CN1022111C

CN1022111C - Cycloolefin type random copolymer compositions

Info

Publication number: CN1022111C
Application number: CN 89100218
Authority: CN
Inventors: 守屋悟; 石本昭夫; 赤名义德; 山本阳造; 岸村小太郎; 池尻文利
Original assignee: Mitsui Petrochemical Industries Ltd
Current assignee: Mitsui Chemical Industry Co Ltd
Priority date: 1988-04-06
Filing date: 1989-01-10
Publication date: 1993-09-15
Anticipated expiration: 2004-01-10
Also published as: CN1036594A

Abstract

In accordance with the present invention, there are provided cycloolefin type random copolymer compositions excellent in heat resistance, chemical resistance, rigidity, impact resistance, etc., which comprise (A) a cycloolefin type random copolymer containing an ethylene component and a cycloolefin component and having an intrinsic viscosity of 0.05-10 dl/g and a softening temperature (TMA) of not lower than 70 degree C, and (B) one or more non-rigid copolymers, and optionally (C) an inorganic filler or organic filler.

Description

Cycloolefin type random copolymer compositions

The present invention relates to cycloolefin type random copolymer compositions, it has good thermotolerance, good thermal ageing, good chemical resistance, excellent solvent-resistance, excellent dielectric characteristic, good rigidity and shock-resistance.

As known to, the synthetic resins that has good equalization characteristic between rigidity and shock strength is polycarbonate, ABS(acrylonitrile-butadiene-styrene (ABS) composition) or the like.For example, polycarbonate is the resin with good rigidity, thermotolerance, thermal ageing properties and shock strength.But polycarbonate relates to a problem like this: that is exactly because they are easy to be corroded by highly basic, so they are relatively poor in chemical resistant properties.Say that further they have higher water-intake rate.Though ABS has good mechanical characteristics, they have so problem, and promptly their chemical resistant properties is relatively poor, further, and owing to the two keys in their molecular structure show relatively poor aspect weather ability and the thermotolerance.

On the other hand, the polyolefine that is widely used as the general use resin has good chemical resistance and solvent resistance.But many polyolefine show bad thermotolerance, crystallizable degree is inadequate and rigidity is bad.In a word, in order to improve polyolefinic rigidity and thermotolerance, can adopt following a kind of method, wherein nucleating agent mixes polyolefine to promote the crystalline growth, perhaps adopts another kind of method, wherein polyolefine is cooled off gradually to promote the crystalline growth.But, be competent by the resulting alleg effect of these methods hardly.The method of mixing in polyolefine such as the third composition of nucleating agent has the danger that damages the various good characteristics of polyolefinic institute's inherent on the contrary, the refrigerative method is lower aspect production efficiency gradually, and relates to along with polyolefinic noncrystalline part reduces and the danger of reduction shock strength.

For example, at United States Patent (USP) the 2nd, 883, in No. 372, the example that ethene and 2, the multipolymer of 3-dihydroxyl-dicyclopentadiene have been used as the multipolymer of ethene and huge comonomer is disclosed.But though described multipolymer has good equilibrium between the rigidity and the transparency, yet this multipolymer is because its glass transition temperature shows bad thermotolerance about 100 ℃.In addition, in the multipolymer of ethene and 5-ethylidene-2-norbornene, also can be observed similar shortcoming.

It is a kind of 1,4,5 that Japanese patent gazette has proposed for No. 14910/1971,8-dimethylene-1,2,3,4,4a, 5,8, the homopolymer of 8a-octalin.But the polymkeric substance that is proposed shows bad thermotolerance and thermal ageing.The Japanese Patent spy opens clear No. 127728/1983 and has further proposed 1,4,5,8-dimethylene-1,2,3,4,4a, 5,8, the multipolymer of the homopolymer of 8a-octalin or described cycloolefin and norbornene-type comonomer carries out ring-opening polymerization effect (ring-opening polymerization polymer) under the condition that they can disclose according to described patent and obtains.But, on main polymer chain, there are these ring-opening polymerization polymers of unsaturated link(age) to have such shortcoming, promptly they have bad thermotolerance and thermal ageing.

In these research process, we find that the cycloolefin type random copolymer of ethene and huge cycloolefin is a synthetic resins, and this resin has good thermotolerance, thermal ageing, chemical resistant properties, solvent resistance, excellent dielectric feature and rigidity.On the basis of above-mentioned discovery, we have worked out the different technical advice that is disclosed in No. the 168708/1985th, Japanese kokai publication sho and Japanese patent application No. 220550/1984,236828/1984,242336/1984 and 95906/1986.Although they are olefin type polymkeric substance, the cycloolefin type random copolymer that proposes has good thermotolerance and rigidity.But they have such problem, and promptly they are easily crisp, and impact resistance is bad.

We do not damage their excellent heat resistance, thermal ageing properties, chemical resistant properties, solvent resistance and dielectric characteristics after deliberation with the rigidity of improving cycloolefin type random copolymer and shock-resistance.As the result of research, we find to include the composition of the cycloolefin type random copolymer of specific softening temperature (TMA) and at least a specific non-rigid multipolymer or by mineral filler and/or organic filler fusion are gone into to comprise that the composition that the described composition of described random copolymers and described non-rigid multipolymer obtains has above-mentioned good characteristic.The present invention carries out on the basis of above-mentioned discovery.

The present invention is intended to solve above-mentioned problems of the prior art, an object of the present invention is to provide the cycloolefin type random copolymer compositions with good thermotolerance, thermal ageing properties, solvent resistance and dielectric characteristics and rigidity and shock-resistance.

The feature of first cycloolefin type random copolymer compositions of the present invention comprise (A) cycloolefin type random copolymer comprise the ethene composition, by at least a cycloolefin composition of logical formula I or (II) representative down, the limiting viscosity [η] that records in 135 ℃ of following naphthalanes is the 0.05-10 deciliter/gram, softening temperature (TMA) is not less than 70 ℃, (B) one or more non-rigid multipolymers that are selected from following group;

(ⅰ) comprise a kind of ethene composition, at least one other alpha-olefin composition and by the cycloolefin type random copolymer of the cycloolefin composition of formula I or (II) expression down, recording limiting viscosity [η] in 135 ℃ of following naphthalanes is the 0.01-10 deciliter/gram, softening temperature (TMA) is lower than 70 ℃

(ⅱ) a kind of noncrystalline extremely low crystalline alpha-olefin type elastomeric copolymers that forms by at least two alpha-olefins,

(ⅲ) by at least two alpha-olefins and the formed a kind of alpha-olefin of at least one non-conjugated diene-diene type elastomeric copolymers,

(ⅳ) aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products, the total amount of described (B) composition accounts for 5-100 part (weight) in described (A) composition 100 parts (weight).

The feature of second kind of cycloolefin type random copolymer compositions comprises:

(A) contain ethene composition and be the 0.05-10 deciliter/gram by the limiting viscosity [η] that the following cycloolefin type random copolymer of the cycloolefin composition of formula I or (II) expression records in 135 ℃ of following naphthalanes, softening temperature (TMA) is not less than 70 ℃,

(B) be selected from one or more non-rigid multipolymer in following group;

(ⅰ) comprise that an ethylene component, at least one other alpha-olefin composition reach the cycloolefin type random copolymer by the cycloolefin composition of following formula I or (II) representative, recording its limiting viscosity [η] in 135 ℃ of following naphthalanes is the 0.01-10 deciliter/gram, its softening temperature (TMA) is under 70 ℃

(ⅳ) aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products,

And

(C) a kind of inorganic filler components or a kind of organic filler composition, the total amount of described (B) composition accounts for 1 to 100 part (weight) in described (A) composition 100 parts (weight), the total amount of described (C) composition accounts for 1 to 100 part (weight) in described (A) composition 100 parts (weight).

Wherein n and m respectively do for oneself the 0 or positive integer, the 1st, are at least 3 positive integer, R ¹To R ¹⁰Represent hydrogen atom, halogen atom or alkyl separately.

First kind of cycloolefin type random copolymer compositions of the present invention comprises described (A) composition and described (B) composition, and described (B) composition accounts for 5-100 part (weight) result in (A) of 100 parts (weight) 6 sides divide makes them have good thermotolerance, thermal ageing properties, chemical resistant properties, solvent resistance, dielectric characteristics, rigidity and shock-resistance.

Second kind of cycloolefin type random copolymer compositions of the present invention comprises described (A) composition, described (B) composition and described (C) composition, respectively account for 1-100 part (weight) at (B) composition and described (C) composition described in described (A) composition 100 parts (weight), the result makes them have good thermotolerance, thermal ageing properties, chemical resistant properties, solvent resistance, dielectric characteristics and shock-resistance.

Fig. 1 is illustrated in the graph of relation of sneaking in the cycloolefin type random copolymer compositions of the present invention between cycloolefin type random copolymer [B] amount (ⅰ) and the shock strength of described composition (beam type intensity).

Fig. 2 is illustrated in the graph of relation of sneaking in the cycloolefin type random copolymer compositions of the present invention between cycloolefin type random copolymer [B] amount (ⅰ) and the softening temperature of described composition (TMA).

Fig. 3 is illustrated in and sneaks into α-cycloolefin type random copolymer [B] in the cycloolefin type random copolymer compositions of the present invention (ⅱ)) amount and the graph of relation between the shock strength (beam type intensity) of described composition.

Fig. 4 is illustrated in the graph of relation of sneaking in the cycloolefin type random copolymer compositions of the present invention between α-cycloolefin type random copolymer [B] amount (ⅱ) and the softening temperature of described composition (TMA).

Fig. 5 is illustrated in the graph of relation of sneaking in the cycloolefin type random copolymer compositions of the present invention between α-cycloolefin-diene type random copolymers [B] amount (ⅲ) and the shock strength of described composition (beam type intensity).

Fig. 6 is illustrated in the graph of relation of sneaking in the cycloolefin type random copolymer compositions of the present invention between α-cycloolefin-diene type random copolymers [B] amount (ⅲ) and the softening temperature of described composition (TMA).

Fig. 7 is illustrated in the graph of relation between the shock strength (beam type intensity) of the amount of sneaking into aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products in the cycloolefin type random copolymer compositions of the present invention and described composition.

Fig. 8 is illustrated in the graph of relation between the softening temperature (TMA) of the amount of sneaking into aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products in the cycloolefin type random copolymer compositions of the present invention and described composition.

Fig. 9 is illustrated in the graph of relation between the shock strength (beam type intensity) of the total amount of sneaking into two or more non-rigid multipolymers (B) in the cycloolefin type random copolymer compositions of the present invention and described composition.

Figure 10 is illustrated in the graph of relation between the softening temperature of the total amount of the non-rigid multipolymer (B) of sneaking in the cycloolefin type random copolymer compositions of the present invention and described composition.

Cycloolefin type random copolymer compositions of the present invention is elaborated as follows:

According to the present invention, the feature of the cycloolefin type random copolymer compositions that provides comprises:

(A) contain ethene composition and be the 0.05-10 deciliter/gram by the inherent viscosity [η] that the cycloolefin type random copolymer of the cycloolefin composition of following formula (I) and (II) expression records in 135 ℃ of lower naphthalanes, softening temperature (TMA) is not less than 70 ℃.

(B) be selected from one or more non-rigid copolymer in following group, comprise:

(ⅰ) comprise a kind of ethene composition, at least a other the alpha-olefin composition and by the cycloolefin type random copolymer of the cycloolefin composition of following formula [I] or [II] expression, recording inherent viscosity [η] in 135 ℃ of lower naphthalanes is the 0.01-10 deciliter/gram, its softening temperature (TMA) is lower than 70 ℃

(ⅱ) by a kind of noncrystalline alpha-olefin type elastomeric copolymers to low crystallization of at least two alpha-olefin forms,

(ⅲ) owing at least two alpha-olefins and the formed a kind of alpha-olefin of at least one non-conjugated diene-diene type elastomeric copolymers,

(ⅳ) aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products. The total amount of described (B) composition accounts for 5-100 part (weight) in described (A) composition 100 parts (weight).

General formula

Wherein n and m respectively do for oneself the 0 or integer, the 1st, are at least 3 positive integer, R¹To R¹⁰Represent separately hydrogen atom, halogen atom or alkyl.

