JPS6411215B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a vulcanized composition of a rubbery ethylene copolymer that has excellent processability and strength properties. There have already been many proposals regarding vulcanized compositions of rubbery copolymers consisting of ethylene, α-olefins having 3 or more carbon atoms, and polyenes. Industrially, ethylene-propylene-polyene rubber-like copolymers have traditionally been considered important, so previous proposals have focused exclusively on ethylene-propylene-polyene copolymers, and therefore fall into the rubber field. Many of the copolymers targeted were those with a content ratio (molar ratio) of ethylene and α-olefin of 85/15 or less. However, rubbery copolymers of ethylene, propylene, and polyene could not be used in fields that require the strength and high performance of raw rubber. As a result of our efforts to obtain a vulcanized composition of ethylene copolymer rubber with excellent strength properties, the present inventors found that α
-Selecting 1-butene as the olefin,
It has been demonstrated that a vulcanized composition of an ethylene copolymer obtained by setting the content ratio of ethylene and α-olefin to a higher ethylene range than the range that has been mainly studied in the past and adopting specific polymerization conditions satisfies the above objectives. I knew. The vulcanized composition of the ethylene copolymer of the present invention, which has particularly excellent strength properties and excellent workability, must satisfy the following conditions. I came to find out something. That is, the present invention comprises [](A) ethylene, 1-butene and a polyene, the polyene being selected from dicyclopentadiene or 5-vinyl-2-norbornene, and (B) ethylene/1-butene (mole ratio) is 86/14
95/5 to 95/5, (C) Iodine number 2 to 40, (D) Intrinsic viscosity [η] measured in decalin at 135°C 1.0 to 4.0 dl/g, (E) Weight average molecular weight/number average molecular weight (Q (F) Ethylene 1 with an ethylene content of 90 mol% showing the same weight average molecular weight (by light scattering method)
- Intrinsic viscosity of butene random copolymer [η] _l
The ratio of [η] to [η]/[η] _l = g ^* 〓 is
0.2 to 0.9, an ethylene/1-butene/polyene copolymer represented by: and a vulcanizing agent. The ethylene copolymer [] blended into the vulcanized composition of the present invention consists of ethylene, 1-butene, and a polyene selected from dicyclopentadiene or 5-vinyl-2-norbornene. Copolymers containing propylene instead of 1-butene are not only hard and have poor elastic properties, but also have poor strength properties. Furthermore, by selecting dicyclopentadiene or 5-vinyl-2-norbornene as the polyene, even if the molecular weight distribution is narrow, g ^* 〓 will be within the above range, resulting in a copolymer with good processability. Content ratio of ethylene/1-butene (mole ratio)
is from 86/14 to 95/5, preferably from 87/13 to 94/6. The content of polyene is such that the iodine value is 2 to 40, preferably 2 to 30, and is usually 1 to 30 in the copolymer.
It is about 20% by weight, especially about 1 to 15% by weight.
Copolymers with an ethylene content less than the above range have low strength, and copolymers with an ethylene content above the above range are hard and have poor elastic properties. Further, when the iodine value of the copolymer is within the above range, the vulcanization rate is fast and the physical properties of the vulcanized rubber are also favorable. The ethylene copolymer has an intrinsic viscosity of 1.0 to 4.0 dl/g, particularly preferably 1.0 to 3.0 dl/g, as measured in decalin at 135°C. Since the intrinsic viscosity is within the above range, both processability and strength properties are good. The ethylene copolymer must have a weight average molecular weight/number average molecular weight (Q amount) in order to have good strength properties.
