JPS5936151A - Cocurable rubber composition - Google Patents

Abstract

PURPOSE:To provide a rubber composition cocurable with any accelerator, capable of giving cocured products of high mechanical strength, comprising a specific proportion of EPDM and specific conjugated diene (co)polymer rubber. CONSTITUTION:The objective composition comprising (A) an ethylene-propylene- nonconjugated diene copolymer rubber and (B) a conjugated diene (co)polymer rubber with the carbon-carbon double bond content of the side chain accounting for >=40wt% (pref. 50-99wt%) in the conjugated diene in such amounts that the weight ratio (A)/(B) falls between 95/5 and 55/45. The component (B) can be prepared by the anionic polymerization of a conjugated diene alone or its mixture containing <=50wt% of an aromatic vinyl compound, using an organolithium compound as initiator and a Lewis based as cocatalyst.

Description

[Detailed description of the invention]

The present invention utilizes ethylene-propylene-nonconjugated tsene copolymer rubber (hereinafter abbreviated as EPDM) and conjugated diene (co)
The present invention relates to a vulcanizable rubber composition comprising a polymer rubber. The deficiencies in ozone resistance, weather resistance, and iJ heat resistance found in conventional conjugated diene (co)polymers such as polyliptadiene rubber, polyisofluorene rubber, and styrene-butadiene rubber can be solved by blending EPDM, which has outstanding performance in these properties. It is supplemented by sulfurization. On the other hand, in order to compensate for the disadvantages of EPDM such as adhesion, the above conjugated diene (co)polymer rubber may be blended entirely. Window frames, heat-resistant hoses, etc. are examples of practical applications in which ozone resistance, weather resistance, heat resistance, adhesiveness, etc. are imparted by blending these EPDMs with conjugated/zo-carbon yarn (co)polymer rubber. However, in this case, the mechanical strength of the blended rubber does not reach the arithmetic average value of both of the single rubbers and decreases, which poses a major practical obstacle. In particular, the tendency for squeezing to occur is remarkable in the region where the ratio of EPDM is high in the blend ratio of EPDM and conjugated diene (co)n (combined rubber). Due to the lack of action and the different solubility of the rubbers of both the vulcanizing agent and the vulcanization accelerator, it is difficult to uniformly co-vulcanize a blend of the two. Wide EPDM and conjugated diene (
It is desirable to provide a covulcanizate which is capable of covulcanization of blends with co)polymer rubbers and has good mechanical strength. Another object of the present invention is to blend EPDM and a conjugated diene (co)polymer rubber at an EPDM II latch ratio to maintain the superiority of its vulcanizable properties, without selecting a specific vulcanization accelerator. The object of the present invention is to provide a rubber composition that is capable of co-vulcanization. The present invention comprises (A) an ethylene-pyrene-nonconjugated diene copolymer rubber and (B) a conjugated diene (co)polymer rubber having at least 40% carbon-carbon double bonds in the side chains of the molecule, The present invention relates to a rubber composition capable of co-vulcanization, characterized in that the weight ratio of component (A) to component (B) is in the range of 95:5 to 55:45. The FJP DM used in the present invention is - [lIi Example Eva, ethylene-propylene di/chloro and entadiene copolymer, ethylene-7') robylene-5-ethylidene-2-norbornene copolymer, ethylene-propylene 1.
4-hexazene conjugate, 1,000-propylene-5
-Bu,. Examples include -2-norbornene copolymer. The conjugated diene (co)polymer rubbers used include conjugated diene (co)polymer rubbers containing 4% or more of 50 polymers of aromatic vinyl monomers, such as polybutadiene rubber,