Cycloolefin type random copolymer (A) and (B) (ⅰ) consisted of cycloolefin type random copolymer of the present invention, cycloolefin random copolymer and (A) and (B) (ⅰ) be the cycloolefin type random copolymer that comprises a kind of ethene composition and a kind of specific cycloolefin composition. Described cycloolefin Composition is the cycloolefin composition by following formula [I] or [II] expression, and in cycloolefin random copolymer, described cycloolefin has formed the structure by general formula [III] or [IV] representative.

General formula

Wherein n and m respectively do for oneself the 0 or positive integer, the 1st, are at least 3 positive integer, R¹To R¹⁰Represent separately hydrogen atom, halogen atom or alkyl.

Wherein n, m, l and R¹To R¹⁰With above-mentioned definition.

Cycloolefin, namely a kind of constituent of cycloolefin type random copolymer is as a kind of composition of cycloolefin type copolymer compositions of the present invention, and it is at least a one group of cycloolefin that comprises by the unsaturated monomer of general formula [I] and [II] expression that is selected from. Cycloolefin by general formula [I] representative can be easy to by the Diels-Alder reaction ring penta 2 rare and suitable alkene condensations be made. Equally, can be at an easy rate by the Diels-Alder reaction cyclopentadiene and suitable alkene condensation be made by the cycloolefin of general formula [II] representative.

Concrete cycloolefin by general formula [I] representative is to exemplify chemical combination season thing such in table 1, or except Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, this class octahydro-naphthalene such as 2-methyl isophthalic acid, 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-third

Base-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-hexyl-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene. 2,3 ,-dimethyl-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-methyl-3-ethyl-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-chloro-Isosorbide-5-Nitrae, 5,8-dimethylene-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-bromo-1,4,5,8-, dimethylene-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-is fluorine-based-Isosorbide-5-Nitrae, and 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2,3 ,-two chloro-Isosorbide-5-Nitraes, 5,8-4 dimethano-1,2,3,4,4a, 5,8, the 8a-octahydro-naphthalene, 2-cyclohexyl-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-normal-butyl-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene, 2-isobutyl group-Isosorbide-5-Nitrae, 5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydro-naphthalene etc., these compounds exemplify in table 2

Table 1

Chemical formula compound title

Table 2

Chemical formula compound title

5,10-dimethyl Fourth Ring-

[4,4,0,1 ^2.5, 1 ^7.10]-3-dodecylene

9-ethyl-11,12-dimethyl Fourth Ring-

[4,4,0,1 ^2.5, 1 ^7.10]-3-dodecylene

9-isobutyl--11,12-dimethyl Fourth Ring

[4,4,0,1 ^2.5, 1 ^7.10]-3-dodecylene

5,8,9,10-tetramethyl-Fourth Ring

[4,4,0,1 ^2.5, 1 ^7.10]-3-dodecylene

Six rings [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]

-4-heptadecene

12-methyl six rings [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]

-4-heptadecene

12-isobutyl-six rings [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]

-4-heptadecene

12-isobutyl-six rings [6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]

-4-heptadecene

1,6,10-trimethylammonium-12-isobutyl-six rings

[6,6,1,1 ^3.6, 1 ^10.13, 0 ^2.7, 0 ^9.14]-4-heptadecene

Eight rings [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.18, 1 ^13.16, 0 ^2.7, 0 ^9.14]

-5-two dodecylenes

15-methyl eight rings

[8，8，0，1 ^2.9，1 ^4.7，1 ^11.18，1 ^13.16，0 ^3.8，0 ^12.17]

-5-two dodecylenes

15-ethyl eight rings

[8，8，0，1 ^2.7，1 ^4.7，1 ^11.18，1 ^13.16，0 ^3.8，0 ^12.17]

-5-two dodecylenes

The concrete cycloolefin of general formula [II] representative is the compound that exemplifies in table 3 and table 4.

Table 3

Chemical formula compound title

1,3-dimethyl five rings

[6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14]-4-cetene

1,6-dimethyl five rings

[6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14]-4-cetene

15,16-dimethyl five rings

[6,6,1,1 ^3.6, 0 ^2.7, 0 ^9.14]-4-cetene

Five rings [6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.14]-4-15 carbenes

1,3-dimethyl five rings

[6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13]-4-15 carbenes

1,6-dimethyl five rings

[6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13]-4-15 carbenes

14,15-dimethyl five rings

[6,5,1,1 ^3.6, 0 ^2.7, 0 ^9.13]-4-15 carbenes

Five rings [6,6,1,1 ^3.8, 0 ^2.7, 0 ^9.14]-4-cetene

Six rings [8,7,0,1 ^2.9, 1 ^4.7, 1 ^11.17, 0 ^3.8, 0 ^12.16]

-5-eicosylene

Six rings [8,8,0,1 ^2.9, 1 ^4.7, 1 ^11.17, 0 ^3.8, 0 ^12.17]

-5-heneicosene

Table 4

Chemical formula compound title

Three rings [4,3,0,1 ^2.5]-3-decene

2-methyl three rings [4,3,0,1 ^2.5]-3-decene

5-methyl-three ring [4,3,0,1 ^2.5]-3-decene

Three rings [4,4,0,1 ^2.5]-3-undecylene

10-methyl-three ring [4,4,0,1 ^2.5]-3-undecylene

Cycloolefin type random copolymer [A] must comprise ethene composition and above-mentioned cycloolefin composition as a kind of composition of cycloolefin type random copolymer compositions of the present invention.But except described two kinds of essential compositions, in the scope that does not hinder the object of the invention, cycloolefin random copolymer [A] can comprise other undersaturated comonomer arbitrarily.But the unsaturated monomer of these optional copolymerization is specially the alpha-olefin of 3 to 20 carbon atoms, as propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decane, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc., in the random copolymers of gained, they are in the scope that is less than with ethene composition equimolar amount.

In cycloolefin type random copolymer [A], the scope that the repeating unit (a) that gets from ethylene derivative exists is 40 to 85 moles of %, scope is 50 to 75 moles of % preferably, the scope of deriving out from cycloolefin or existing for the repeating unit of cycloolefin (b) is 15 to 60 moles of %, and scope is 25 to 50 moles of % preferably.Repeating unit (a) is done linear and random arrangement basically.Cycloolefin type random copolymer [A] is essentially linear and does not contain the crosslinking structure of gel formation, and its available following fact confirms to be that described multipolymer can be dissolved in insulation admirably among 135 ℃ of following naphthalanes.

The limiting viscosity [η] that records cycloolefin random copolymer [A] in 135 ℃ of following naphthalanes is the 0.05-10 deciliter/gram, is 0.08-5dl/g preferably.

The softening temperature (TMA) of the cycloolefin type multipolymer [A] that records with thermodynamic analyzer is not less than 70 ℃, is preferably in 90-150 ℃ of scope, and best is 100-200 ℃.In addition, the glass transition temperature (Tg) of described cycloolefin type random copolymer [A] in 50-230 ℃ of scope, is 70-210 ℃ usually preferably.

The crystallinity index of the cycloolefin type multipolymer [A] that records with x-ray diffractometer is in the scope of 0-10%, is 0-7% preferably, and that best is 0-5%.

Cycloolefin type random copolymer [B] (ⅰ), it is a kind of composition of cycloolefin type random copolymer compositions of the present invention, the composition that must comprise is a kind of ethene composition and aforesaid cycloolefin composition, and except described two kinds of essential compositions, must comprise that further other at least a unsaturated copolymerisable monomer composition is as a kind of essential composition.At least a unsaturated copolymerisable monomer of this class specifically includes the alpha-olefin of 3 to 20 carbon atoms such as propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc., in the random copolymers of gained, its amount is in the scope that is not more than the unitary equimolar amount of ethene composition.

Cycloolefin type random copolymer [B] (ⅰ) in, the scope that exists of the repeating unit of deriving out from ethene (a) is 40 to 99 moles of %, be 75 to 98 moles of % preferably, the amount scope of the repeating unit of deriving out from cycloolefin (b) is 1 to 40 mole of %, be 1 to 15 mole of % preferably, the amount scope of the repeating unit (c) of deriving out from least a alpha-olefin except that ethene is 1 to 45 mole of %, be 1 to 35 mole of % preferably, repeating unit (a) and (b) and (c) make linear fusion and random arrangement basically.Cycloolefin type random copolymer [B] (ⅰ) comes down to linearly, does not contain the crosslinking structure of gel formation, and it can be confirmed that promptly described multipolymer can be dissolved in admirably and remaining in 135 ℃ of following naphthalanes by such fact.

Alpha-olefin elastomer copolymer [B] (ⅱ) can be used as a kind of composition of cycloolefin type random copolymer of the present invention, it be by at least two kinds of alpha-olefins form noncrystalline to low crystalline multipolymer.Available particularly (ⅰ) ethylene-and (ⅱ) propylene-alpha-olefin copolymers rubber is as described composition [B] (ⅱ).Constitute the example alpha-olefin of 3 to 20 carbon atoms normally of the alpha-olefin of described (ⅰ) ethylene-, as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or their mixture.In the middle of them, propylene or 1-butylene are particularly desirable.

The example that constitutes the alpha-olefin of described (ⅱ) propylene-alpha-olefin copolymers rubber is generally alpha-olefin such as 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or their mixture of 4 to 20 carbon atoms.Among them, 1-butylene is particularly desirable.

Ethene and the molar ratio of alpha-olefin in (ⅰ) ethylene-are that the kind according to alpha-olefin is different and change, but its molar ratio normally in 30/70 to 95/5 scope, be from 50/50 to 95/5 preferably.When alpha-olefin was propylene, described molar ratio scope preferably was 50/50 to 90/10, and when alpha-olefin had 4 or more carbon atoms, described molar ratio was preferably in 80/20 to 95/5 scope.

Propylene with in (ⅱ) propylene-alpha-olefin copolymers rubber the molar ratio of alpha-olefin be to change according to the kind of alpha-olefin, but its preferably scope be 50/50 to 95/5.When alpha-olefin was 1-butylene, described molar ratio was preferably in 50/50 to 90/10 scope, and when alpha-olefin had 5 or more carbon atoms, described molar ratio scope preferably was 80/20 to 95/5.

Record alpha-olefin type elastomer copolymer [B] crystallinity index (ⅱ) with x-ray diffractometer and be preferably in the 0-50% scope, then better in 0-25%.

Recording alpha-olefin type elastomer copolymer [B] limiting viscosity [η] scope (ⅱ) in 135 ℃ of following naphthalanes is the 0.2-10 deciliter/gram, and surveying preferably in 135 ℃ of following naphthalanes, scope is the 1-5 deciliter/gram.Its density is preferably in 0.82-0.96 gram/cubic centimetre scope, is preferably 0.84-0.92 gram/cubic centimetre.

Be used for alpha-olefin type elastomer copolymer of the present invention [B] (ⅱ) can be graft modification multipolymer, this graft modification multipolymer with being selected from grafted monomer 0.01 to the 5%(weight of unsaturated carboxylic acid or derivatives thereof), use 0.1 to 4%(weight preferably), carry out modification.

Be used for the unsaturated carboxylic acid of alpha-olefin type elastomer copolymer of the present invention [B] modification (ⅱ) and the example of its derivative and comprise these unsaturated carboxylic acids; as vinylformic acid, toxilic acid, fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, Ba Dousuan, iso-crotonic acid, gram acid (nadic ucid) (interior cis-dicyclo [2 with receiving; 2; 1] heptan-5-alkene-2; and their derivative such as acyl halide, acid amides, imide, acid anhydrides, ester etc. the 3-dicarboxylic acid) etc..The object lesson of described derivative comprises Malaysia acyl chlorides, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, toxilic acid glycidyl ester etc.Among them, preferably unsaturated dicarboxylic acid or its acid anhydrides, toxilic acid, gram acid and their acid anhydrides are particularly desirable with receiving.

By with a kind of grafted monomer that is selected from described unsaturated carboxylic acid and described derivative with any kind of ordinary method grafting-be copolymerized to alpha-olefin type elastomer copolymer [B] can the production modification on (ⅱ) the alpha-olefin type elastomer copolymer.For example, modification the alpha-olefin type elastomer copolymer can be with the preparation of such method, wherein said alpha-olefin type elastomer copolymer is a fused, inwardly add grafted monomer and carry out graft polymerization reaction, or the elastomerics interpolymer can prepare with such method, wherein said alpha-olefin type elastomer copolymer is dissolved in a kind of solvent, inwardly adds grafted monomer and carries out graft copolymerization.In each reaction, be to make grafted monomer carry out graft reaction in the presence of the radical initiator of graft copolymerization effect effectively preferably.This graft reaction normally carries out under 60 to 350 ℃.The amount of used radical initiator accounts for 0.001 to 1 part (weight) usually in ethene-alpha-olefin random copolymers 100 parts (weight).

