JPS627223B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vulcanized composition of ethylene/α-olefin/polyene copolymer rubber, and more specifically to a vulcanized composition of terpolymer rubber having a wide molecular weight distribution and a unique polyene distribution. be. Generally, vulcanized compositions of ethylene/α-olefin/polyene ternary copolymer rubber such as ethylene/propylene/polyene ternary copolymer rubber and ethylene/1-butene/polyene ternary copolymer rubber are weather resistant and ozone resistant. Because it has excellent properties such as hardness and heat resistance, it is known to be used in automobile materials, electric wire materials, building materials, industrial materials, plastic blend materials, etc. As for the physical properties required of the vulcanized composition of ethylene/α-olefin/polyene copolymer rubber used for such uses, it is desirable that the composition has excellent processability and, at the same time, excellent vulcanization physical properties. It is well known that a broad molecular weight distribution is necessary for good processability. However, according to the methods that have been shown in the literature, ethylene
If we widen the molecular weight distribution to improve the processability of α-olefin/polyene copolymer rubber, its vulcanized properties will significantly deteriorate; on the other hand, the only way to improve the vulcanized properties is to narrow the molecular weight distribution. However, there was no known means for obtaining an ethylene/α-olefin/polyene copolymer rubber that had poor processability and had excellent processability and vulcanizable properties at the same time. As a result of studying a manufacturing method for obtaining a copolymer rubber with excellent vulcanizable properties and processability, the present inventors discovered that the objective could be achieved by adopting very limited polymerization conditions. I learned. Such a copolymer rubber is characterized by a wide molecular weight distribution, a high polyene content in the high molecular weight component, and a low polyene content in the low molecular weight component. In conventional copolymer rubbers, as the molecular weight distribution becomes wider, the amount of polyene in the high molecular weight component decreases, which is extremely lower than the average polyene content in the copolymer rubber. The properties of rubber can be said to be unique, and the vulcanized composition of the copolymer rubber is also unique in that it has excellent physical properties and processability. That is, according to the present invention, (i) (A) consists of ethylene, an α-olefin having 3 to 10 carbon atoms, and a polyene; (B) ethylene/the above α-olefin (molar ratio);
is 50/50 to 95/5, (C) Iodine number is 5 to 50, (D) Intrinsic viscosity measured in decalin at 135°C is
1.0 to 6.0 dl/g, (E) Q value (weight average molecular weight/number average molecular weight) is 3 to 15, (F) Iodine value index α ₁ of low molecular weight component and iodine value index α ₂ of high molecular weight component A vulcanized composition of an ethylene copolymer rubber is provided, which contains a random ethylene copolymer rubber with −10.0≦α ₁ ≦0.0 and 0.0≦α ₂ ≦10.0, respectively, and (ii) a vulcanizing agent. 3 to 10 carbon atoms which is a constituent component of the random ethylene copolymer rubber constituting the vulcanized composition of the present invention
Examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and mixtures thereof. A particularly preferred α-olefin is propylene or 1
-Butene. In addition, as a polyene component of copolymer rubber,
1,4-hexadiene, 1,6-octadiene,
2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-
linear non-conjugated dienes such as octadiene, cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinylnorbornene,
5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-
Cyclic non-conjugated dienes such as 2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,
Representative examples include trienes such as 2-norbornadiene, 1,3,7-octatriene, and 1,4,9-decatriene. Suitable polyenes are cyclic non-conjugated dienes, especially dicyclopentadiene or 5-ethylidene-2-norbornene. The ratio (mole ratio) of ethylene and α-olefin in the copolymer rubber is in the range of 50/50 to 95/5, and is selected so that the copolymer has rubbery properties. If the ethylene content is less than 50 mol% in the above ratio, a vulcanized rubber with good vulcanized physical properties cannot be obtained, so it is not preferable. The preferred range of the above ratio varies depending on the type of α-olefin; for example, when the α-olefin is propylene, the above ratio is usually 50/50 to 90/10, particularly 60/40 to 87/13, α- When the olefin has 4 or more carbon atoms, the above ratio is usually 80/20 or
95/5, especially 85/15 to 95/5 is preferred. Note that these content ratios can be determined from absorbance measurement using an infrared spectrophotometer or intensity measurement using a ¹³ CNMR spectrometer. The polyene content in the copolymer rubber can be adjusted depending on the iodine value, and the iodine value is usually 5 to 5.