Examples include polyisogrene rubber, butadiene-isoprene rubber, styrene-phtadiene rubber, styrene-isoprene rubber, and styrene-butadiene-ingrene rubber. In the present invention, the carbon-carbon bicar bond shoulder line of the molecular side chain in the conjugated diene part of the conjugated diene nail base body comb is at least 40%, preferably 50%. Again”-
For eyes, 99% is preferred. By setting the content to 40% or more, the effects of the present invention can be obtained without using a specific vulcanization accelerator. Furthermore, if the aromatic vinyl content exceeds 5() mass ratio, the properties of the rubber composition will not be lost and the elongation will be extremely low. In this
It means a bond and a 3,4 bond. The conjugated diene (co)polymer rubber in the present invention is produced by using an inorganic lithium compound as a vehicle starting material (c) and a Lewis base such as an ether or a tertiary amine as a co-catalyst. It can be obtained by anionically polymerizing a conjugated diene mixture containing at least 100% of diene. Conjugated diene and (-7, for example, butadiene, imprene, etc. are used, and aromatic vinyl monomers include styrene, (ethylnutyrene, p-methylstyrene, vinyl toluene, etc., and styrene is preferred.) Polymerization Examples of initiators include alkyllithiums, such as n-butyllithium, (8)-butyllithium, te
Monolithium compounds such as rt-butyllithium and amyllithium, and dilithium compounds such as tetramethylene dilithium are preferably used. Examples of Lewis bases include monoethers and polyethers such as tetrahydrofuran, dioxane, dimethoxyethane, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether, as well as triethylamine and tributylamino N. N,N',N'-tetramethylethylenediamine, ta3R amine, hexamethylphosphorimide, and the like are used. Particularly suitable are tetrahydro7rane, ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and N,N,N',N'-tetramethylethylenecyane. The desired microstructure of the conjugated diene (co)polymer of the present invention,
That is, the amount of carbon-carbon double bond gold in the molecular side button can be obtained by appropriately adjusting the type and amount of Lewis base or the polymerization temperature. In the combination reaction, a solvent is also used as necessary. As the solvent, a solvent inert to the lithium compound is used, and toluene, benzene, cyclohexane, hezotane, hexane, etc. are preferably used. The lubricant base is used in an amount of 0.05 mol to 2000 mol based on lithium. For example, when using die=r-lene glycol dimeralyl, -Del Fc as the Lewis base, the amount used is 0.
．． 5 to 10 mol is particularly desirable. The undercarriage temperature is usually preferably -20°C or higher. History 0-15
0°C is more preferred in practice. The polymerization method is - constant temperature v(
: It can be carried out under controlled conditions, still initially at low temperature and then at elevated temperature. Further, the conjugated diene (co)polymer of the present invention may be a polymer having a bond between a metal such as silicon, kermanium, or tin and carbon in the main chain of the molecule. In order to incorporate a polymer that breaks the bonds between metals such as silicon, kermanium, and tin and carbon into the main chain of the molecule, for example, the living organisms generated in the anionic polymerization using the Tr-lithium catalytic converter W are used. Coupling reaction between the end of the 71 coalescence and a silicide (obtained from C). Examples include kermanium tetrachloride.The mixing ratio of the rubber composition EPDM of the present invention and the conjugated diene (co)polymer rubber is 95 to 5515 to 45 in terms of gravity. If the rubber composition exceeds 55%, the effect of the present invention cannot be obtained, and if it is less than 55 wt. equipment, e.g. turnon roll, panha 11