must be less than 3, preferably between 2.5 and 2.9. The Q value is measured as follows according to "Gel Permeation Chromatography" written by Takeuchi and published by Maruzen. (1) Using standard polystyrene with a known molecular weight (manufactured by Toyo Soda Co., Ltd., monodispersed polystyrene), 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. (iv) Thereafter, it is filtered through a 1μ Millipore filter at 135°C to 140°C. (e) Apply the filtrate to GPC. GPC measurement conditions It was carried out under the following conditions. (a) Equipment Wester 200 type (b) Column Toyo Soda S-type (Mix type) (c) Sample amount 2ml (d) Temperature 135℃ (e) Flow rate 1ml/min Total number of theoretical plates of column 2 ×10 ⁴ to 4 × 10 ⁴ (measured value in acetone) The ethylene copolymer has a weight average molecular weight <M> _W (light scattering method ). To express this in another way, the intrinsic viscosity of the copolymer of the present invention is [η] (measured at 135°C in decalin),
When the weight average molecular weight at that time is <M> _W ,
<M> Linear ethylene/1-butene random copolymer with a molecular weight of _W (ethylene content 90 mol%)
Let the intrinsic viscosity of [η] _l be ([η] _l =7.60×10 ^-4 〈M
〉
^0.664 _W ) [η]/[η] When defined as _l = g ^* 〓, g ^* 〓 is 0.2 to 0.9, preferably 0.3 to
It is in the range of 0.8. The ethylene/1-butene random copolymer was prepared by mixing ethylene and 1-butene in hexane using VOCl ₃ and ethylaluminum sesquihalide.
- Obtained by copolymerizing butene. As mentioned above, the fact that g ^* 〓 shows a value considerably smaller than 1 suggests the existence of a cross-linked structure in addition to short chain branching due to 1-butene, which is a copolymerization component with ethylene. This shows the difference from conventional ethylene copolymers which have only short chain branches. However, the copolymers of the present invention are not highly crosslinked because they are soluble in boiling hexane. Since g ^* 〓 exhibits a value considerably smaller than 1 in this way, the processability (extrudability) is good despite the small Q value. If g ^* 〓 exceeds 0.9, workability is poor. The quality of the extrudability was determined by using a capillary flow tester to test the copolymer rubber under two different extrusion stresses (S ₁ = 1 x 10 ⁶ dyne/cm ² , S ₂ = 1 x 10 ⁵ dyne/cm 2 ).
cm ² ) at 100°C for a certain period of time to determine the respective extrusion amounts M ₁ and M ₂ , and I value (extrudability index) =
It is calculated as M ₁ /M ₂ . Here, the larger the I value, the better the extrudability. The ethylene copolymer also has a normal JISA hardness.
It ranges from about 50 to 85. In addition, the stress at break measured based on JIS K6301 is usually 30Kg/cm ² or more,
The elongation at break is usually 200 to 2000%. Vulcanizing agent blended into the vulcanizing composition of the present invention []
Sulfur compounds such as peroxide, sulfur, sulfur monochloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, magnesium oxide, zinc white, Examples include metal compounds such as red lead. Among these, sulfur or peroxide is preferred. When performing sulfur vulcanization, sulfur is usually added to 100 parts by weight of the rubber component.
It is used in a proportion of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight. Further, a vulcanization accelerator can be used if necessary. As the vulcanization accelerator, N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N,N-diisopropyl-2-benzothiazole-sulfenamide, 2-mercaptobenzothiazole, 2-
Thiazoles such as (2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio)benzothiazole, and benzothiazyl-disulfide; diphenylguanidine, triphenylguanidine, di-ortho-tolylguanidine , orthotolyl biguanide, guanidine-based products such as diphenylguanidine phthalate; acetaldehyde-aniline reaction products; aldehyde amines such as butyraldehyde-aniline condensates, hexamethylenetetramine, acetaldehyde ammonia, or aldehyde-
Ammonia type; Imidazoline type such as 2-mercaptoimidazoline; Thiourea type such as thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, di-ortho-tolylthiourea; Tetramethylthiuram monosulfide, tetramethylthiuram disulfide Thiuram series such as hydride, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, dipentane methylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, ethyl thiuram Examples include dithioate salts such as zinc enyldithiocarbamate, zinc butylphenyldithiocarbamate, residual sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, and tellurium diethyldithiocarbamate; xanthate systems such as zinc dibutylxanthate; and the like. These vulcanization accelerators are generally 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 of the rubber component. Other types of vulcanizing agents that may be incorporated into the vulcanizing compositions of the present invention include peroxides. Peroxides used for this purpose include dicumyl peroxide, 1,1'-di(t-
butylperoxy)-3,3,5-trimethylcyclohexane, di-(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,
Examples include 5-di-(t-butylperoxy)hexane. In addition, as a vulcanizing agent at that time, sulfur, sulfur compounds such as dipentane methylene thiuram tetrasulfide, polyfunctional compounds such as ethylene dimethacrylate, divinylbenzene, diallyl phthalate, metaphenylene bismaleimide, and toluylene bismaleimide are used. oxime compounds such as p-quinone dioxium and p,p'-dibenzoylquinone oxime can be used alone or in combination. When performing the above vulcanization, other additives such as activators, dispersants, fillers, plasticizers, tackifiers, colorants, foaming agents, foaming aids, lubricants, anti-aging agents, and other additives may be added 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 oils, lubricating oils, 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, palmitic 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. Foaming aids such as sulfonyl hydrazide, toluenesulfonylhydrazide, calcium azide, para-toluenesulfonyl azide,
Phthalic acid, urea, etc. can be used. Although it varies depending on the type of vulcanizing agent, the temperature is usually 100 to 250℃, preferably 120 to 200℃.