50, preferably 5 to 40. If the iodine value is less than 5, a sufficient vulcanization effect will not be observed, and if the iodine value is more than 50, gel will likely occur during polymerization. If the molecular weight of the random ethylene copolymer rubber constituting the vulcanized composition of the present invention is less than [η] = 1, it will be difficult to roll it, and if it exceeds [η] = 6, it will be difficult to calender it, and furthermore, it will be extruded. For reasons such as irritation of the skin, the intrinsic viscosity [η] measured in decalin at 135° C. by a multi-point method is usually 1.0 to 6.0 dl/g, preferably 1.2 to 4.0 dl/g. The molecular weight distribution of the random ethylene copolymer rubber constituting the vulcanized composition of the present invention is an important factor that indicates the difficulty of processability, and the Q value described below is usually in the range of 3 to 15, preferably 4 to 12. It's summery. The Q value was measured as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Maruzen. (1) Using standard polystyrene with a known molecular weight (monodispersed polystyrene manufactured by Toyo Soda Co., Ltd.), calculate the molecular weight M and its GPC (Gel Permeation
Chromatograph) count and create a correlation diagram (calibration curve) between molecular weight M and EV (Elution Volume). The concentration at this time is 0.02wt%. (2) Obtain a GPC pattern of the sample using the GPC measurement method, and find M using the above (1). The sample preparation conditions and GPC measurement conditions at that time are as follows. <Sample Preparation> (a) Aliquot the sample into an Erlenmeyer flask together with o-dichlorobenzene solvent to a concentration of 0.04 wt%. (b) Add 0.1 wt% of the anti-aging agent 2,6-di-tert-butyl-p-cresol to the polymer solution to the Erlenmeyer flask containing the sample. (c) Heat the Erlenmeyer flask to 140°C and stir for about 30 minutes to dissolve. (d) Then, pass through a 1 μm Millipore filter at 135°C to 140°C. (e) Apply the liquid to GPC. <GPC measurement conditions> Measurement was carried out under the following conditions. (a) Equipment 200 type (b) manufactured by Waters Co. Column S-type (Mix type) manufactured by Toyo Soda (c) Sample amount 2 ml (d) Flow rate 1 ml/in (e) Temperature 135°C Copolymer rubber of the present invention The most important point is that
The iodine value index α ₁ of the low molecular weight component and the iodine value index α ₂ of the high molecular weight component satisfy the following formula. That is, −10.0≦α ₁ ≦0.0, 0.0≦α ₂ ≦10.0, preferably −10.0≦α ₁ ≦−0.5, 0.5≦α ₂ ≦10.0, particularly preferably −10.0≦α _{1 ≦} −1.0, 1.0 The range is ≦α ₂ ≦10.0. Here, the low molecular weight component, high molecular weight component, and iodine value index α ₁ and α ₂ are defined by the following explanation. (1) Separate the copolymer rubber into 12 to 20 fractions by column fractionation. Measure the iodine number and intrinsic viscosity of each fraction. The separation conditions are as follows. (a) 100-200 mesh glass beads 800-
Coat 10-15 g of sample in 1000 ml. (b) Toluene/acetone = 80/ as elution solvent
Using a 20Vol% mixed solvent, the temperature was raised stepwise from 0℃ to 55℃, and 2 fractions were added as 1 fraction.