The example of radical initiator comprises organo-peroxide and organic peracid ester, as benzoyl peroxide, dichlorobenzoperoxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (phenylformic acid superoxide) hexin-3,1,4-two (t-butyl peroxy sec.-propyl) benzene, lauroyl peroxide, the peracetic acid tertiary butyl ester, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-2,2,5-dimethyl-(t-butylperoxy) hexane, t-butyl perbenzoate, cross the toluylic acid tertiary butyl ester, cross the isopropylformic acid tertiary butyl ester, cross secondary sad tertiary butyl ester, cross the PIVALIC ACID CRUDE (25) tertiary butyl ester, cross PIVALIC ACID CRUDE (25) cumyl ester and cross the diethylacetic acid tertiary butyl ester; Also has azo-compound such as Diisopropyl azodicarboxylate, azo isopropylformic acid dimethyl esters etc., among this, preferably dialkyl such as dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 1,4-two (t-butylperoxy sec.-propyl) benzene etc.

Described alpha-olefin type elastomer copolymer [B] (ⅱ) in, by to ethylene-propylene random copolymer or ethene-alpha-olefin random copolymers.It is particularly desirable that (its ethylene content is 35 to 50 moles of %, and crystallinity index is not higher than 5%) carries out the graft modification multipolymer that modification obtains with the derivative that is selected from described unsaturated carboxylic acid and it, because they show the best effect of improving shock-resistance.

Alpha-olefin diene type elastomer copolymer [B] as a kind of composition of cycloolefin type copolymer compositions of the present invention is the multipolymer of at least two kinds of alkene and at least a non-conjugated diene (ⅲ).Concrete used be (ⅰ) ethene-alpha-olefin-diene copolymers rubber and (ⅱ) propylene-alpha-olefin-diene copolymers rubber as [B] described composition (ⅲ).

The alpha-olefin that constitutes (ⅰ) ethene-alpha-olefin-diene copolymers rubber has 3 to 20 carbon atoms usually, as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or their mixture.Among this, preferably propylene or 1-butylene.

The alpha-olefin that constitutes (ⅱ) propylene-alpha-olefin-diene copolymers rubber has 4 to 20 carbon atoms usually, as 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene or their mixture.Among this, 1-butylene is particularly desirable.

For (ⅰ) ethene-alpha-olefin-diene copolymers rubber or (ⅱ) diene of propylene-alpha-olefin-diene copolymers rubber form example and comprise linear non-conjugated diene, as 1,4-hexadiene, 1,6-octadiene, 2-methyl isophthalic acid, 5-hexadiene, 6-methyl isophthalic acid .5-heptadiene, 7-methyl isophthalic acid .6-octadiene etc.; Non-conjugated cyclenes such as tetrahydrobenzene, cyclopentadiene, methyl tetrahydroindene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornylene, 6-chloromethyl-5-isopropylidene-2-norbornylene, 2,3-diisopropylidene-5-norbornylene, 2-ethylidene-3-isopropylidene-5-norbornylene, 2-propenyl-2,2-norbornadiene etc.Among them, preferably 1,4-hexadiene and non-conjugated cyclic diolefine, dicyclopentadiene or 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, 5-ethylidene-2-norbornene, 1,4-hexadiene and 1,4-octadiene are particularly desirable.

The ethene in (ⅰ) ethene-alpha-olefin-diene copolymers rubber and the molar ratio of alpha-olefin are to change according to the kind of alpha-olefin, but preferably scope 50/50 to 95/5.When alpha-olefin was propylene, scope was 50/50 to 90/10 preferably for described molar ratio, and when alpha-olefin had 4 or more carbon atoms, described molar ratio scope preferably was 80/20 to 95/5.

The content of diene composition is in 0.5 to 10 mole of % scope, preferably at 0.5 to 5 mole of % in copolymer rubber.

The propylene in (ⅱ) propylene-alpha-olefin-diene copolymers rubber and the molar ratio of alpha-olefin are to change according to the type of alpha-olefin, but preferably in 50/50 to 95/5 scope.When alpha-olefin was 1-butylene, described molar ratio was preferably in 50/50 to 90/10 scope, and had 5 or during more carbon atoms, described mol ratio is preferably in 80/20 to 95/5 scope when alpha-olefin.

The content of diene composition is 0.5 to 5 mole of % in 0.5 to 10 mole of % scope preferably in copolymer rubber.

Alpha-olefin-diene type elastomer copolymer [B] crystallinity index (ⅲ) that records with x-ray diffractometer in the 0-10% scope, is 0-5% preferably better.

The alpha-olefin that records in 135 ℃ of following naphthalanes-diene type elastomer copolymer [B] limiting viscosity [η] (ⅲ) is the 1-5 deciliter/gram in the scope of 0.1-10 deciliter/gram preferably.Its iodine number is 5-25 in the 1-30 scope preferably, and its density is 0.85-0.90 gram/cubic centimetre preferably in 0.82-1.00 gram/cubic centimetre scope.

As the hydrocarbon conjugated diene copolymer of aromatic ethylene fundamental mode of a composition of cycloolefin type random copolymer compositions of the present invention or its hydride [B] (a) styrene-butadiene copolymer rubber (ⅳ) specifically, (b) styrene-butadiene-styrene block copolymer rubber, (c) styrene-isoprene block copolymer rubber, (d) styrene isoprene styrene block copolymer (SIS) rubber, (e) hydrogenated styrene-butadiene-styrene block copolymers rubber, (f) hydrogenated styrene-isoprene-styrene block copolymer etc.The molar ratio of vinylbenzene and divinyl is preferably in 0/100 to 60/40 scope in (a) styrene-butadiene copolymer rubber.The vinylbenzene in (b) styrene-butadiene-styrene block copolymer rubber and the molar ratio of divinyl are preferably in 0/100 to 60/40 scope, in the cinnamic polymerization degree in each block is preferably in 0 to 5000 scope, in the polymerization degree of each block divinyl preferably in about 10 to 20000 scopes.The molar ratio of vinylbenzene and isoprene is preferably in 0/100 to 60/40 scope in (c) styrene-isoprene block copolymer rubber.The molar ratio of vinylbenzene and isoprene is preferably in from 0/100 to 60/40 scope in (d) styrene isoprene styrene block copolymer (SIS) rubber, in each block in more about 0 to 5000 scope of the cinnamic polymerization degree, in each block in more about 10 to 20000 scopes of the polymerization degree of isoprene.(e) hydrogenated styrene-butadiene-styrene block copolymers rubber is copolymer rubber, wherein in described styrene-butadiene-styrene block copolymer rubber remaining two keys by in the weight ratio of partial hydrogenation and vinylbenzene and rubber part from 0/100 to 50/50 scope more fortunately.(f) hydrogenated styrene-butadiene-styrene block copolymers rubber is copolymer rubber, wherein the weight ratio of remaining two key partial hydrogenations and vinylbenzene and rubber part more fortunately in 0/100 to 50/50 scope in described styrene butadiene-propylene-ethylene block copolymerization thing rubber.

Use the GPC(gel permeation chromatography, solvent: neighbour-dichlorobenzene, 140 ℃) record the molecular-weight average M of aromatic vinyl hydro carbons conjugated diene block copolymer in 500 to 2000000 scopes, preferably in 10000 to 1000000 scopes, its density is 0.88-0.96 gram/cubic centimetre preferably in 0.80 to 1.10 gram/cubic centimetre scope.

In the present invention, aforesaid non-rigid multipolymer (ⅰ) to (ⅳ) can use or have concurrently uses together two or more in them separately, and sneaks in the cycloolefin type random copolymer compositions.When described non-rigid multipolymer can be used in combination, any combination of non-rigid multipolymer (ⅰ) to (ⅳ) all can be used.

In cycloolefin type random copolymer compositions of the present invention, the total amount of used non-rigid multipolymer (B) accounts for 5 to 100 parts (weight) in cycloolefin type random copolymer [A] 100 parts (weight), account for 7 to 80 parts (weight) preferably, preferably account for 10 to 70 parts (weight).When the total amount of non-rigid multipolymer [B] has accounted in cycloolefin type random copolymer [A] 100 parts (weight) when being less than 5 parts (weight), though composition has good rigidity, but they show bad shock-resistance, and when the total amount of non-rigid multipolymer [B] during more than 100 parts (weight), the balanced variation between the rigidity of composition very low and rigidity and the shock strength.

Fig. 1 represents to sneak into the amount of cycloolefin type random copolymer [B] of cycloolefin type random copolymer compositions of the present invention and the graph of relation between the described shock strength (beam type intensity).

As ise apparent from FIG. 1, when cycloolefin type random copolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock-resistance of the cycloolefin type random copolymer compositions of gained is obviously improved.

Fig. 2 is illustrated in the graph of relation between the softening temperature (TMA) of the amount of the cycloolefin type random copolymer [B] of sneaking in the cycloolefin type random copolymer compositions of the present invention and described composition.

As ise apparent from FIG. 2, even when until 30%(weight) cycloolefin type random copolymer [B] and cycloolefin type random copolymer [A] when mixing, can be surprisingly found out that the softening temperature (TMA) of cycloolefin type random copolymer compositions does not reduce.

When until about 30%(weight) cycloolefin type random copolymer [B] when sneaking into cycloolefin type random copolymer [A], the shock-resistance of cycloolefin type copolymer compositions is greatly improved and thermotolerance does not reduce yet.

In Fig. 1 and 2, zero mark is represented embodiment 1 to 3 and comparative example's 1 value, ● mark is represented embodiment 4 and comparative example's 2 value, the mark is represented embodiment 5 to 7 and comparative example's 3 value, the ■ mark is represented embodiment 8,9 and comparative example's 4 value, the △ mark is represented embodiment 10,11 and comparative example's 5 value, ▲ represent the value of embodiment 12 and 13, represent embodiment 14,15 and comparative example's 6 value.

Fig. 3 is illustrated in the graph of relation between the shock strength (beam type intensity) of the amount of sneaking into alpha-olefin type elastomer copolymer [B] in the cycloolefin type random copolymer and described composition.

As ise apparent from FIG. 3, when alpha-olefin type elastomer copolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock strength of cycloolefin type random copolymer compositions improves significantly.

Fig. 4 is illustrated in the amount of sneaking into alpha-olefin type elastomer copolymer [B] in the cycloolefin type random copolymer compositions and the graph of relation between the described composition softening temperature (TMA).

As ise apparent from FIG. 4, when until about 30%(weight) alpha-olefin type elastomer copolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, can be surprisingly found out that the softening temperature (TMA) of cycloolefin type random copolymer compositions descends hardly.

When until about 30%(weight) alpha-olefin type elastomer copolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock-resistance of cycloolefin type random copolymer compositions is greatly improved, and thermotolerance does not reduce yet.

In Fig. 3 and Fig. 4, zero mark is represented the value of embodiment 16 to 20 and comparing embodiment 7, the mark is represented the value of embodiment 21 to 23 and comparing embodiment 8, ● mark is represented the value of embodiment 26,27 and comparing embodiment 10, and the △ mark is represented the value of embodiment 28,29 and comparing embodiment 11.

Fig. 5 is illustrated in the amount of sneaking into alpha-olefin-two hydrocarbon type elastomer copolymer [B] in the cycloolefin type random copolymer compositions of the present invention and the graph of relation between the described composition shock strength (beam type intensity).

Can find out obviously that from Fig. 5 when alpha-olefin-diene type elastomer copolymer [B] and cycloolefin type random copolymer [A] when mixing, the shock-resistance of the cycloolefin type random copolymer compositions of gained is significantly improved.

Fig. 6 is illustrated in the graph of relation between the softening temperature (TMA) of the amount of sneaking into alpha-olefin-diene elastomer multipolymer [B] in the cycloolefin type random copolymer compositions of the present invention and described composition.

Can find out obviously that from Fig. 6 even when until alpha-olefin-diene type elastomer copolymer [B] of about 30 weight % and cycloolefin type random copolymer [A] when mixing, the softening temperature of cycloolefin type random copolymer compositions descends astoundingly.

As above-mentioned, when until about 30%(weight) alpha-olefin-diene type elastomer copolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock-resistance of cycloolefin type random copolymer compositions is significantly improved, and thermotolerance does not reduce yet.