It is recommended that the treatment be carried out for 10 to 60 minutes, preferably 20 to 40 minutes. In particular, when peroxide vulcanization is performed, the vulcanization time is preferably about four times the half-life of the peroxide. The vulcanized composition of the present invention has, for example, roll processability,
It also has excellent extrusion processability. Furthermore, even if the filler is added in an amount larger than the maximum amount allowed depending on the purpose of use of the conventional ethylene-propylene-polyene copolymer rubber vulcanizate, the ethylene copolymer of the present invention cannot be vulcanized. The material has high strength, so conventional ethylene
Vulcanization having a practical strength equivalent to that of a vulcanized composition of propylene/polyene copolymer rubber can be obtained, and therefore a vulcanized product can be produced at a lower cost. Especially calcium carbonate, which is extremely cheap among fillers.
Non-reinforcing fillers such as talc and clay usually reduce the strength of vulcanizates, but even if a large amount of such fillers are added to the vulcanized composition of the ethylene copolymer of the present invention, the strength does not decrease. Conventional ethylene
A vulcanizate having the same strength as propylene/polyene copolymer rubber can be produced at an extremely low cost. Therefore, with the vulcanized composition of the ethylene copolymer of the present invention, a high-strength vulcanized product can be obtained by appropriately selecting the type and amount of filler, and it is possible to obtain a vulcanized product with high strength by appropriately selecting the type and amount of filler. A vulcanizate having the same strength as a rubber vulcanizate can be obtained at a lower cost, and the vulcanizate also has rubber-like properties. The vulcanized composition of the ethylene copolymer of the present invention is usually 100 kg/kg even when no filler is added.
cm ² or more, especially tensile strength of 120Kg/cm ² or more and 200%
In particular, it shows a growth of more than 300%. When a filler is added, the properties are further improved. In particular, from the vulcanized composition of the ethylene copolymer of the present invention, an excellent insulating layer can be obtained by covering the current-carrying part of a power transmission wire in a cylindrical shape by a commonly employed known method. In other words, the insulation layer of power transmission wires, especially high-voltage power transmission wires of 10,000 volts or more, is required to have a high level of electrical properties and strength, but the dielectric loss tangent (%) of the insulation layer
In order to make the vulcanized composition of the copolymer of the present invention less than 0.3, a conductive wire that can be used as a current-carrying part of the wire even if the amount of softener, plasticizer, and filler added to the vulcanized composition of the copolymer of the present invention is reduced is compounded in an extruder. During the extrusion process in which the rubber is covered in a cylindrical shape, the outer surface of the cylinder maintains sufficient smoothness, so the resulting insulating layer has sufficient AC breakdown voltage resistance and is resistant to tensile stress during vulcanization. Combined with the advantage of having a strength at break of 100 kg/cm ² or more, it is extremely excellent as an insulating layer for high-voltage power transmission lines, and functions as an insulating layer for high-voltage power transmission of up to 70,000 volts. With conventional vulcanized compositions of ethylene-propylene-polyene copolymer rubber, it is not possible to obtain an insulating layer that satisfies all of strength, processability, and electrical properties in a well-balanced manner. The limit was that it could be used for insulating layers. When producing an insulating layer for power transmission wires from the vulcanized composition of the ethylene copolymer of the present invention, the amount of filler is 50 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight of the copolymer of the present invention. The blending amount is 30 parts by weight or less, and the amount of softener and/or plasticizer is 7 parts by weight or less, preferably 5 parts by weight or less. In addition, low-voltage power transmission wires, insulating layers of marine wires, insulating layers of automobile ignition cables, plug caps, ignition caps,