Take ~3 elution solutions. If it is necessary to elute at a temperature of 55°C or higher, elute with toluene solvent. (c) After concentrating the eluate to an appropriate amount, precipitate it in methanol, vacuum dry the precipitate, and measure its weight. (2) Create a cumulative curve in order of molecular weight of the fractionated products, and divide into three parts: 20 wt% on the low molecular weight side, 20 wt% on the high molecular weight side, and the remaining 60 wt%. When the component on the low molecular weight side is L and the component on the high molecular weight side is H,
Measure the iodine value and molecular weight of each. (3) Let the iodine value of L be I _L and the iodine value of H be I _H , and let the average iodine value of the sample be. Then, the molecular weight of L is M _L , the average molecular weight is M H , and the molecular weight of H is M _H
When , α ₁ =I _L −, α ₂ =I _H − are defined. At this time, the relationship M _L << M _H is satisfied. Most of the conventionally proposed ethylene/α-olefin/polyene copolymer rubbers with a wide molecular weight distribution have α ₁ of 1 or more and α ₂ of −1.0 or less, and even those with a narrow molecular weight distribution have α ₁ of 0. larger and α ₂ is smaller than 0, both of which are α ₁
was larger than _α2 . Such copolymer rubbers do not have excellent processability or vulcanizable properties. To produce the random ethylene copolymer rubber constituting the vulcanized composition of the present invention, (a) VO(OR) _o X _3-
o (However _, R is an aliphatic hydrocarbon _group , , X′ is formed from a halogen, an organoaluminum compound represented by 1.0<p≦1.25), and
Ethylene,
An α-olefin having 3 to 10 carbon atoms and a polyene may be copolymerized. Specific examples of vanadium compounds represented by the above general formula include VO( _OCH3 ) _Cl2 , VO( _OCH3 ) _2Cl ,
VO( _OCH3 ) ₃ , VO( _OC2H5 ) _{Cl2 ,} VO
(OC ₂ H ₅ ) ₁ . ₅ Cl ₁ . ₅ , VO (OC ₂ H ₅ ) ₂ Cl, VO
(OC ₂ H ₅ ) ₃ , VO ( _{OC 2} H ₅ ) _{1.5 Br 1.5 ,} VO
(OC ₃ H ₇ ) _{Cl 2} , VO ( _{OC 3} H ₇ ) _1.5 Cl _1.5 , VO
(OC ₃ H ₇ ) ₂ Cl, VO (OC ₃ H ₇ ) ₃ , VO (On-C ₄ H ₉ )
Cl ₂ , VO (On-C ₄ C ₉ ) ₂ Cl, VO (O-
isoC ₄ H ₉ ) ₂ Cl, VO (O-secC ₄ H ₉ ) ₃ , VO
Examples include (OC ₅ H _{11 ) 1.5} Cl _1.5 or a mixture thereof _. Among these, those in which n in the above formula is in the range of 1≦n≦2 are particularly preferred, and vanadium compounds in which R is C ₂ H ₅ are especially preferred. These are for example VOCl ₃
and alcohol, or VOCl ₃
It can be easily produced by reacting with VO(OR) ₃ . Even if VOCl ₃ or VCl ₄ is used instead of such a vanadium compound, the desired results cannot be obtained. In copolymerization, the type of organoaluminum compound and the amount used are also important. That is,
As the organic aluminum compound, it is necessary to use those shown in (b) above. In the above formula, 1.0<
Must be p≦1.25, preferably 1.0<
p<1.20. Even if p≦1.0 in the above formula is used as the organoaluminum compound, it is not preferable because a gel is formed during polymerization and the vulcanized physical properties are also deteriorated.