In Fig. 5 and Fig. 6, zero mark is represented the value of embodiment 35 to 41 and comparing embodiment 13, the mark is represented embodiment 42 to 44 and comparative example's 14 value, ● mark is represented embodiment 45,46 and comparative example's 15 value, the ■ mark is represented embodiment 47,48 and comparative example's 16 value, and the △ mark is represented embodiment 49,50 and comparative example 17.

Fig. 7 is illustrated in the graph of relation between the shock strength (cantilever-type impact strength) of the amount of sneaking into aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products [B] in the cycloolefin type random copolymer compositions of the present invention and described composition.

Can find out obviously that from Fig. 7 when aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products [B] and cycloolefin type random copolymer [A] when mixing, the shock-resistance of the cycloolefin type random copolymer compositions of gained improves significantly.

Fig. 8 is illustrated in the graph of relation between the softening temperature (TMA) of the amount of sneaking into aromatic ethylene fundamental mode hydrocarbon polymer conjugated diene copolymer or its hydrogenated products [B] in the cycloolefin type random copolymer of the present invention and described composition.

Can obviously find out from Fig. 8, even when until the aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer of about 30 weight % or its hydrogenated products [B] and cycloolefin type random copolymer [A] when mixing mutually, the softening Wen Fang (TMA) of cycloolefin type random copolymer compositions descends astoundingly.

As mentioned above, when until about 30%(weight) aromatic ethylene fundamental mode hydro carbons conjugated diene copolymer or its hydrogenated products [B] and cycloolefin type random copolymer [A] when mixing, the shock-resistance of cycloolefin type random copolymer compositions improves significantly, and thermotolerance does not reduce.

In Fig. 7 and Fig. 8, zero mark is represented embodiment 51 to 57 and comparative example's 18 value, the mark is represented the value of embodiment 58 to 60, ● mark is represented embodiment 61,62 and comparative example's 20 value, the ■ mark is represented embodiment 63,64 and comparative example's 21 value, and the △ mark is represented embodiment 65,66 and comparative example's 22 value.

Fig. 9 is illustrated in the graph of relation between the shock strength (beam type intensity) of the amount of sneaking into non-rigid multipolymer [B] in the cycloolefin type random copolymer compositions of the present invention and described composition.

Can find out obviously that from Fig. 9 when non-rigid multipolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock-resistance of cycloolefin type random copolymer compositions is significantly improved.

Figure 10 is illustrated in the amount of the non-rigid multipolymer [B] of sneaking in the cycloolefin type random copolymer compositions and the graph of relation between the described composition softening temperature (TMA).

As ise apparent from FIG. 10, even when until about 30%(weight) non-rigid multipolymer [B] and cycloolefin type random copolymer [A] when mixing, the softening temperature of cycloolefin type random copolymer compositions (TMA) reduces astoundingly.

As mentioned above, when until about 30%(weight) non-rigid multipolymer [B] and cycloolefin type random copolymer [A] when mixing mutually, the shock-resistance of cycloolefin type random copolymer compositions is obviously improved, thermotolerance does not reduce.

In Fig. 9 and Figure 10, zero mark is represented embodiment 67 to 72 and comparative example's 23 value, the mark is represented embodiment 73 to 77 and comparative example's 24 value, ● mark is represented embodiment 78 to 80 and comparative example's 25 value, the ■ mark is represented embodiment 81,82 and comparative example's 26 value, and the △ mark is represented embodiment 83 and 84 and comparative example 27 value.

Second kind of cycloolefin type random copolymer compositions of the present invention also contains inorganic or organic filler composition (C) except containing described cycloolefin type random copolymer [A] and described non-rigid multipolymer (B).

The object lesson of mineral filler comprises silica, silica-alumina, glass powder, granulated glass sphere, glass fibre, glasscloth, glass fibre clump, asbestos, graphite, carbon fiber, carbon cloth, carbon fiber clump, titanium oxide, molybdenumdisulphide, magnesium hydroxide, talcum powder, sellaite, metal powder, wire etc.

The filamentary material that the object lesson of organic filler comprises Wholly aromatic polyamide as poly-terephthaloyl-p-phenylenediamine, poly-terephthaloyl isophthaloyl-p-phenylenediamine, poly-isophthaloyl-p-phenylenediamine, poly-isophthaloyl--phenylenediamine etc.Perhaps such as the filamentary material of the polymeric amide of polyamide fibre 66, polyamide fibre 6, polyamide fibre 10 etc.

Filamentary material can be forms such as monofilament, strand, cloth, clump.

Two or more being used in combination in them can be used or get to these mineral fillers or organic filler separately.

Mineral filler or organic filler are sneaked into cycloolefin type random copolymer compositions as different purposes.For example, they as the flame-proof material that improves the thermotolerance of composition or composition, give that described composition is painted, the rigidity of improving them or suppress purpose such as demoulding post shrinkage factor.The appropriate amount that they use can satisfy according to the needs that composition plans to use.

In second kind of cycloolefin type random copolymer compositions of the present invention, the total amount of non-rigid multipolymer (B) accounts for 1 to 100 part (weight) and accounts for 5 to 50 parts (weight) preferably in cycloolefin type random copolymer (A) 100 parts (weight), preferably account for 5 to 50 parts (weight), the amount of mineral filler or organic filler (C) accounts for 1 to 100 part (weight) in cyclic hydrocarbon type random copolymers (A) 100 parts (weight), be 5 to 100 parts (weight) preferably, preferably account for 5 to 50 parts (weight).Shock-resistance reduces when the total amount of non-rigid multipolymer (B) is less than 1 part (weight) in cycloolefin type random copolymer (A) 100 parts (weight), and rigidity reduction when the total amount of non-rigid multipolymer (B) surpasses 100 parts (weight).

When mineral filler or organic filler (C) amount in cycloolefin type multipolymer (A) 100 parts (weight) surpassed 100 parts (weight), the moldability of composition was degenerated.

Constitute the cycloolefin random copolymer (A) of cycloolefin type random copolymer compositions of the present invention and (B) (ⅰ) all can under appropriate condition, be prepared, make under the Japanese Patent spy opens in clear 168708/1985,120816/1986,115912/1986,115916/1986,95905/1986,95906/1986,271308/1986 and 272216/1986 this condition of method ground of design according to the applicant.

In preparation cycloolefin type random copolymer compositions of the present invention, can use various known methods comprises, as a kind of method be, separately prepare cycloolefin type random copolymer (A) and non-rigid multipolymer (B), the multipolymer (A) that makes and (B) stir by extruding machine then and obtain required composition, a kind of solution blending means is, multipolymer (A) and (B) be dissolved in the suitable solvent respectively fully wherein, for example, such as heptane, hexane, decane, the stable hydrocarbon of hexanaphthene etc., or such as toluene, benzene, the aromatic hydrocarbon of dimethylbenzene etc., and relevant solution mixed obtain required composition, perhaps a kind of method is a multipolymer (A) and (B) prepare separately by the polymerization reactor that separates wherein, and the polymkeric substance of gained mixes with the third container and obtains required composition.

The limiting viscosity [η] that records cycloolefin type random copolymer compositions of the present invention in 130 ℃ of following naphthalanes is in 0.05-10 deciliter/gram scope, be the 0.2-3 deciliter/gram preferably, record the softening temperature (TMA) of described composition in 80-250 ℃ of scope with thermodynamic analyzer, be preferably 100-200 ℃, the glass transition temperature of described composition is 90-210 ℃ preferably in 70-230 ℃ of scope.

Cycloolefin type random copolymer compositions has aforesaid cycloolefin type multipolymer (A) and aforesaid non-rigid multipolymer (B), and described arbitrarily inorganic or organic filler.But, except mentioned component, this composition can with thermo-stabilizer, the Weather-stable agent, antisticking agent, the slippage agent, anti-agglomerating agent, anti-fog agent, lubricant, dyestuff, pigment, natural oil, synthetic oil, wax etc. mix mutually, can suitably determine the consumption of these additives, for example, the blended stablizer comprises that specifically the acids anti-aging agent is as four [3-(3 arbitrarily, the 5-di-tert-butyl-hydroxy phenyl) propionic acid methylene ester] methane, β-(3, the 5-di-tert-butyl-hydroxy phenyl) alkyl propionates, 2, two [the 3-(3 of 2 ' oxamido-, the 5-di-tert-butyl-hydroxy phenyl) ethyl propionate] etc., fatty acid metal salt such as Zinic stearas, Magnesium Stearate, 12-oxystearic acid calcium etc., and the fatty ester of polyvalent alcohol such as glyceryl monostearate, glyceryl monolaurate, distearin, distearyl acid tetramethylolmethane, three tristearin or tetramethylolmethane etc.These compounds can be sneaked into composition with separately or combining.For example, can carry out combination like this, promptly four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid methylene acid esters] methane can with the combining of Magnesium Stearate or glyceryl monostearate etc.

Cycloolefin type random copolymer compositions of the present invention comprises cycloolefin type random copolymer (A), cycloolefin type random copolymer (B) and mineral filler arbitrarily or organic filler, wherein said multipolymer (B) and described mineral filler or organic filler (C) exist with specific amount in described multipolymer (A) 100 parts (weight), and said composition has good thermotolerance, thermal ageing properties, chemical resistant properties, solvent resistance, dielectric characteristics, rigidity and shock-resistance.

Use below the present invention with reference to embodiment and do more detailed elaboration.Various physical propertys pointed among the embodiment are measured or are calculated according to follow procedure.

(1) softening temperature (TMA): make with thermodynamic analyzer TMA10(Seiko Denshi K.K), the hot deformation behavior by the test thin slice of 1 mm thick records softening temperature.That is, vertically be positioned over the loads of using 50 grams on the quartzy pin of test on the thin slice, the speed with 5 ℃/minute of test thin slices heats up simultaneously, the desirable softening temperature (TMA) of doing of temperature that is risen to during 0.1 millimeter of needle penetration test thin slice.

(2) shock strength: with Izod impact test instrument (Toyo Seiki K.K preparation), test film (long: 63.8 millimeters, wide: 12.7 millimeters) is pressed into the thin slice of 2 mm thick, and fluting (0.25 millimeter) is tested under 23 ℃ in the above.

(3) rigidity modulus (modulus in flexure): use Instron tensile tester, test film is (long: 16.8 millimeters, wide: 12.7 millimeters) be pressed into the thin slice of 2 mm thick, comprising that compression speed is 5 millimeters/minute, the distance of upholder is to test under the condition of 32 millimeters and 23 ℃ temperature.

Izod test and pliability test are that carry out 3 days after pressurization.

Polymerization embodiment 1a

Preparation with multipolymer (A) of at least 70 ℃ of softening temperatures

2 liters of glass polymerization reactor of agitating vane are equipped with in employing, in ethene and 1,4,5, and 8-dimethano--1,2,3,4,4a, 5,8, the 8a-octalin (structural formula:

Under be called for short DMON).Here it is, and it is 60 grams per liters that the hexane solution of the DMON that continues to pack in polymerization reactor makes the DMON concentration in polymerization reactor, VO(OC ₂H ₅) Cl ₂Solution be used as catalyzer in the hexanaphthene, as a result the alum concentration of polymerization reactor become 0.9 mmole/liter, a kind of sesquialter ethylaluminium chloride (Al(C ₂H ₅) _1.5Cl _1.5) cyclohexane solution, the result make the aluminum concentration in the polymerization reactor become 7.2 mmoles/liter, make the polymerization liquefaction in the polymerization reactor remain 1 liter yet take polymeric liquid constantly away from the bottom of polymerization reactor.Simultaneously, feed ethene with 85 liters/hour speed, pass to hydrogen with 6 liters/hour speed to the top of polymerization reactor, and with the logical nitrogen of 45 liters/hour speed.When being chilled to 10 ℃ by refrigerant cycle, the outside of polymerization reactor cover one cover that matches carries out copolyreaction.

Interpolymerization is carried out under above-mentioned condition, so can obtain to comprise the polymerization reaction mixture of ethene DMON random copolymers.In the polymerization liquid that takes out from reactor bottom, add a spot of Virahol and stop polyreaction.Then, in the common mixing tank of polymerization liquid impouring one, have polymerization liquid triple acetone in this mixing tank, impeller simultaneously, thus precipitation obtains required multipolymer.Sedimentary multipolymer can be collected by filtering, and is scattered in the acetone, and the concentration that makes polymkeric substance is about 50 grams per liters, and multipolymer was handled 2 hours when the boiling point of propyl alcohol.After carrying out above-mentioned processing, collect multipolymer by filtering, and the dried overnight (12 hours) in the time of 120 ℃ down that reduces pressure.