Electrical insulating parts around automobile engines, such as distributor caps, and general insulating electrical parts, such as condenser caps and cable joint covers, are not required to have very high electrical properties, and the filler of the present invention can be used as a filler. The blending amount is appropriately selected within the range of 250 parts by weight at most for the copolymer and 100 parts by weight for the softener and/or plasticizer depending on the strength required for the above-mentioned part. Of course, in the case of such an electrical insulating material, the solid volume resistivity is preferably 1×10 ¹⁴ Ω・cm or more, so it is preferable to use a filler with non-electrical properties as a filler, and it is unavoidable to use carbon. If black is used, it should be used in an amount of not more than 25 parts by weight, preferably not more than 5 parts by weight, based on 100 parts by weight of the copolymer. Furthermore, automobile exterior parts such as bumpers, bumper fillers, bumper rub stops, hover riders, and side protection moldings can be manufactured from the vulcanized composition of the ethylene copolymer of the present invention, and these have high strength and heat resistance. It has excellent weather resistance and rubber-like properties. In this case, based on 100 parts by weight of the ethylene copolymer of the present invention, a softener or
And when the amount of plasticizer is X parts by weight and the amount of filler is Y parts by weight, 0≦X+Y≦300 and 0
≦X≦75, preferably 0≦X+Y≦250 and 0≦
It is preferable to satisfy X≦50. Furthermore, hoses, sheets for roofing, gaskets, etc. can be manufactured from the vulcanized composition of the ethylene copolymer of the present invention. In addition, by blending a foaming agent and vulcanizing and foaming, the foam has a specific gravity strength defined as TB/D, where the strength at break is TB (Kg/m ² ) and the apparent specific gravity strength is D. Flexible foams are obtained and are used for thermal insulation, electrical insulation, flotation materials, cushioning materials, soundproofing materials, etc., and foams made from polyethylene foam and ethylene-propylene-polyene copolymer rubber are used. It can fill in the middle area. The ethylene copolymer constituting the vulcanized composition of the present invention is prepared in a hydrocarbon medium by (a) VO(OR) _o X _3-o (wherein R is a hydrocarbon group,
X is a halogen, a vanadium compound represented by the formula 0<n≦3) and (b) R′mAlX′ _3-n (wherein R′ is a hydrocarbon group,
X′ is formed from a halogen and an organoaluminum compound represented by 1<m<1.5), and in the presence of a catalyst having an Al/V (molar ratio) of 5 or more, at a temperature of 40°C to 100°C,
The content ratio (mole ratio) of ethylene and 1-butene is
It can be obtained by copolymerizing ethylene, 1-butene, and the above-mentioned polyene so that the iodine value is 86/14 to 95/5 and the iodine value is 2 to 40. In the vanadium compound represented by the above general formula, R is an aliphatic, alicyclic or aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, usually having 1 to 20 carbon atoms, particularly preferably 1 to 20 carbon atoms. 3. Also, n is 0<n≦3, preferably 1
The range is ≦n≦1.5. Specific examples of vanadium compounds represented by the above general formula include VO( _OCH3 ) _Cl2 , VO( _OCH3 ) _2Cl ,