If a copolymer rubber having a large molecular weight distribution (Q value) is used, it is not possible to obtain a copolymer rubber having a large molecular weight distribution (Q value). (b) above
The organoaluminum compound represented by . for example
R′ ₁ . ₅ AlX′ ₁ . ₅ and R′AlX′ ₂ or R′AlX′ ₂ and
R′ ₂ AlX′, or R′AlX _{′ 2 and} R′ _1.5 AlX′ _1.5
R′ ₂ AlX′ may be mixed and used in a ratio such that the average composition is shown in formula (b). In the formula, R' represents an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, etc., and is particularly preferably an alkyl group having 1 to 6 carbon atoms, and X' represents fluorine, chlorine, bromine or iodine, Particularly preferred is chlorine. More specifically, the proportion that satisfies the above formula is
_{A mixture of C2H5AlCl2 and} ( _{C2H5 ) 1.5AlCl1.5 ,}
A mixture _of isoC ₄ H ₉ AlCl ₂ and (isoC ₄ H _{9 ) 1.5 AlCl 1.5} ,
Examples include a mixture _of (C ₂ H _{5 )} AlCl and (isoC ₄ H ₉ ) _1.5 AlCl _1.5 . In order to obtain the copolymer rubber, the ratio of the organic aluminum compound and the bahadium compound used is important, and it is desirable that Al/V (atomic ratio) be 2 or more and less than 5. When the Al/V (atomic ratio) is less than 2, there are many disadvantages in the polymerization operation, such as the formation of a solvent-insoluble gel-like copolymer during polymerization, and the resulting copolymer rubber has a poor polyene distribution. It has the following drawback. When Al/V (atomic ratio) is 5 or more, the catalyst activity is low and the molecular weight distribution Q
The drawback is that it is difficult to obtain a copolymer rubber with a large value. In the copolymerization of the present invention, 40 to 100°C,
Excellent results are obtained when the copolymerization is carried out preferably at a polymerization temperature of 50 to 80°C. Preferably, the copolymerization is carried out in an inert solvent.
For example, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, kerosene, alicyclic hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene, toluene, xylene, ethyl chloride, chloro Halogenated hydrocarbons such as benzene can be used alone or in combination as a solvent. Alternatively, an excess of α-olefin may be used as the reaction medium. The copolymerization is preferably carried out at a concentration of the vanadium compound in the reaction medium of from 0.01 to 5 mmol/, in particular from 0.1 to 2 mmol/. Further, the organoaluminum compound is used in a ratio such that the Al/V (atomic ratio) is 2 or more and less than 5, as described above. The polymerization temperature is maintained at 40 to 100°C, preferably 50 to 80°C, and the polymerization pressure is generally maintained at 0 to 50 Kg/cm ² , preferably 0 to 20 Kg/cm ² . The copolymerization can be carried out either batchwise or continuously, but in order to obtain a copolymerized rubber having the above-mentioned properties, it is preferable to carry out the copolymerization continuously. In that case, the average residence time in the polymerization tank should be
It is preferably about 300 minutes, particularly about 10 to 250 minutes. The copolymerization is also preferably carried out under conditions such that the copolymerized rubber is soluble in the reaction medium. The intrinsic viscosity and ethylene content of the copolymer rubber can be controlled primarily by varying the hydrogen concentration used for molecular weight control and the ratio of ethylene to α-olefin in the monomer mixture to be reacted. I can do it. In the vulcanized composition of the present invention, the random ethylene copolymer rubber can be used in fields where vulcanized rubber has conventionally been used by vulcanizing it as it is or by mixing it with other synthetic rubber or natural rubber. I can do it. The vulcanizing agents constituting the vulcanizing composition of the present invention include peroxide, sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dimethyldithiocarbamine. Examples include sulfur compounds such as selenium oxide, and metal compounds such as magnesium oxide, zinc white, and red lead. Sulfur is usually 0.1 to 10 parts by weight per 100 parts by weight of the rubber component.
It is used in proportions by weight, preferably from 0.5 to 5 parts by weight. Additionally, a vulcanization accelerator can be used if necessary. As a vulcanization accelerator, N-cyclohexyl-2-benzothiazole-sulfenamide,
N-oxydiethylene-2-benzothiazole-
Sulfenamide, N,N-diisopropyl-2
-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2
- Thiazoles such as (2,6-diethyl-4-morpholinothio)benzothiazole and benzothiazyl-disulfide; diphenylguanidine, dolphenylguanidine, di-orthotolylguanidine, orthotolyl biguanide, diphenylguanidine phthalate, etc. Guanidine series;
Acetaldehyde-aniline reaction product; Butyraldehyde-aniline condensate; Aldehyde amine such as hexamethylenetetramine, acetaldehyde ammonia, or aldehyde-ammonia system; 2
- Imidazolines such as mercaptoimidazoline; thiocarbanilide, diethylthiourea, thiourea series such as dibutylthiourea, trimethylthiourea, di-ortho-tolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram Thiuram series such as disulfide, tetrabutylthiuram disulfide, dipentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, di-n-
Dithioate salts such as zinc butyldithiocarbamate, zinc ethyl phenyl dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate; xanthate systems such as zinc dibutylxanthate; etc. can be mentioned. These vulcanization accelerators are the ethylene copolymer rubber components.
