereof were changed. The graft amount is shown in Table 7.

Next, each of the obtained modified ethylene / α-olefin copolymers was blended with the ethylene / DMON copolymer used in Example 1 in the same manner as in Example 1 to obtain respective test pieces. A physical property test was performed on each test piece, and the results are shown in Table 8.

(Examples 8 to 10) Copolymers having different component ratios as shown in Table 7 were used as the ethylene / α-olefin copolymer (a), and the polycyclic (meth) copolymer to be graft-polymerized was used. Graft polymerization was carried out in the same manner as in Example 1 except that the structure of the acrylate monomer (b) and the amount thereof were changed. The graft amount is shown in Table 7.

Example 11 1500 g of ethylene-propylene copolymer (intrinsic viscosity at 135 ° C. in decalin [η] 1.3 dl / g, ethylene content 80 mol%, crystallinity 15%) was placed in a glass reactor in a nitrogen atmosphere. Dissolved in p-xylene 7.5 at 125 ° C. Thereafter, 500 ml of a p-xylene solution of MTCD and dicumyl peroxide (0.16 g / 10 ml of dicumyl peroxide) were continuously supplied from separate conduits over 4 hours, and finally 900 g of MTCD,
10.0 g of dicumyl peroxide was fed into the system. After the completion of the supply, the reaction was further continued for 2 hours. After the completion of the reaction, the system was cooled to around room temperature, and the reaction solution was poured into a large excess of methyl ethyl ketone (in a mixer) to precipitate and precipitate an MTCD-grafted ethylene-propylene copolymer. I let it. After filtering the grafted ethylene / propylene copolymer, it was further washed repeatedly with methyl ethyl ketone, and dried under reduced pressure at 50 ° C. for 10 hours to obtain a target MTCD grafted ethylene / propylene copolymer. The graft amount of MTCD is 6%, and its MFR is 0.3 g / 10
Min (230 ° C.).

(Example 12) Graft polymerization was carried out in the same manner as in Example 11 except that the TDM of Example 11 was replaced with (III), which is the 9-methyl group of the MTCD used in Example 6, as shown in Table 7. The grafted amount of the obtained modified ethylene / propylene copolymer of 9-methyl MTCD was 7%.

(Example 13) Ethylene / propylene copolymer 100 used in Example 11
Parts by weight, 50 parts by weight of MTCD, 2,5-dimethyl-2,5-di (tert.
-Butyl peroxy) hexyne-3 0.2 parts by weight was thoroughly mixed with a Henschel mixer, and MTCD and the above-mentioned peroxide were impregnated into a copolymer rubber.
(0 ° C.), and extruded under kneading conditions with a residence time of 2.3 minutes. The obtained MTCD graft-modified ethylene / propylene copolymer rubber was a translucent solid substance having a white tinge, and the graft amount of MTCD was 5%. The MFR is 0.3g /
10 minutes (230 ° C.).

(Example 14) As shown in Table 10, the MTCD of Example 13 was subjected to graft polymerization in the same manner as Example 13 except that (III) was used as the 9-methyl group of the MTCD used in Example 6. The grafting amount of the obtained modified ethylene / α-olefin copolymer of 9-methyl MTCD was 6%.

(Reference Example 1) An unmodified ethylene / propylene / ENB copolymer is used for the ethylene / DMON copolymer used in Example 1 (Example 1).
A blend composition was obtained in the same manner as in Example 1 except that the raw materials used in the synthesis of the above were blended. A test piece was punched from the obtained sheet, and the same physical property test as in Example 1 was performed. Table 8 shows the results.

(Comparative Example 1) A sheet was prepared only from the ethylene / DMON copolymer used in Examples 1 to 14, and a test piece was punched out of the obtained sheet to perform the same physical property test as in Example 1. Table 8 shows the results.

Claims (6)

(57) [Claims] (1) An ethylene / α-olefin copolymer (a) having an ethylene content of 50 to 95 mol% with respect to 40 to 98 parts by weight of the general formula [I] or [II] Wherein, N and M are both integers of 0, 1, 2 or 3, L is the 3 or 4, R ₀ ^1, one of R ₀ ² is an (meth) acryloyl oxyl group And the other is a hydrogen atom, and X ¹ and X ² are each a direct bond, or a lower alkylene group selected from a methylene group, an ethylene group, a propylene group and a butylene group, or an X ¹ and X ² group selected from an oxyethylene group and an oxypropylene group. An oxygen lower alkylene group, R ^{1 to} R ⁸ are a hydrogen atom, or a lower alkyl group selected from a methyl group, an ethyl group, a propyl group, and a butyl group, or a halogen group; R ⁹ and R ¹⁰ are a hydrogen atom; Or methyl group, ethyl group, propyl group, lower alkyl group selected from butyl group, or ethylidene group, propylidene group,
Or a halogen group]. (B) 2
To 60 parts by weight by graft polymerization (where (a) +
(B) is selected to be 100 parts by weight). A modified ethylene / α-olefin copolymer. 2. An ethylene / α-olefin copolymer (a) having an ethylene content of 50 to 95 mol% based on the general formula [I] or [II] Wherein, N and M are both 0, 1, 2 or 3 of an integer, L is 3 or 4, one of R ₀ ^1, R ₀ ² is (meth)
An acroyloxyl group, the other being a hydrogen atom,
X ¹ and X ² are both a direct bond, or a methylene group, an ethylene group, a lower alkylene group selected from a propylene group and a butylene group, or an oxygen-containing lower alkylene group selected from an oxyethylene group and an oxypropylene group, ¹
To R ⁸ are a hydrogen atom, or a methyl group, an ethyl group, a propyl group, a lower alkyl group selected from a butyl group, or a halogen group, R ⁹ and R ¹⁰ are a hydrogen atom, or a methyl group,
A lower alkyl group selected from an ethyl group, a propyl group, and a butyl group, or an ethylidene group, a propylidene group, or a halogen group]. Modified ethylene α
-A method for producing an olefin copolymer. 3. The method according to claim 2, wherein the graft polymerization is carried out after the ethylene / α-olefin copolymer (a) is in an aqueous dispersion state. 4. A peroxide and, if necessary, a crosslinking aid are added to the aqueous dispersion of the ethylene / α-olefin copolymer (a) to carry out a crosslinking reaction under heating to polymerize, followed by graft polymerization. The method of claim 3, wherein: 5. The method according to claim 2, wherein the graft polymerization is carried out in the presence of an organic solvent. 6. The method according to claim 2, wherein the graft polymerization is carried out while the ethylene / α-olefin copolymer (a) is melted.