- Raw rubber and various commonly used compounding agents can be mixed using mixers, kneaders, extruders, etc. The comb composition of the present invention is capable of being vulcanized under commonly used vulcanization accelerators and under vulcanization conditions F, without depending on a specific vulcanization accelerator. The rubber composition of the present invention takes advantage of its characteristics to be used in window frames, door sealing materials, door coverings, side heating hoses (radiator hoses, heater hoses, etc.), heat-resistant belts, electric current bale hoses, roofings, J-Ther I Lip,
Can be applied to tire → noid walls and other industrial products. Next, the present invention will be explained in more detail with reference to Examples. The microstructure of the conjugated diene (co)polymer rubber used in the same example was determined by the infrared absorption spectroscopy method (Moreo method) I/(-.
- Determined from a calibration curve by infrared absorption spectroscopy based on the absorption of the phenyl group = Aromatic monovinyl-conjugated diene polymer rubber used in Examples 1 to 17 and Comparative Examples 1 to 13, conjugated The diene (co)based rubber was obtained by the polymerization method of -F. 5BR-A: 2.5~ of cyclohexane, 125 g of sutyrene, 3759 sitadiene, 2 tetrahydrofuran in a nitrogen-substituted 5t autoclave
After charging 002 and adjusting the temperature of the thread to 10°C, n-BuLiO13F was added and the reaction heat was removed without removing it, and the conversion rate reached 100%. Nitokaji was added. After removing the solvent, it was dried with a roll at 100°C to obtain a polymer. 5BR-B: A nitrogen-substituted 5t autoclave was charged with 2.5 Kf of cyclohexane, 125 r of nutylene, 3752 of butanoene, and 2002 of 1-trahydrofuran, and after adjusting the temperature of the thread to 10°C, 39 of n-BuLiO was added. After confirming 100% conversion by polymerizing without removing the reaction heat, 0.29/10 cc' of tin tetrachloride/chlorohexane was added, and after 30 minutes, 24-di-t-butylcatechol 37 was added to methanol 5- and added. After removing the solvent, it was dried with a roll at 100°C to obtain a polymer. 5BR-C: A polymer was obtained in the same manner as 5BR-A except that tetrahydrofuran/ was changed to 15OL/. 5BR-D: A polymer was obtained in the same manner as 5BR-A except that tetrahydrofuran was added to 1002 in C. A polymer was obtained in the same manner as SBR-E: 5Bxt-A except that 402 was used instead of tetrahydrofuran 17. 5BR-ir: A polymer was obtained in the same manner as in the production method of 5BR-A except that 202 was used instead of tetrahydrofuran. 5BR-G: Sunalene 3 in the manufacturing method of 5BR-A
002, Getatsuen 200ri, Tetrahydro 7ran 15
02, n-Bul, io, and 359 were changed (to obtain 71 solimer.・Diethylene glycol methyl ether (1,59) was charged at 60°C, and n-Bu
I, i 0.211+Fukomi, reacted. Reached 100% polymerization conversion/? After X, 2,4-di-t-butylcatechol 3? Dissolve in methanol 5-. Added j7. After removing the solvent, it was dried in an i'J-L at 0°C to obtain Polymer 1. PBD-I: In the production method of PBD-H (diethylene glycol 0.0211, n-BuLlO, 211
Obtain the polymer in the same way, except for changing . IR-J: Nitrogen 11] □ Exchanged 5t mate crepe with 2.5 odor of toluene, 5 inoprene (1 (19, NOETI L/glycol dimethyladeca (1,59) and heated to 60℃, n-13uLi
015? I gave it to him and caused him to react. Polymerization conversion rate 1
After reaching 00%, dissolve λ4-der and monobutylcatechol 32 in 5 parts methanol and add (7). After removing the solvent, vacuum dry at 50°C to obtain a polymer. To IR: -J except that diethylene glycol dimethyl ether (1,1f. n -BuLi (1,2f/) was used [■ Coco