It is usually used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight per 100 parts by weight. Peroxides used in peroxide vulcanization include dicumyl peroxide, 1,1′-di(t-
butylperoxy)-3,3,5-trimethylcyclohexane, di(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5
-di(t-butylperoxy)hexane, 2,5
-dimethyl-2,5-di(t-butylperoxy)hexyne and the like. In addition, as a vulcanization aid at that time, sulfur, sulfur compounds such as dipentamethylenethiuram tetrasulfide, polyesters such as ethylene dimethacrylate, divinylbenzene, diallyl phthalate, metaphenylene bismaleimide, and toluylene bismaleimide are used. Functional monomer, p-quinone dioxime,
Oxime compounds such as p,p'-dibenzoylquinone oxime can be used alone or in combination. The vulcanized composition of the present invention may contain other additives such as activators, dispersants, fillers, plasticizers, tackifiers, colorants, foaming agents, foaming aids, lubricants, anti-aging agents, and other additives as necessary. Can be used together. Examples of fillers include inorganic fillers such as carbon black, white carbon (silicic acid compounds), calcium carbonate, talc, and clay; high styrene resins, coumaron indene resins, phenolic resins, lignin, modified melamine resins, petroleum resins, etc. Mention may be made of organic fillers. Among these, inorganic fillers are particularly preferably used. Softeners include process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum softeners such as petrolatum; coal tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fatty oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, valmitic acid, barium stearate, calcium stearate, and zinc laurate; petroleum Examples include synthetic polymeric substances such as resins. Plasticizers include phthalate esters, adipate esters, sebacate esters, phosphoric acid, etc. Tackifiers include coumaron indene resin, terpene/phenol resin, xylene/
Colorants such as formalin resin, inorganic and organic pigments, blowing agents such as sodium bicarbonate, ammonium carbonate, N,N'-dinitrosopentamethylenetetramine, azocarbonamide, azobisisobutyronitrile, benzene. Sulfonyl hydrazide, toluenesulfonyl hydrazide, calcium amide, para-toluenesulfonyl azide, etc. As the foaming aid, salicylic acid, phthalic acid, urea, etc. can be used. Further, the compound can be manufactured by a known method using an open roll mill, a Banbury mixer, a kneader, or the like. Vulcanization method is usually 100℃~250℃, preferably 120℃
At a temperature of ℃ ~ 200℃, vulcanization time usually 10 minutes ~ 60 minutes,
Preferably, it can be carried out for 20 minutes or 40 minutes. In particular, when performing peroxide vulcanization, the vulcanization time is preferably about four times the half-life of the peroxide. Next, the present invention will be explained in more detail with reference to examples. Example 1 A ternary copolymerization reaction of ethylene, propylene, and dicyclopentadiene was continuously carried out using 15 stainless steel polymerization vessels equipped with stirring blades. That is, hexane is continuously supplied as a polymerization solvent from the top of the polymerization vessel at a rate of 5 per hour. On the other hand, the polymerization liquid is continuously drawn out from the lower part of the polymerization vessel so that the polymerization liquid in the polymerization vessel is always 5. As a catalyst, (A) a reaction product of vanadium oxytrichloride and ethyl alcohol (the molar ratio of vanadium oxytrichloride and ethyl alcohol was adjusted to 1/1 in the catalyst adjustment vessel) was added to the polymerization vessel. Also, (B) ethylaluminum sesquichloride [(C ₂ H ₅ ) _{1.5 AlCl 1.5} ] and ethyl aluminum dichloride [(C _{2 H 5 )} AlCl ₂ ] (the molar ratio of ethylaluminum sesquichloride and ethylaluminum dichloride is 3/7)
) was adjusted so that the concentration of aluminum atoms in the polymerization vessel was 2.4 mmol/