VO( _OCH3 ) ₃ , VO( _OCH2H5 ) _{Cl2 ,} VO( _{OC2H5 )
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 (OC―
C ₄ H ₉ ) ₂ Cl, VO (OisoC ₄ H ₉ ) ₂ Cl, VO
Examples include (OsecC ₄ H ₉ ) ₃ , VO(OC ₅ H ₁₁ ) _1.5 Cl _1.5 or a mixture thereof. these are
Reacting VOCl ₃ with alcohol, or
It can be easily obtained by reacting VOCl3 and VO(OR _{)3 .} In the above formula of the organoaluminum compound, m is 1 and
1.5, particularly preferably in the range 1.2≦m≦1.4. The organoaluminum compound is, for example,
R′AlX′ ₂ and R′ _1.5 AlX′ _1.5 and or R′ ₂ AlX′,
It is prepared by mixing so that the average composition is as shown in the above formula. Of course, m
The R′s need not be the same. in particular,
A mixture of C ₂ H ₅ AlCl ₂ and (C ₂ H ₅ ) _1.5 AlCl _1.5 in arbitrary proportions, isoC ₄ H ₉ A mixture of AlCl ₂ and (isoC ₄ H ₉ ) _1.5 AlCl _1.5 in arbitrary proportions, C ₂ H ₅ AlCl ₂ and (isoC ₄ H ₉ ) _1.5 AlCl _1.5
For example, a mixture of the following in any ratio can be used. The ratio of the organoaluminum compound to the vanadium compound used is such that Al/V (molar ratio) is 5 or more, preferably 30 or less, and particularly preferably 7 to 20. Copolymerization is carried out in a hydrocarbon medium. For example, hexane, heptane, octane, dodecane,
Aliphatic hydrocarbons such as kerosene, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene may be used alone or in combination as a solvent. Or 1
- An excess of butene 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 0.01 to 5 mmol/, preferably 0.1 to 2 mmol/. Further, the organoaluminum compound is prepared so that the Al/V (molar ratio) is 5 or more, preferably 30 or less, and particularly preferably 7 to 20, as described above. Polymerization temperature is 40 to 100℃,
Preferably the temperature is 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 . For controlling the molecular weight of the copolymer rubber, a molecular weight controlling agent such as hydrogen may be present as appropriate. Next, an example will be explained. Example 1 A ternary copolymerization reaction of ethylene, 1-butene, 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 (prepared in a catalyst preparation container so that the molar ratio of vanadium oxytrichloride to ethyl alcohol was 1/1) was added in a polymerization vessel. (B) A mixture of ethylaluminum sesquichloride [(C ₂ H ₅ ) _1.5 AlCl _1.5 ] and ethylaluminum dichloride [(C ₂ H ₅ )AlCl ₂ ] (ethyl (The molar ratio of aluminum sesquichloride and ethylaluminum dichloride was prepared to be 7/3) were continuously introduced into the polymerization vessel from the top of the polymerization vessel so that the concentration of aluminum atoms in the polymerization vessel was 7.0 mmol/. supplied.
Additionally, a mixed gas of ethylene and 1-butene (55 mol% ethylene, 45 mol% 1-butene) was fed from the top of the polymerization vessel at a rate of 650 mol/hour, and hydrogen gas as a molecular weight regulator was fed at a rate of 1.3/hour. Dicyclopentadiene is 30g/hour from the top of the polymerization vessel.
Continuously feed at a speed of 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 7.2 Kg/cm ² (gauge). When the copolymerization reaction is carried out under the conditions described above, an ethylene/1-butene/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 separated from the solvent by steam stripping treatment, and then dried under reduced pressure at 80°C overnight. Through the above operations, an ethylene/1-butene/dicyclopentadiene copolymer was obtained at a rate of 315 g/hour. The ethylene content of the copolymer measured by infrared absorption spectroscopy was 90.2 mol%, the intrinsic viscosity [η] measured in decalin at 135°C was 1.34 dl/g, the iodine value was 9.6, the Q value was 2.7, and the g ^* 〓0.62. Ta. A 1 mm thick sheet made of this copolymer based on JIS K6758 has a stress at break of 92 Kg/cm ² and an elongation at break of 1080%, measured based on JIS K6301.