The ethene DMON-random copolymers (A) that obtains like this ¹³It is 59% that the C-NMR analyser records ethylene unit, and recording its limiting viscosity in 135 ℃ of following naphthalanes is 0.42 deciliter/gram, and its softening temperature (TMA) is 154 ℃.

Polymerization embodiment 1b

Have softening temperature and be at least the preparation of 70 ℃ multipolymer (A)

In embodiment 1b, use with embodiment 1a similar methods and carry out copolyreaction.After copolyreaction fully, the multipolymer of gained is precipitated out, and reclaims throw out and decompression and 120 ℃ of following dried overnight.

The ethene DMON multipolymer (A) that obtains is like this used ¹³It is 59% that the C-NMR analyser records ethylene unit, and recording its limiting viscosity [η] in 135 ℃ of following naphthalanes is 0.60 deciliter/gram, and its softening temperature (TMA) is 111 ℃.

Polymerization embodiment 2

Preparation method with multipolymer (A) of a limiting viscosity [η] is different from the preparation method of multipolymer (A) among the polymerization embodiment 1a

Except DMON in polymerization reactor, VO(OC ₂H ₅) Cl ₂With the feeding speed of the concentration of sesquialter tonsilon lithium and ethene, hydrogen and nitrogen as shown in table 5 outside, other is all identical with polymerization embodiment 1a to continue to carry out identical copolyreaction.Interpolymerization fully after, resulting multipolymer precipitates, and reclaims throw out, and as 1a120 ℃ of polymerization embodiment and decompression under drying 12 hours.The ethene DMON multipolymer (A) that obtains is like this used ¹³It is 58 moles of % that the C-NMR analyser records the unit, and recording its limiting viscosity [η] under 135 ℃ of naphthalanes is 0.94 minute/gram, and softening temperature is 170 ℃

Polymerization embodiment 3

Preparation method with multipolymer (A) of limiting viscosity [η] is not used in the preparation method of multipolymer (A) among the polymerization embodiment 1a

Except the DMON in polymerization reactor, VO(OC ₂H ₅) Cl ₂With the feeding speed of the concentration of sesquialter tonsilon lithium and ethene, hydrogen and nitrogen as shown in table 5 outside, other as polymerization embodiment 1a, carry out same copolyreaction constantly, after interpolymerization is complete, resulting multipolymer precipitates, reclaim throw out and as among the polymerization embodiment 1a under 120 ℃ of decompressions dried overnight (12 hours).The ethene DMON multipolymer (A) of gained is used ¹³It is 67 moles of % that the C-NMR analyser records ethylene unit, and recording limiting viscosity [η] in 135 ℃ of following naphthalanes is 0.60 deciliter/gram, and softening temperature (TMA) is 111 ℃.

Table 5

Polymerization embodiment 2 polymerization embodiment 3

VO（OC ₂H ₅） Cl ₂（mmol/l） 0.9 0.9

Sesquialter tonsilon lithium (mmol/l) 7.2 7.2

The DMON grams per liter) 60 30

Ethene (rise/hour) 100 85

Hydrogen (rise/hour) 0.2 0.2

Nitrogen (rise/hour) 45 45

Polymerization embodiment 4

Have softening temperature and be lower than the preparation of 70 ℃ multipolymer (B)

Except send into DMON, VO(OC to polymerization reactor ₂H ₅) Cl ₂With sesquialter tonsilon lithium, their concentration be followed successively by 15 grams per liters, 0.5 mmole/liter and 4 mmoles/liter, and the speed that feeds ethene, propylene, hydrogen and nitrogen in polymerization reactor is followed successively by 45 liters/hour, 15 liters/hour, 0.2 liter/hour and 25 liters/hour, and polymerization temperature is outside 10 ℃, and other are the same with polymerization embodiment 1a to carry out similar copolyreaction.Interpolymerization fully after, required multipolymer precipitates, collecting precipitation and as among the polymerization embodiment 1a under 120 ℃ and decompression dry 12 hours.

The ethylene, propylene DMON multipolymer of mentioning like this (B) is used ¹³It is that 76 unit mole %, propylene units are 17 moles of % that the C-NMR analyser records ethylene unit, and the limiting viscosity [η] that records in 135 ℃ of following naphthalanes is 0.89 a liter/gram, and softening temperature (TMA) is-10 ℃.

The preparation that polymerization embodiment 5 has the multipolymer (B) of limiting viscosity [η] is different from the preparation of multipolymer among the polymerization embodiment 4 (B)

Except DMON in copolymerization reactor, VO(OC ₂H ₅) Cl ₂With the concentration of sesquialter tonsilon lithium and feed the speed of ethene, propylene, hydrogen and nitrogen as shown in table 6 outside, other carry out the similar copolymer reaction as embodiment 4.Interpolymerization fully after, resulting multipolymer precipitates, collecting precipitation and as polymerization embodiment 1a 120 ℃ of following drying under reduced pressure 12 hours.

The ethylene, propylene DMON multipolymer (B) that obtains is like this used ¹³The ethylene unit that the C-NMR analyser records is 69 moles of %, and propylene units is 21 moles of %, and the limiting viscosity [η] that records in 135 ℃ of following naphthalanes is 1.44 deciliter/gram, and its softening temperature is-4 ℃.

Polymerization embodiment 6

Preparation with multipolymer (B) of limiting viscosity [η] is different from the preparation of polymkeric substance among the polymerization embodiment 4 (B)

Except DMON, VO(OC in the polymerization reactor ₂H ₅) Cl ₂With the concentration of sesquialter tonsilon lithium and feed the speed of ethene, propylene, hydrogen and nitrogen as shown in table 6 outside, other carry out the similar copolyreaction as polymerization embodiment 4.After copolymerization fully, resulting multipolymer precipitates, collecting precipitation and as embodiment 1a 120 ℃ of following drying under reduced pressure 12 hours.

The ethylene, propylene DMON multipolymer (B) that obtains is like this used ¹³The ethylene unit that the C-NMR analyser records is 76 moles of %, and propylene units is 16 moles of %, and the limiting viscosity [η] that records in 135 ℃ of following naphthalanes is 0.98 deciliter/gram, and its softening temperature (TMA) is-8 ℃.

Table 6

Polymerization embodiment 5 polymerization embodiment 6

VO（OC ₂H ₅） Cl ₂（mmol/l） 0.5 0.5

Sesquialter tonsilon lithium (mmol/l) 44

The DMON grams per liter) 20 15

Ethene (rise/hour) 45 45

Propylene (rise/hour) 30 15

Hydrogen (rise/hour) 0.1 0.1

Nitrogen 25 25

Embodiment 1

Pours 2 liters of cyclic ethylenes in multipolymer (B) 15 grams (weight ratio: (A)/(B)=85/15) that in polymerization embodiment 3, obtain among resulting multipolymer (A) 85 gram and the polymerization embodiment 5, and 70 ℃ down dissolving simultaneously fully stirring obtain a kind of uniform solution.Be settled out a kind of (A)/(B) mixture in 2 liters of acetone of the homogeneous solution impouring that obtains like this.The mixture that obtains like this spends the night at 120 ℃ of following drying under reduced pressure.

In (A)/(B) mixture that obtains like this, mix account for resin (A) and (B) four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid methylene radical ester] methane primary of 5% of total amount be stablizer.Mediate the miscellany of being carried with Brabender plastograph down at 190 ℃, and obtain the compacting thin slice that thickness is 2mm at 240 ℃ of dip molds.Trier is made flakiness, and carries out shock test, pliability test and measurement TMB.It is found that it is 40.0 kilograms of cm/that mixture has cantilever-type impact strength, modulus in flexure is 22100 kg/cm, and crooked yield-point should be 830 kg/cm, and softening temperature is 108 ℃.Obtainable like this mixture has good rigidity, thermotolerance and shock strength.

The comparative example 1

Prepared multipolymer (A) obtains the compacting thin slice of 2 mm thick at 240 ℃ of dip molds in polymerization embodiment 3.Trier is made the similar methods measure softening temperature that flakiness carries out shock test, pliability test and uses embodiment 1.It is 2.0 kilograms of cm/that sample is found the beam type intensity that has, and modulus in flexure is 28900 kg/cm, and crooked yield point stress is 870 kg/cm, and softening temperature is 110 ℃.Therefore, though this sample has good rigidity and thermotolerance, its poor impact resistance is also enbrittled.

Embodiment 2 to 4

The multipolymer (B) that makes in the multipolymer that makes among the polymerization embodiment 1a and 3 (A) and polymerization embodiment 4 and 5 mixes as embodiment 1, and its weight ratio is as shown in table 7, and with the identical method assessment of embodiment 1.The result is as shown in table 7.

Comparative example 2 and 3

Polymerization embodiment 1a assesses with embodiment 1 identical method with 2 multipolymers that make (A).The result is as shown in table 7.Though sample has good rigidity and thermotolerance, its shock-resistance is low and be brittle.

Embodiment 5

The multipolymer (B) 20 that multipolymer (A) 80 grams that made by polymerization embodiment 2 and polymerization embodiment 6 make restrain mix in the mixture of forming (weight ratio: (A)/(B)=80/20) account for resin (A) and (B) four [3-(3,5-di-t-butyl-hydroxy phenyl) propionic acid methylene radical ester] methane of 0.5% of total amount as stablizer.This mixture mediates and uses the method identical with embodiment 1 to assess under 190 ℃ with Brabender plastograph.The result is as shown in table 7.Can obtain a kind of composition and have good rigidity, thermotolerance and shock-resistance.

Embodiment 6 and 7

It is as shown in table 7 that the multipolymer (B) that multipolymer (A) and the polymerization embodiment 6 of preparation make among the polymerization embodiment 2 mixes its weight ratio with the method for embodiment 5, and assess with the method for embodiment 5.The result is as shown in table 7.

Embodiment 8 to 15

Multipolymer (A) pointed in the table 8 makes in the method for polymerization embodiment 1a basically, it with table 8 in the multipolymer that in the method for polymerization embodiment 4, makes basically (B) pointed out mix mutually with the method for embodiment 5, its weight ratio is as shown in table 8, and assesses with the method for embodiment 5.

The comparative example 4 to 6

Pointed multipolymer (A) is that the method for following polymerization embodiment 1a makes basically in the table 8, and it is to test like that by comparative example 1.The result is as shown in table 9.Though sample has good rigidity and thermotolerance, their shock-resistance is low, and is brittle.

Embodiment 16

The 90 gram multipolymers (A) and the 10 gram ethylene-propylene random copolymers (B) (ethylene/propene=80/20 mole %) (weight ratio: (A)/(B)=90/10) that will prepare in polymerization embodiment 3 are poured in 2 liters of hexanaphthenes, and in about 70 ℃ of following abundant stirring and dissolving.The homogeneous phase solution of this generation is poured in 2 liters of acetone, and the mixture of a kind of to precipitate (A)/(B), the mixture that obtains thus are under reduced pressure in 120 ℃ of dried overnight.

Should (A)/(B) mixture be attached to 0.05%(based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of gross weight as stablizer.This mixture in 190 ℃ by adopting Brabender plastics meter to knead, and in 240 ℃ of compression moldings to obtain the compressing tablet of 2 millimeters thickness.This compressing tablet is washed into test piece, and the test that experiences a shock, stirring test and TMA measure.Find that should outstandingly with thing cantilever-type impact strength be arranged is 9.4 kilograms of cm/, modulus in flexure is that 23000 kg/cm and TMA are 110 ℃, and resultant mixture all is excellent on rigidity, thermotolerance and shock strength.

The comparative example 7

The multipolymer (A) of preparation carries out compression molding to mention the compressing tablet of 2 millimeters thickness in 240 ℃ in polymerization embodiment 3.Test the test piece that compressing tablets are washed into embodiment 16 identical methods.The cantilever-type impact strength that found that test piece is that 2.0 kilograms of cm/, flexural modulus are 28900 kg/cm, stress in flexible yield-point is that 870 kg/cm and TMA are 110 ℃, yet, the sample shock strength is low, and be crisp, though it is excellent in rigidity and thermotolerance.