Each was continuously supplied into the polymerization vessel from the upper part of the polymerization vessel. In addition, a mixed gas of ethylene and propylene (36 mol% ethylene, propylene
64 mol%) at a rate of 610 per hour, and hydrogen gas as a molecular weight regulator at a rate of 1.0 per hour. Dicyclopentadiene is continuously fed from the top of the polymerization vessel at a rate of 25 g/hour. The copolymerization reaction was carried out at 60°C by circulating hot water through a jacket attached to the outside of the polymerization vessel. In this case, the pressure inside the polymerization vessel was 8 Kg/cm ² (gauge). When the copolymerization reaction is carried out under the conditions described above, an ethylene-propylene-dicyclopentadiene copolymer can be obtained in a uniform solution state. A small amount of methanol was added to the polymerization liquid taken out from the bottom of the polymerization vessel to stop the polymerization reaction, and the polymer was taken out by steam stripping treatment, and then heated to 80°C.
It was dried under reduced pressure for one day and night. Through the above operations, an ethylene-propylene-dicyclopentadiene copolymer was obtained at a rate of 300 g/hour. The ethylene content of the copolymer measured by infrared absorption spectroscopy was 72.2 mol%, the intrinsic viscosity [η] measured in decalin at 135°C was 2.25 dl/g,
The iodine value was 9.5. 100 parts by weight of the obtained copolymer, 5 parts by weight of zinc white, 1.5 parts by weight of stearic acid, 65 parts by weight of carbon black (SEAST H: manufactured by Tokai Carbon Co., Ltd.), naphthenic oil (Sansen 4240, manufactured by Nippon Sun Oil Co., Ltd.) 30 parts by weight, 0.5 parts by weight of 2-mercaptone benzothiazole, 1.5 parts by weight of tetramethylthiuram monosulfide, and 1.5 parts by weight of sulfur.
Roll temperature 50℃ using 8 inch open roll
A mixture was prepared by kneading for 30 minutes. At this time, the state of biting and winding of the compound into the roll was observed, and the roll processability was evaluated on a 5-point scale.5: The rubber band was in complete contact with the roll, and the bank was rotating smoothly. 4...The band sometimes separates from the roll surface between the top of the roll and the bank. 3...The band separates from the roll surface between the top of the roll and the bank. 2...The band does not come into close contact with the roll surface, and the roll cannot be processed without touching it with your hands. 1...The band does not come into close contact with the roll surface at all, and roll processing cannot be performed unless the band is attached with a hanging hand. I went there. The roll processability in this example was 5. Also, with a capillary flow tester
The extrudability of the compound was observed at 80℃, and the extruded skin was evaluated on a five-point scale as an index of processability. 5... No surface unevenness at all, good gloss 4... Almost no surface unevenness, no gloss 3... Surface unevenness Slightly uneven, no gloss 2: Surface unevenness, no gloss 1: Large surface unevenness, no gloss at all. The extrudability in this example was 5. As a result of characterizing the obtained polymer, the iodine value index α ₁ and α ₂ were −2.5 and +3.5, respectively, and the molecular weight distribution Q value measured by GPC was 6.2. Next, the obtained compound was press-vulcanized at 160° C. for 30 minutes, and the obtained vulcanizate was subjected to a tensile test according to JIS K6301. The vulcanized physical properties were 300% modulus of 150 Kg/cm ² , tensile strength of 250 Kg/cm ² and elongation of 440%. Examples 2 to 15, Comparative Examples 1 to 13 The polymerization was carried out in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 1. The obtained copolymer was prepared in Example 1.
The same formulation as above was carried out, the processability was determined, and the material was vulcanized in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 2.