It had a JISA hardness of 73. In addition, the I value (extrudability index) of this copolymer is 55
It was hot. Furthermore, 100 parts by weight of copolymer, 5 parts by weight of zinc white,
1.5 parts by weight of stearic acid, 55 parts by weight of carbon black (Seest H; manufactured by Tokai Carbon), naphthenic oil (Sansen 4240; manufactured by Nippon Sun Oil Co., Ltd.)
10 parts by weight, 0.5 2-mercaptobenzothiazole
Parts by weight, tetramethylthiuram monosulfide
A blend was prepared by kneading 1.5 parts by weight of sulfur and 1.0 parts by weight using 8-inch open rolls at a roll temperature of 50°C for 30 minutes. The resulting compound was then press-vulcanized at 160° C. for 30 minutes, and the resulting vulcanizate was subjected to a tensile test according to JIS K6301. The vulcanized physical properties were 300% modulus 155 Kg/cm ² , stress at break 294 Kg/cm ² , elongation at break 500%, and JISA hardness 84. Further, a pure rubber compound obtained by removing carbon black and naphthenic oil from the above-mentioned compound system was similarly press-cured at 160° C. for 30 minutes, and the resulting vulcanizate was subjected to a tensile test according to JIS K6301. Vulcanized physical properties are stress at break 250Kg/cm ² and elongation at break.
It was 680%. Examples 2 to 5, Comparative Examples 1 to 9 In Example 1, copolymers with different properties were obtained by changing various polymerization conditions. The obtained copolymer was evaluated in the same manner as in Example 1. Polymerization conditions, copolymer properties, etc. are shown in Tables 1 and 2.

【table】

[Table] 〓Ethylene + 1-butene〓
Methyl-1-pentene

【table】

[Table] Example 6 Copolymer of Example 1, Example 3, and Example 4 800
Using g, according to the recipe shown in Table 3, 8
With inch open roll, roll temperature 75℃/
The mixture was kneaded at 80°C (front roll/back roll) for 20 minutes to obtain an unvulcanized compounded rubber. This compounded rubber was heated under a pressure of 150 kg/cm ² for 30 minutes using a press heated to 160°C to form a 14 cm x 12 cm
A vulcanized sheet with a thickness of 2 mm was produced. JIS No. 3 dumbbells were punched out from this sheet and pulled at a tensile speed of 500 in an atmosphere of 25℃ according to the method specified in JIS K6301.
The stress at break TB (Kg/cm ² ) and elongation at break EB (%) were measured using mm/min. In addition, the hardness HS (JIS A) was measured according to the same JIS regulations. In addition, a sample was taken from the vulcanized sheet and the AC breakdown voltage and dielectric loss tangent at 25°C and 500V were measured using the Schering-Prisisi method at a voltage increase rate of 1KV/sec. Separately, the unvulcanized compounded rubber is processed using a 50mmφ extruder (L/
D = 10, compression ratio = 6, Garvey dye),
The appearance of the surface of the strands obtained by extrusion at an extrusion temperature of 105° C. and a rotational speed of 40 rpm was observed, and the extrusion texture was evaluated in five grades as an index of extrusion processability. 5... No surface irregularities at all, good gloss 4... Almost no surface irregularities, no gloss 3... Slight surface irregularities, no gloss 2... Surface irregularities, no gloss 1... Large surface irregularities, No gloss at all The above results are shown in Table 4.

【table】

【table】

Claims (1)

[Claims] 1 [] (A) consisting of ethylene, 1-butene and a polyene, the polyene being selected from dicyclopentadiene or 5-vinyl-2-norbornene, (B) ethylene/1-butene (mole ratio) is 86/14
95/5 to 95/5, (C) Iodine number 2 to 40, (D) Intrinsic viscosity [η] measured in decalin at 135°C 1.0 to 4.0 dl/g, (E) Weight average molecular weight/number average molecular weight (Q (F) Ethylene 1 with an ethylene content of 90 mol% showing the same weight average molecular weight (by light scattering method)
- Intrinsic viscosity of butene random copolymer [η] _l
The ratio of [η] to [η]/[η] _l = g ^* 〓 is
0.2 to 0.9, an ethylene/1-butene/polyene copolymer represented by: and a vulcanizing agent.