Embodiment 17 and 18

The multipolymer (A) and the ethylene propylene copolymer (B) of preparation in polymerization embodiment 3, except multipolymer is with the part by weight mixing pointed in table 10, be method processing and evaluation by embodiment 16, it the results are shown in table 10, and resulting constituent is excellent in rigidity and thermotolerance and shock strength.

Embodiment 19

Pointed prepared multipolymer (A) and the ethene-butene-1 copolymer (B) in polymerization embodiment 3 of table 10 is to mix with the weight ratio that table 10 is given, and handles and estimate with embodiment 16 identical methods.The result shows as table 10.Thereby obtaining a kind of constituent is that excellent its shock strength is higher in rigidity and thermotolerance.

Embodiment 20

The 80 gram multipolymers (A) of pointed preparation in polymerization embodiment 3 and the mixture (weight ratio: (A)/(B)=80/20) of 20 gram ethene-butene-1 copolymers (B) in table 10, join 0.5%(with resin (A) and (B) gross weight serve as that basis four [methylene radical-3-(3,5-two-tertiary butyl-4-hydroxy phenyl) propionic acid] methane is as stablizer.This mixture is kneaded by adopting mine-laying cloth to step on the plastics meter in 190 ℃, and with the identical method evaluation of embodiment 16.It the results are shown in table 10.Resultant a kind of constituent is excellent in rigidity and thermotolerance and shock resistance.

The comparative example 8

To obtain the compressing tablet of 2 millimeters thickness, its evaluation is to adopt to carry out as the same procedure of embodiment 16 to the multipolymer (A) of preparation in 240 ℃ of compression moldings in polymerization embodiment 2.It the results are shown in table 10, found that this sample is low on shock-resistance to be, and is crisp, though it is excellent on rigidity and thermotolerance.

Embodiment 21 and 23

The prepared multipolymer (A) in polymerization embodiment 2 of given weight ratio and the mixture of ethylene propylene copolymer (B) in table 10 are with the method for embodiment 16 and handle and estimate.It the results are shown in table 10, can resulting constituent rigidity and thermotolerance be excellent with and resistance property higher.

Embodiment 24 to 29

Shown in the table 11 is to mix with the weight that the method table 11 of embodiment 20 is given by the multipolymer (A) and the alpha-olefin type random copolymers shown in the table 11 of the method for polymerization embodiment 2 preparation basically, and with the method evaluation of embodiment 20.

The comparative example 9 to 11

The multipolymer of the method preparation of pressing polymerization embodiment 2 basically shown in the table 12 is with comparative example 7 method test.It the results are shown in table 12.Found that sample is low on shock strength, and be crisp, though they are excellent on rigid heat resistant.

Embodiment 30

Will be in polymerization embodiment 1a resulting 90%(weight) ethene polycyclic olefin copolymer in the Henshel mixing machine with 10%(weight) the ethylene, propylene random copolymers that passes through x-ray measurement with 5% crystalline indice (be designated hereinafter simply as EPC-1, a kind of ethylene content is 80 moles of %, and MFR is that 4.6 grams were 0.865 gram/cubic centimetre with density in/10 minutes) mix mutually.This mixture is kneaded and horizontal bar screw extrusion press (temperature is: 230 ℃) extrusion molding by 40 millimeters of φ in fusion, and granulation.This particle is to obtain being used to estimate the test piece of physicals by injection molding (tube temperature: 240 ℃, 70 ℃ of mould temperature).

The test piece that obtains thus is through flexure test (ASTMD790) and arm sling beam type shock test (ASTMD256, undeclared).It the results are shown in table 13.

Embodiment 31

Except adopting 70%(weight) the process of repetition embodiment 30, ethene polycyclic olefin polymkeric substance and 70%(weight) EPC-1 outside, with method same among the embodiment 30, can obtain using the test piece of the crop rational faculty that judges and carrying out flexure test and shock test.It the results are shown in table 13.

Embodiment 32

The ethene 1-butylene random copolymers that has 25% crystallization coefficient except by X-ray measuring the time.Ethylene content is that 92 moles of %, MFR are that 18 grams/10 minutes and density are 0.995 gram/cubic centimetre) replace outside the EPC-1, heavily cover the process of embodiment 30, with the test piece that is used to estimate physicals of method preparation identical among the embodiment 30, and carry out flexure test and Izod impact test.It the results are shown in table 13.

Embodiment 33

Have ethylene, propylene random copolymers (ethylene content is that 40 moles of %, MFR are that 1.0 grams/10 minutes and density are 0.858 gram/cubic centimetre) the replacement EPC-1 of 1% crystallization coefficient except adopting by x-ray measurement, the process of heavily covering embodiment 30 is used to estimate the test piece of physicals with method preparation identical among the embodiment 30, and carrying out flexure test and shock test, it the results are shown in table 13.

Embodiment 34

Heavily cover the process of embodiment 30, but be 15% except adopting crystallization coefficient by X-ray measuring; The ethene butene-1 copolymer of the modification of MFR:5 gram/10.5 replaces EPC-1, and the ethene 1-ethylene copolymer of this modification is to be that 17% ethene 1-butylene random copolymers (ethylene content is that 89 moles of %, MFR are that 4.0/10 parts of grams and density are 0.885 gram/cubic centimetre) obtains by the maleic anhydride graft copolymerization with 0.5 part (weight) at the crystallization coefficient with X-ray measuring of 100 parts (weight).Prepare the test piece that is used to estimate physicals with embodiment 30 same procedure, parallel flexure test and Izod impact test, it the results are shown in table 13.

The comparative example 12

Heavily cover the process of embodiment 30, but except only replacing the constituent of embodiment 30 with ethene polycyclic olefin multipolymer, and with injection-molded to prepare outside the test piece.Carry out flexure test and Izod impact test.It the results are shown in table 13.

Embodiment 35

To in polymerization embodiment 3, restrain ethylene, propylene 2-ethylidene-2-norbornylene random copolymerss (B) (ethylene/propylene/diene=66/33/3 mole %) by resulting 80 gram multipolymers (A) and 20, (weight ratio: (A)/(B)=80/20) pours 2 liters of hexanaphthenes into, and in about 70 ℃ of dissolvings under stirring completely.Resulting homogeneous phase solution is poured into to the 2 upright acetone with deposition (A)/(B) mixture.This mixture spends the night at 120 ℃ of drying under reduced pressure.

(A)/(B) mixture of obtaining thus add with resin (A) and (B) gross weight serve as stablizer among four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of basic 0.5%.Then, this mixture adopts Brabender plastics meter to knead at 190 ℃, and obtains the compressing tablet of 2 millimeters thickness at 240 ℃ of compression moldings.Compressing tablet is washed into test piece, and carries out shock test, flexure test and measure TMA.The cantilever-type impact strength that found that this mixture is 53.4 kilograms of cm/, and modulus in flexure is that the stress of 16000 kg/cm, flexible yield-point is 590 kg/cm.So resultant mixture is excellent in rigidity and thermotolerance and shock strength.

The comparative example 13

By polymerization according to the prepared multipolymer (A) of embodiment 3 at 240 ℃ of pressing molds to obtain the compressing tablet of 2 millimeters thickness.With with embodiment 35 same procedure, this sheet is washed into test piece, and tests.The cantilever-type impact strength that found that this test piece is 20 kilograms of cm/, and flexural modulus is 28900 kg/cm, and the stress of flexible yield-point is that 870 kg/cm and TMA are 111 ℃.Therefore, find that impact strength of samples is low and is crisp, though it is excellent on rigidity and thermotolerance.

Embodiment 36 and 37

Adopt same procedure in embodiment 35 to handle according to the prepared multipolymer (A) of polymerization embodiment 3 and ethylene, propylene 5-second diene-2-norbornylene random copolymers (B) (ethylene/propene /=66/31/3 mole %) with the weight ratio mixture that provides by table 14 and the results are shown in table 14 with it.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

Embodiment 38 and 39

According to the multipolymer (A) and the weight ratio mixture of ethylene, propylene 5-second diene-2-norbornylene random copolymers (B) (ethylene/propylene/diene=67/31/2 mole %) of polymerization embodiment 3 preparations, adopt the same procedure in embodiment 35 to handle and estimate to provide by table 14.It the results are shown in table 14.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

Embodiment 40 and 41

The mixture of the weight ratio of being given with table 14 according to the multipolymer (A) of polymerization embodiment 3 preparation and ethylene, propylene Dicyclopentadiene (DCPD) random copolymers (B) (ethylene/propylene/diene=67/31/1 mole %), and be used in method identical among the embodiment 35 and handle and estimate.It the results are shown in table 14.

Embodiment 42

According to the prepared 80 gram multipolymers (A) and 20 of polymerization embodiment 2 restrain ethylene/propene 5-second diene-2-norbornylene random copolymerss (B) (ethylene/propylene/diene=66/31/3 mole %(weight ratio: (A)/(B)=80/20) be attached to 0.5% based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of gross weight as the mixture of stablizer.This mixture at 190 ℃ by adopting Brabender plastics meter to knead and with the identical method evaluation among the embodiment 35.It the results are shown in table 14.Resultant composition is excellent on rigidity and thermotolerance and shock strength.

The comparative example 14

According to the multipolymer (A) of polymerization embodiment 2 preparation at 240 ℃ of pressing molds to obtain the compressing tablet of 2 millimeters thickness.Prepare test piece, evaluation according to the method identical with embodiment 35, though and find on rigidity and thermotolerance, to be excellent, be low and be crisp in shock strength.

Embodiment 43 and 44

The alpha-olefin diene copolymers (B) that provides according to the multipolymer (A) of polymerization embodiment 2 preparation with at table 14 mixes with the same procedure of embodiment 42, and this mixture is estimated.It the results are shown in table 14.

Embodiment 43 to 50

The mixture of the alpha-olefin-diene elastomer (B) shown in multipolymer shown in the table 15 (A) and the table 15 is handled and is estimated with the method identical with embodiment 42.Resultant constituent is excellent in rigidity and thermotolerance and shock strength.

The comparative example 15 to 17

Multipolymer shown in the table 16 (A) be with the identical method of embodiment 14 is handled and is estimated.It the results are shown in table 16

Embodiment 51

Resulting 90 gram multipolymers (A) and 10 gram styrene-butadiene-styrene block copolymer (B) (density: 0.94 gram/cubic centimetre among the polymerization embodiment 3, trade mark Cariflex TR1102, the product of Shell Kagaku KK) (weight ratio: (A)/(B)=90/10) dry mixture be attached to respectively 0.5% and 0.3% based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of gross weight and dilauryl thiodipropionic acid ester as stablizer.This resulting mixture is kneaded by employing Brabender plastics meter at 190 ℃, and prepare the compressing tablet of 1 millimeter thickness compressing tablet and 2 millimeters thickness respectively in 240 ℃ of compression moldings, these sheet punching out become test piece, and carry out shock test, flexure test and mensuration TMA.

The cantilever-type impact strength that found that mixture is that 5.0 kilograms of cm/, flexural modulus are that 23000 kg/cm and TMA are 111 ℃.Therefore, be excellent with resultant mixture in rigidity and thermotolerance and shock strength.

The comparative example 18

Two kinds of compressing tablets that prepare 1 millimeter and 2 millimeters thickness according to polymerization embodiment 3 prepared multipolymers (A) at 240 ℃ of compression moldings.Test by embodiment 51 same procedure simultaneously.Found that the cantilever-type impact strength of this sample is that 2.0 kilograms of cm/, flexural modulus are 28900 kg/cm, is that 870 kg/cm and TMA are 111 ℃ at the stress of flexible yield-point.Therefore, though it is excellent, find that this sample is low and is crisp in shock resistance on rigidity and thermotolerance.

Embodiment 52 and 53

According to polymerization embodiment 3 resulting multipolymers (A) and styrene-butadiene-styrene block copolymer (B) (density: 0.94 gram/cubic centimetre, trade mark Cariflex TR1102, the product of Shell Kagaku KK) weight ratio is estimated with the same procedure of embodiment 51 by the mixture that table 17 provides.It the results are shown in table 17.Resultant constituent is excellent and impacts strong degree in rigidity and thermotolerance.Embodiment 54

According to polymerization embodiment 3 resulting multipolymers (A) and hydrogenant styrene-butadiene-styrene block copolymer (B) (density: the trade mark 0.90 gram/cubic centimetre): Clayfon G1657, the product of Shell Kagaku KK) ((A)/(B) weight ratio is provided by table 17), mixture, estimate with method identical among the embodiment 51.It the results are shown in table 17, and resultant constituent is excellent in rigidity and thermotolerance and shock strength.