【table】

【table】

[Table] Example 16 In Example 1, instead of dicyclopentadiene, 5-ethylidene-2- was added at a rate of 28 g/hour.
The supply of norbornene was changed, and a mixed gas of ethylene and propylene (45 mol% ethylene, 55 mol% propylene) was supplied from the top of the polymerization reactor at a rate of 550 mol% per hour.
The same operation was repeated except that hydrogen gas was supplied at a rate of 2.0 g/hour, and a copolymer was obtained at a rate of 340 g/hour. The copolymer had an ethylene content of 76.1 mol%, an intrinsic viscosity [η] of 1.59 dl/g, and an iodine value of 14.2. Characterization was carried out in the same manner as in Example 1, and the iodine value indices α ₁ and α ₂ were -2.3 and +3.6, respectively, and the Q value of the molecular weight distribution by GPC was 6.4. A blend of the obtained copolymer was prepared in the same manner as in Example 1. As a result of evaluating roll processability and extrudability in the same manner as in Example 1, both scores were 5. Furthermore, the obtained formulation was heated to 160℃.
Press vulcanize for 30 minutes, and the resulting vulcanizate is JIS
A tensile test was conducted using K6301. The physical properties of vulcanization are
300% modulus 152Kg/cm ² , tensile strength 248Kg/cm ² ,
The growth was 460%. Example 17 In Example 1, 5-ethylidene-2-norbornene was supplied at a rate of 28 g/hour instead of dicyclopentadiene, and the vanadium atomic concentration in the polymerization vessel was 0.4 mmol/hour and the aluminum atomic concentration was 1.6. A mixed gas of ethylene and propylene (51 mol% ethylene, 49 mol% propylene) was supplied from the top of the polymerization vessel at a rate of 490 mmol/hour, and hydrogen gas was further supplied at a rate of 3.8 mmol/hour. The same operation was repeated except that the copolymer was fed at a rate of 300 g/hour. The ethylene content of the copolymer is 81.6 mol%, the intrinsic viscosity [η] 1.44 dl/g, the iodine value 16.8, and α ₁ =-
2.1, α ₂ =+3.2, and Q value was 5.8. A blend of the obtained copolymer was prepared in the same manner as in Example 1. As a result of evaluating roll processability and extrudability in the same manner as in Example 1, both scores were 5. Furthermore, the obtained formulation was heated to 160℃.
Press vulcanize for 30 minutes, and the resulting vulcanizate is JIS
A tensile test was conducted using K6301. The physical properties of vulcanization are
300% modulus 163Kg/cm ² , tensile strength 265Kg/cm ² ,
The growth was 430%. Example 18 In Example 1, dicyclopentadiene was changed to be fed at a rate of 31 g/hour, and a mixed gas of ethylene and 1-butene (53 mol% ethylene, 47 mol% 1-butene) was introduced from the top of the polymerization vessel. 650 per hour
The same operation was repeated except that hydrogen gas was supplied at a rate of 0.5 g/hour, and a copolymer was obtained at a rate of 275 g/hour. The copolymer had an ethylene content of 88.7 mol%, an intrinsic viscosity [η] of 1.04 dl/g, and an iodine value of 9.3. In this case, α ₁ =−2.2 and α ₂ =+3.0. Moreover, the Q value was 5.9. A blend of the obtained copolymer was prepared in the same manner as in Example 1. As a result of evaluating roll processability and extrudability in the same manner as in Example 1, both scores were 5. Furthermore, the obtained formulation was heated to 160℃.