['C to get a polymer. PHI-L: Toluene 2 to nitrogen-substituted mate crepe
．． 5, 250 t, Ingshi'n 25 (
H' and 0.52 diethylene glycol methyl ether were charged, 'J was heated to 60°C, and n -BuLi O,2f
was prepared and reacted. After the polymerization conversion rate reached 100%, 4-di-t-butylcatechol 3S' was dissolved in methanol 5- and added. After removing the solvent, vacuum drying was performed at 50°C to obtain a polymer. PBI-M: In the method for producing PBI-L, diethylene glycol dimethyl, v=-fle01? , n −
A polymer was obtained in the same manner except that BuLi O,285' was used. Table 1 shows common parts among the formulations of the examples of the present invention and comparative examples, and the evaluation method. Table 1 1. Distribution list* I ASTllilI NαN-330*2 Vulcanization accelerator manufactured by Daien Shinko Kagaku Kogyo Tetramethylthiuram monosulfide *3 Vulcanization accelerator manufactured by Ouchi Shinko Ka♀ Kogyo Mercaptobenzothiazole *4 Kakuri manufactured by Iruuchi Shinko Kagaku Kogyo Sulfur accelerator N--,/chlorhexol-2-benzothia crusulfen ryomid M+on (1,00% modulus l: J
IS K 6301B 13 S Tear compression set (100°C x 24 hrs):〕(l''22]Kouyu Ue'':ヱJ- Obtained by the above/This Nunalene-Ptaduene Rubber 8BR
- Mixed printing of A-G and SBR1502 and EPDM 8.
as shown in Table 2, using the blending formula car 1 in Table 1,
Vulcanization was completed in 20 minutes at 60°C. The evaluation results are shown in Table 2. Comparative Examples 1 and 2 are rubber compositions using styrene-butadiene rubber whose 1,2 bond sensitivity is outside the range specified in 96, and have inferior mechanical strength compared to Examples 1 to 5. ing. Comparative Example 3 is a saw rubber composition using a styrene-butanoene rubber in which the amount of bound styrene is outside the range of the present invention, and compared to Examples 1 to 5, the properties of the rubber composition are not lost. Elongation has decreased significantly. Examples 6 to 9 and Comparative Examples 4 to 5 Styrene-butadiene rubber 5BR- obtained above
The mixing proportions of A, C-F and SBR1502 and EPDM were as shown in Table 3, and using the blending recipe-2 in Table 1, 16
Vulcanization was performed at 0°C for 20 minutes. The evaluation results are shown in Table 3. Examples 6 to 9 are rubber compositions using styrene-butadiene rubber with a 1.2 bond strength outside the range of the present invention, and are rubber compositions with superior mechanical strength compared to Comparative Examples 4 to 5. It is clear that Using the 5BR-A and F obtained above, and varying the mixing ratio with EPDM as shown in Table 4, Vulcanization was carried out at 160°C for 20 minutes using compounding recipe-2 in Table 1. The evaluation results are shown in Table 4. Examples 1 () to 11, which have the mixing ratio of the present invention, were outside this range. It is clear that the rubber composition has excellent mechanical strength when compared with Comparative Examples 6 to 7. Table 4 Example 12.13 and Comparative Example 8.9 Polygetadiene obtained above Rubber PBD-H,I
and EPI)M in the mixing ratio shown in Table 5, and vulcanization was carried out at 160° C. for 20 minutes using the formulations 1 and 2 shown in Table 1. The evaluation results are shown in Table 5. The polybutadiene rubber of Example 12.13 is a rubber composition with superior mechanical strength compared to Comparison 918.9, which is a comb composition using a material with 1.2 bonds outside the range of the present invention. It is clear that Table 5 Examples 14 and 15. and Comparative Example 10.11 The polyurethane rubber IR-J obtained above was mixed with EPDM at a mixing ratio as shown in Table 6, using the formulations -1 and -2 in Table 1, at 160°C, Vulcanization was performed for 20 minutes. The evaluation results are shown in Table 6. The polyurethane rubber of Example 14.15 was compared with Comparative Example 10.11, which is a rubber composition using a rubber composition in which the sum of 1.2 binding amount and 3.4 bonding amount is outside the range of the present invention. It is clear that the rubber composition has excellent mechanical strength. Table 6 Example 16. -17 and Comparative Example 12.13 Butadiene-in-play 7 rubber FB I-L obtained above,
The mixing ratio of M and EPDM is as shown in Table 7, and
Vulcanization was performed at 160°C for 20 minutes using the formulations -1 and -2 shown in the table. The evaluation results are shown in Table 7. The butadiene-in-prene rubber of Example 16.17 is 1.
J) A rubber composition with excellent mechanical strength compared to Comparative Example 12.13, which is a rubber composition using a rubber composition in which the sum of the amount of 2 bonds and the amount of 3,4 bonds is outside the range of the present invention. That is obvious. Table 7

Claims (1)

[Claims] (11(A) Ethylene-Zolopyrene-Nonconjugated Phenone (
A co-vulcanizable co-curable co-polymer co-composition comprising a co-polymer co-polymer and a co-vulcanizable co-curable co-polymer co-op, characterized in that the weight ratio of the co-curable component to the (B) calming component is in the range of 95:5 to 55:45. 2+ The rubber composition according to item 1, wherein the conjugated diene (co)polymer copolymer is obtained by anionically polymerizing a conjugated diene (co)polymer mixture containing 50% by weight or less of a polymerized vinyl compound.