Embodiment 55

According to polymerization embodiment 3 prepared multipolymer (A) and styrene isoprene styrene block copolymer (SIS) (B) (density: 0.92 gram/cubic centimetre, the trade mark: Cariflex TR1107, the product of Shell Kagaku KK) mixture of ((A)/(B) weight ratio is provided by table 17) is estimated with embodiment 51 identical methods.It the results are shown in table 17, and resultant composition is excellent in rigidity and thermotolerance and high shock strength.

Embodiment 56 and 57

According to polymerization embodiment 3 resulting multipolymers (A) and styrene-butadiene copolymer (B) (density: 0.94 gram/cubic centimetre, the trade mark: Nipol 1502, Nippon Geon Co., the product of Ltd) weight ratio of its (A)/(B) is estimated with embodiment 51 identical methods by the mixture that table 17 provides.It the results are shown in table 17, resultant composition on rigidity and thermotolerance and impact intensity be excellent.

Embodiment 58

Estimate with embodiment 51 identical methods according to the prepared multipolymer (A) of polymerization embodiment 2 and the mixture of styrene-butadiene-styrene block copolymer (B) (density: the trade mark: Cariflex 1,102 0.94 gram/cubic centimetre), the product of Shell Kagaku KK) ((A)/(B) weight ratio is provided by table 17).It the results are shown in table 17.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

The comparative example 19

According to the prepared multipolymer (A) of polymerization embodiment 2 at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.To testing from the resulting test piece of compressing tablet.It the results are shown in table 17.They are excellent on rigidity and thermotolerance though found that this sheet, are low in shock strength, and are crisp.

Embodiment 59 and 60

According to embodiment 2 prepared multipolymer (A) and styrene-butadiene-styrene block copolymer (B) (density: 0.90 gram/cubic centimetre, the trade mark: Clayton G 1657, the product of Shell Kagku KK), the weight ratio of its (A)/(B) is estimated with embodiment 51 identical methods by the mixture that table 17 provides.It the results are shown in table 17.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

Embodiment 61 to 66.

Basically estimate with embodiment 51 identical methods with the mixture of vinylbenzene-conjugated diene block copolymer (B) (providing) (weight ratio of (A)/(B) is provided by table 17) according to the multipolymer (A) (form and provide) of the method for polymerization embodiment 1b preparation by table 17 by table 17.It the results are shown in table 17.The composition that draws rigidity and thermotolerance be excellent and shock strength higher.

The comparative example 20 to 22

Basically estimate with comparative example 19 same procedure according to the multipolymer (A) (component is provided by table 17) of the method for polymerization embodiment 1b preparation, it the results are shown in table 17.

Embodiment 67

Resulting 40 gram multipolymers (A) in polymerization embodiment 1b, (contain 80 moles of % ethylene unit and have 15% crystallization coefficient at the prepared 5 gram cycloolefin type random copolymerss (B1) (being designated hereinafter simply as TDR) of polymerization embodiment 5 and 5 gram ethylene-propylene random copolymers (B2) (being designated hereinafter simply as EPR), density is that 0.88 gram/cubic centimetre and limiting viscosity are [η]=2.2dl/g(weight ratio=80/10/10) dry mixture respectively in conjunction with four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl)-propionic acid] methane and dilauryl thiodipropionic acid ester of 0.5% and 0.3% based on resin (A) and gross weight (B).This mixture 190 ℃ by adopting Brabender plastics meter to knead, and in 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.These compressing tablets are washed into test piece, and carry out shock test, flexure test and mensuration TMA.

The cantilever-type impact strength that found that this mixture is 40.2 kilograms of cm/, and flexural modulus is that 1900 kg/cm and TMA are 110 ℃.Resultant mixture is in rigidity and heat-resisting and be excellent in resistance to impact shock.

The comparative example 23

By the prepared multipolymer (A) of polymerization embodiment 3 at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.This sheet is tested with embodiment 67 identical methods.

Found that its cantilever-type impact strength of this sample is that 2.0 kilograms of cm/, modulus in flexure are that 2890 kilograms/cubic centimetre, the stress of flexible yield-point are that 870 kg/cm and TMA are 110 ℃.Though finding this sample is excellent on rigidity and need are hot, shock strength is low and is crisp.

Embodiment 68

By polymerization embodiment 3 prepared multipolymer (A), TDR(B) and styrene-butadiene-styrene block copolymer (being designated hereinafter simply as SBS) (B) (density:: 0.94 gram/cubic centimetre, trade names: Carifex TR1102, Shell Kagaku KK production) mixture of (weight ratio is provided by table 18) is estimated with embodiment 67 identical methods.It the results are shown in table 18, and resultant composition is excellent shock strength in rigidity and thermotolerance.

Embodiment 69

According to the prepared multipolymer (A) of embodiment 3 and ethylene-propylene-diene copolymer [(being designated hereinafter simply as EPDM) (B) (ethylene/propene/5-second diene-2-norbornylene=66/31/3 mole %[η]=2.1dl/g, sulphur value: 22, density, 0.87 mixture gram/square centimeter) is estimated with the same procedure of embodiment 67, (A)/(B) (B) weight ratio provides in table 18.It the results are shown in table 18.Resulting constituent is excellent in rigidity and thermotolerance and shock strength.

Embodiment 70 to 72

Multipolymer (A), EPH(B according to polymerization embodiment 3 preparations) and mixture SBS(B), its weight ratio provides in table 18 with embodiment 67 identical methods and estimates.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

Embodiment 73 to 77

According to polymerization embodiment 2 prepared multipolymer (A), EPDM(B ₁) and SBS(B ₂) mixture, its weight ratio provides in table 18, estimates with embodiment 67 identical methods.It the results are shown in table 18.Resultant composition is excellent in rigidity and thermotolerance and shock strength.

The comparative example 24

According to the prepared copolymer A of polymerization embodiment 2 with the method evaluation identical with comparative example 23.It the results are shown in table 18.Though found that this sample is excellent on rigidity and thermotolerance, shock strength is low, and is crisp.

Embodiment 78 to 80

Basically by the multipolymer that in table 18, shows (A), the EPR(B of the method for polymerization embodiment 1b preparation ₁) and EPDM(B ₂) mixture, its weight ratio is estimated with embodiment 67 identical methods by providing in the table 18.It the results are shown in table 18.Resultant composition is excellent and shock strength is high in rigidity and thermotolerance.

Embodiment 81 and 82

Basically by the copolymer A that in table 18, shows, the EPDM(B of the method for polymerization embodiment 1b preparation ₁) and SBS(B ₂) mixture, its weight ratio is estimated with embodiment 67 identical methods by providing in the table 18.It the results are shown in table 18.Resultant composition is excellent and shock strength is high in rigidity and thermotolerance.

Embodiment 83 and 84

Basically by the method for polymerization embodiment 1b multipolymer (A), TDR(B preparation, that in table 18, show ₁) and SBS(B ₂) mixture, its weight ratio is to estimate with embodiment 67 identical methods by providing in the table 18.It the results are shown in the table 18.The composition that obtains is excellent on rigidity and thermotolerance and shock resistance is high.

The comparative example 25 to 27

Basically the method multipolymer (A) preparation, that show in table 18 by polymerization embodiment 1b is to estimate with comparative example's 23 identical methods.It the results are shown in the table 18.Though found that them is excellent on rigidity and thermotolerance, is low on shock strength and is crisp.

In following embodiment, adopted the strand rope GR-S-3A(GF of the glass roving cut-out of (1) Asahi Fiber Glass) or the white aluminum oxide of Fujimi ^#4000(WA) as stopping composition.

Embodiment 85

Carry out dry blending according to the multipolymer (B) that provides in the multipolymer (A) of polymerization embodiment 3 preparation and the table 19, they are that method by polymerization embodiment 3 is with weight ratio 80/10 preparation basically.The mixture of doing add respectively 0.5% and 0.3% based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of gross weight and dilauryl thiodipropionic acid ester as stablizer.This dry mixture is kneaded in 30 millimeters Bitruders of φ and is carried out dry blending with 10% the GF based on resin (A) and resin (B) gross weight at 220 ℃.Resulting mixture is kneaded in 30 millimeters Bitruders of φ at 220 ℃, and in 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.These sheets are washed into test piece and the test that experiences a shock, flexure test and TMA measure.

The otch cantilevered shock strength of finding this mixture is that 6 kilograms of cm/, initial bending modulus are that 31000 kg/cm and TMA are 113 ℃.Resulting mixture is excellent on rigidity, thermotolerance and shock strength.

The comparative example 28

The multipolymer that in polymerization embodiment 3, obtains (A) at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 mm thick.These compressing tablets are washed into test piece, and the test that experiences a shock, flexure test and TMA measure.

Find that it is that 2 kilograms of cm/, initial deflection modulus are that 28900 kg/cm and TMA are 111 ℃ that test piece has otch cantilevered shock strength.Therefore, the mixture of this sample and embodiment 85 is inferior in shock strength, initial deflection modulus and thermotolerance relatively.

Embodiment 86 and 87

The multipolymer that provides in table 19 (A) and (B) and the mixture of the blending ratio that provides with table 19 of stopping composition (C) is estimated with embodiment 85 identical methods.It the results are shown in table 19.Resultant composition is excellent on rigidity, thermotolerance and shock strength.

Embodiment 88 to 90

The multipolymer that provides in table 19 (A) and (B) and the mixture of the blending ratio that provides with table 19 of stopping composition (C) is with the identical method evaluation of embodiment 85.It the results are shown in table 19.Resultant composition is excellent on rigidity, thermotolerance and shock strength.

The comparative example 29

The multipolymer (A) that provides at table 19 is with the identical method evaluation of comparing embodiment 28.Its result shows as table 19.This sample on rigidity, thermotolerance and shock strength inferior to the mixture of embodiment 88 to 90.

Embodiment 91 to 93

The multipolymer that in table 19, provides (A) and (B) and stopping composition (C) with the mixture of the blending ratio that provides in the table 19, estimate with embodiment 85 identical methods.It the results are shown in table 19.Resultant composition is excellent on rigidity, thermotolerance and shock strength.

The comparative example 30

The multipolymer that provides in table 19 (A) is with the method evaluation identical with comparative example 28.It the results are shown in table 19.This sample on rigidity, thermotolerance and shock strength inferior to the composition of embodiment 91 to 93.

Embodiment 94

Multipolymer that obtains in polymerization embodiment 3 (A) and ethylene, propylene random copolymers (B) (ethylene/propene=80/20 mole %) mix with 80/10 weight ratio.This dry mixture be attached to respectively 0.5% and 0.3% based on four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of resin (A) and gross weight (B) and dilauryl thiodipropionic acid ester as stablizer.Resulting mixture is kneaded in the Bitruder of 30 millimeters of φ at 220 ℃, and and 10% weight based on resin (A) and (B) GF of gross weight carry out dry blend.The miscellany that produces is kneaded in 30 millimeters Bitruders of φ at 240 ℃, and in 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 mm thick.Make test piece from this compressing tablet, and the test that experiences a shock, flexure test and TMA measure.

Found that it is 7 kilograms of cm/that this mixture has otch cantilevered shock strength, the initial deflection modulus is that 30600 kg/cm and TMA are 114 ℃.Resulting mixture is excellent on rigidity, thermotolerance and shock strength.

The comparative example 31

In polymerization embodiment 3 multipolymer (A) of preparation at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 mm thick.These compressing tablets are cut into test piece and the test that experiences a shock, flexure test and TMA measure.

Found that it is that 2 kilograms of cm/, initial deflection modulus are that 28900 kg/cm and TMA are 110 ℃ that this test piece has otch cantilevered shock strength.This sample aspect shock strength, initial deflection modulus and thermotolerance inferior to the composition of embodiment 94.Embodiment 95 and 96

The multipolymer that in table 20, provides (A) and (B) and stopping composition (C) with the mixture of the blending ratio that provides in the table 20 with the identical method evaluation of embodiment 94.It the results are shown in the table 20.Resultant composition is excellent on rigidity, thermotolerance and shock strength.

Embodiment 97 to 99

The multipolymer that in table 20, provides (A) and (B) and stopping composition (C) with the mixture of the blending ratio that provides in the table 20, with the identical method evaluation of embodiment 94.Base the results are shown in the table 20.The composition that obtains is excellent on rigidity, thermotolerance and shock strength.