Press vulcanize for 30 minutes, and the resulting vulcanizate is JIS
A tensile test was conducted using K6301. The physical properties of vulcanization are
300% modulus 173Kg/cm ² , tensile strength 278Kg/cm ² ,
The growth was 430%. Example 19 In Example 1, instead of dicyclopentadiene, 5-ethylidene-2-
Norbornene was supplied, the vanadium atom concentration in the polymerization vessel was changed to 1.0 mmol/, the aluminum atom concentration was changed to 4.0 mmol/, and a mixed gas of ethylene and propylene (30 mol% ethylene, 30 mol% ethylene, The same operation was repeated except that propylene (70 mol%) was supplied at a rate of 600 g/hr, and hydrogen gas was supplied at a rate of 3.8 g/hr to obtain a copolymer at a rate of 280 g/hr. . The ethylene content of the copolymer is 64.8 mol%,
The intrinsic viscosity [η] was 1.30 dl/g and the iodine value was 22.8. In this case, α ₁ = −3.0 and α ₂ = +3.5
It was hot. Moreover, the Q value was 6.1. A blend of the obtained copolymer was prepared in the same manner as in Example 1. As a result of evaluating roll processability and extrudability in the same manner as in Example 1, both scores were 5. Further, the obtained formulation was heated at 160℃ for 30
Press vulcanize for a minute, and the resulting vulcanizate is JIS K6301
A tensile test was conducted using Vulcanized physical properties are 300%
Modulus 120Kg/cm ² , Tensile strength 235Kg/cm ² , Elongation
It was 460%. Example 20 The same operation as in Example 1 was repeated except that hydrogen gas was supplied at a rate of 0.8 g/hr, and a copolymer was obtained at a rate of 280 g/hr. The copolymer had an ethylene content of 71.5 mol%, an intrinsic viscosity [η] of 3.14 dl/g, and an iodine value of 9.7.
In this case, α ₁ =−2.0 and α ₂ =+2.5.
Moreover, the Q value was 6.8. A blend of the obtained copolymer was prepared in the same manner as in Example 1. As a result of evaluating roll processability and extrudability in the same manner as in Example 1, both scores were 5. Furthermore, the obtained formulation was heated to 160℃.
Press vulcanize for 30 minutes, and the resulting vulcanizate is JIS
A tensile test was conducted using K6301. Vulcanized physical properties are
300% modulus 150Kg/cm ² , tensile strength 263Kg/cm ² ,
The growth was 430%. Examples 21-22 The same procedure as in Example 1 was carried out except that the polymerization conditions were changed as shown in Table 3. The obtained copolymer was vulcanized in the same manner as in Example 1, and its physical properties were measured. The results are shown in Table 4.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (i) (A) consisting of ethylene, an α-olefin having 3 to 10 carbon atoms, and a polyene; (B) ethylene/the above α-olefin (molar ratio)
50/50 to 95/5, (C) Iodine value 5 to 50, (D) Intrinsic viscosity measured in decalin at 135°C
1.0 to 6.0 dl/g, (E) Q value (weight average molecular weight/number average molecular weight) is 3 to 15, (F) Iodine value index α ₁ of low molecular weight component and iodine value number α ₂ of high molecular weight component A vulcanized composition of an ethylene copolymer rubber, comprising: a random ethylene copolymer rubber in which −10.0≦α ₁ ≦0.0 and 0.0≦α ₂ ≦10.0, respectively, and (ii) a vulcanizing agent. 2. The vulcanized composition according to claim 1, wherein the ethylene copolymer rubber has a Q value of 4 to 12. 3. The vulcanized composition according to claim 1, wherein α ₁ and α ₂ of the ethylene copolymer rubber are −10.0≦α ₁ ≦−1.0 and 1.0≦α ₂ ≦10.0, respectively. 4 The α-olefin of ethylene copolymer rubber is propylene, and the ethylene/propylene (molar ratio)
50/50 to 90/10. 5 α-olefin of ethylene copolymer rubber is 1-
Butene, ethylene/1-butene (mole ratio)
The vulcanized composition according to claim 1, wherein the ratio is from 80/20 to 95/5. 6. The vulcanized composition according to claim 1, wherein the polyene of the ethylene copolymer rubber is a non-conjugated diene. 7. The vulcanized composition according to claim 6, wherein the non-conjugated diene of the ethylene copolymer rubber is a cyclic non-conjugated diene. 8 The cyclic nonconjugated diene of ethylene copolymer rubber is
The vulcanized composition according to claim 7, which is 5-ethylidene-2-norbornene or dicyclopentadiene.