The comparative example 32

The multipolymer that provides in table 20 (A) is with the identical method evaluation of comparative example 31.It the results are shown in table 20.This sample on rigidity, thermotolerance and shock strength inferior to the mixture of embodiment 97 to 99.

Embodiment 100 to 102

The multipolymer that provides in table 20 (A) and (B) and the mixture of the blending ratio that provides with table 20 of stopping composition (C) is with the identical method evaluation of embodiment 94.It the results are shown in the table 20.Resultant composition is excellent on rigidity, thermotolerance and shock strength.

The comparative example 33

The multipolymer that provides in table 20 (A) is estimated with comparative example's 31 identical methods.It the results are shown in the table 20.This sample aspect rigidity, thermotolerance and shock strength inferior to the mixture of embodiment 100 to 102.

Embodiment 103

The multipolymer that obtains in polymerization embodiment 3 (A) carries out dry blending with the weight ratio of ethylene, propylene 5-second diene-2-norbornylene random copolymers (B) (ethylene/propylene/diene=63/31/3 mole %) with 80/10.This dry mixture be attached to respectively 0.5% and 0.3% based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl) propionic acid] methane of gross weight and dimyrene base thiodipropionic acid ester as stablizer.Resulting mixture and 10% weight based on resin (A) and (B) GF of gross weight carry out dry blending.The dry mixture of Xing Chenging is kneaded in the Bitruder of 30 millimeters of φ in 240 ℃ thus, and in 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.Be cut into test piece from these compressing tablets, and the test that experiences a shock, flexure test and TMA measure.

Found that it is that 8 kilograms of cm/, initial bending modulus are that 31100 kg/cm and TMA are 114 ℃ that this mixture has the notched izod shock strength.Resulting mixture is excellent at rigidity, thermotolerance and shock strength interarea.

The comparative example 34

The copolymer A that in polymerization embodiment 3, obtains at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 mm thick.Make test piece from compressing tablet, and the test that experiences a shock, flexure test and TMA measure.

Found that it is that 2 kilograms of cm/, initial deflection modulus are that 28900 kg/cm and TMA are 111 ℃ that sample has otch cantilevered shock strength.This sample aspect rigidity, initial deflection modulus and thermotolerance inferior to the mixture of embodiment 103.

Embodiment 104 and 105

The multipolymer that in table 21, provides (A) and (B) and stopping composition (C) with the mixture of the weight ratio that provides in the table 21, estimate with embodiment 103 identical methods.It the results are shown in the table 21.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock strength.

Embodiment 106 to 108

The multipolymer that in table 21, provides (A) and (B) and stopping composition (C) with the mixture of the weight ratio that provides in the table 21, estimate with embodiment 103 identical methods.It the results are shown in the table 21.The composition that obtains is excellent on rigidity, thermotolerance and shock strength.

The comparative example 35

The multipolymer that provides in table 21 (A) is estimated with comparative example's 34 identical methods.It the results are shown in the table 21.This sample aspect rigidity, thermotolerance and shock strength inferior to the composition of embodiment 106 to 108.

Embodiment 109 to 111

The multipolymer that provides in table 21 (A) and (B) and the mixture of the ratio of mixture that provides with table 21 of stopping composition (C) is estimated with embodiment 103 identical methods.It the results are shown in the table 21.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock strength.

The comparative example 36

The multipolymer that provides in table 21 (A) is estimated with comparative example's 34 identical methods.It the results are shown in the table 21.This sample aspect rigidity, thermotolerance and shock strength inferior to the composition of embodiment 109 to 111.

Embodiment 112

Multipolymer that obtains in polymerization embodiment 3 (A) and vinylbenzene fourth hexichol styrol copolymer (B) (density: 0.94 gram/cubic centimetre, trade names: Cariflex TR1102, the product of Shell Kagaku KK) carry out dry blending with 80/10 weight ratio.This dry mixture be admixed to respectively 0.5% and 0.3% based on resin (A) and (B) four [methylene radical-3-(3,5-two-Te-butyl-4-hydroxy phenyl)-propionic acid] methane of gross weight and dimyrene base sulphur propionic ester as stablizer.The mixture that is produced is kneaded in the Bitruder of 30 millimeters of φ at 220 ℃, and with 10% based on resin (A) and (B) GF of gross weight carry out dry blending.The dry mixture of Xing Chenging is kneaded in 30 millimeters Bitruders of φ at 220 ℃ then thus, and at 240 compression moldings to prepare the compressing tablet of 1 millimeter and 2 mm thick.Be cut into test piece from these compressing tablets, and the test that experiences a shock, flexure test and TMA measure.

Found that it is that 8 kilograms of cm/, initial deflection modulus are that 31000 kg/cm and TMA are 115 ℃ that said composition has the notched izod shock strength.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock strength.

The comparative example 37

In polymerization embodiment 3 resulting multipolymer (A) at 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.These compressing tablets are cut into test piece and the test that experiences a shock, flexure test and TMA measure.

Find that it is 2 kilograms of cm/that this test piece has otch cantilevered shock strength, the initial deflection modulus is that 28900 kg/cm and TMA are 111 ℃.This sample aspect shock strength, initial bending modulus and thermotolerance inferior to the mixture of embodiment 112.

Embodiment 113 and 114

The multipolymer that in table 22, provides (A) and (B) and stopping composition (C) with the mixture of the blending ratio that provides in the table 22, estimate with embodiment 112 identical methods.It the results are shown in table 22.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock strength.

Embodiment 115 to 117

The multipolymer that in table 22, provides (A) and (B) and stopping composition (C) with the mixture of the blending ratio that provides in the table 22, estimate with embodiment 112 identical methods.It the results are shown in the table 22.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock strength.

The comparative example 38

The multipolymer that provides in table 22 (A) is estimated with method identical among the comparative example 37.It the results are shown in the table 22.This sample aspect rigidity, thermotolerance and shock strength inferior to the composition of embodiment 115 to 117.

Embodiment 118

The multipolymer that in polymerization embodiment 3, obtains (A), cyclenes hydro carbons random copolymers (B) (being designated hereinafter simply as TDR) that in polymerization embodiment 5, obtains and ethylene-propylene random copolymer (B) (being designated hereinafter simply as EPR), containing ethylene unit is 80 moles of %, and to have the crystallization coefficient be 5%, density is that 0.88 gram/cubic centimetre and limiting viscosity [η] are 2.2dl/g(weight ratio=80/5/5) dry mixture, respectively in conjunction with 0.5% and 0.3% with resin (A), (B), (B) gross weight is that four [methylene radical-3-(3,5-spy-butyl-4-hydroxy phenyl) propionic acid] methane on basis and dimyrene base sulphur propionic ester are as stablizer.The GF based on resin (A), (B), (B) gross weight of this dry mixture and 10% weight carries out dry blending.The mixture that produces is kneaded in 30 millimeters Bitruders of φ in 220 ℃, and in 240 ℃ of compression moldings to prepare the compressing tablet of 1 millimeter and 2 millimeters thickness.Be cut into test piece by these compressing tablets, and the test that experiences a shock, flexure test and TMA measure.

In conjunction with finding that said composition has notched impact strength is that 6 kilograms of cm/, initial deflection modulus are that 30900 kg/cm and TMA are 114 ℃.Resultant composition is excellent in rigidity, thermotolerance and shock resistance.

The comparative example 39

In estimating with the compressing tablet for preparing 1 millimeter and 2 mm thick at 240 ℃ of compression moldings, these compressing tablets are washed into test piece and the test that experiences a shock to the multipolymer (A) that obtains in polymerization embodiment 3, and flexure test and TMA measure.

Found that it is that 2 kilograms of cm/, initial deflection modulus are that 28900 kg/cm and TMA are 111 ℃ that this sample has notched impact strength.This sample aspect shock strength, initial bending modulus and thermotolerance inferior to the mixture of embodiment 118.

Embodiment 119

The TDR(B that in multipolymer (A) that polymerization embodiment 3 obtains and table 23, provides), (B) (density: 0.94 gram/cubic centimetre of styrene-butadiene-styrene block copolymer (being designated hereinafter simply as SBS), trade names: Cariflex TR1102, the product of Shell Kagaku KK) and the mixture of GF, the ratio that provides in table 23 is handled and is estimated with the method identical with embodiment 118.It the results are shown in the table 23.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock resistance.

Embodiment 120

The multipolymer that obtains in polymerization embodiment 3 (A) ethylene-propylene-diene copolymer (being designated hereinafter simply as EPDM) is (ethylene/propene/5-second diene-2-norbornylene=66/31/3 mole %, [η]=2.1dl/g (B), iodine number: 22, density: SBS(B 0.87 gram/cubic centimetre)) and the mixture of GF in table 23, to provide the mixture of blending ratio, handle and estimate with embodiment 118 identical methods.It the results are shown in the table 23.Resultant composition is being excellent aspect rigidity, thermotolerance and the shock resistance.

Embodiment 121 to 123

Basically by the multipolymer (A), multipolymer (B) and (B) that in table 23, provide and the ratio of mixture of stopping composition (C) that provide by table 23 of the preparation of the method for polymerization embodiment 3, handle and estimate with embodiment 118 identical methods to provide by table 23.It the results are shown in the table 23.Resultant composition is excellent in rigidity, thermotolerance and shock resistance.The comparative example 40

The multipolymer that provides in table 23 (A) is estimated with comparative example's 39 identical methods.It the results are shown in the table 23.This sample aspect rigidity, thermotolerance and shock strength inferior to the composition of embodiment 121.

Claims

1, a kind of cycloolefin type random copolymerization composition is characterized in that:

(A) cycloolefin type random copolymer by logical formula I or (II) representative of the cycloolefin composition of the ethylene component that contains 40-85 mole % of 100 parts of weight and 60-15 mole %, it has in naphthalane and to be 0.05 to 10 part in the limiting viscosity [η] of 135 ℃ of mensuration and to rise/restrain, softening temperature (TMA) is 100-200 ℃, glass transition temp be 70-210 ℃ and crystalline indice be 0-7% and

(B) be selected from based on one or more of 7-80 part weight of (A) components of 100 parts of weight and comprise following group non-rigid multipolymer:

(i) a kind of cycloolefin type random copolymer that contains the cycloolefin component of 75-98 mole % ethylene component, 1-35 mole % alpha-olefin component and 1-15 mole % by logical formula I or (II) representative, it has, and the limiting viscosity [η] in 135 ℃ of mensuration is lower than 70 ℃ for 0.01-10 deciliter/gram and softening temperature (TMA) in naphthalane

(ii) a kind of non--crystallinity to low crystallinity alpha-olefin type elastocopolymer be selected from 1. have 35 to 50 moles of % of ethylene content be not more than 5% ethylene/propylene olefinic random copolymer with the crystallinity index, and 2. by with being selected from the graft modification multipolymer that unsaturated carboxylic acid and the monomer modified ethylene/alpha-olefin of derivatives graft thereof obtain;

(iii) a kind ofly contain the diene component of 0.5 to 5 mole of % and have the alpha-olefin diene type elastomer copolymer that crystalline indice is 0-5%, system is selected from 1. ethylene/propene/unconjugated cyclic diolefine multipolymer, 2. ethene/1-butylene/unconjugated cyclic diolefine multipolymer and 3. propylene/1-butene/unconjugated cyclic diolefine multipolymer, and (iv) a kind ofly have a 0.80-1.10 gram per centimeter ³The vinylbenzene of density/diene copolymers system is selected from 1. styrene-butadiene copolymer rubber, 2. styrene-butadiene-styrene block copolymer rubber, 3. styrene-isoprene copolymer rubber, 4. styrene isoprene styrene block copolymer (SIS) rubber, 5. hydrogenant styrene-butadiene-styrene block copolymer rubber and hydrogenant styrene isoprene styrene block copolymer (SIS) rubber;

In the formula: n and m respectively are 0 or positive integer, and 1 for being 3 integer at least, and R ¹To R ¹⁰Each represents hydrogen atom, halogen atom or hydrocarbyl group.

2, composition as claimed in claim 1 is characterized in that (i) the described alpha-olefin that is different from ethene in the component (B) at cycloolefin type random copolymer is to be selected from propylene and butylene.

3, composition as claimed in claim 1 is characterized in that described composition further comprises: a kind of inorganic filler or organic filler (C) are with such ratio: (C) component is 1 to 100 part (weight) in the component of per 100 parts (weight) (A).