WO2016177327A1 - 氯丁二烯橡胶组合物、硫化成型体及其用途 - Google Patents

氯丁二烯橡胶组合物、硫化成型体及其用途 Download PDF

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WO2016177327A1
WO2016177327A1 PCT/CN2016/080989 CN2016080989W WO2016177327A1 WO 2016177327 A1 WO2016177327 A1 WO 2016177327A1 CN 2016080989 W CN2016080989 W CN 2016080989W WO 2016177327 A1 WO2016177327 A1 WO 2016177327A1
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polyvinyl chloride
chloroprene rubber
rubber composition
mass
polychloroprene
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PCT/CN2016/080989
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English (en)
French (fr)
Inventor
山岸宇一郎
户谷英树
藤井信彦
张虹梅
封驰
张勇
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电化株式会社
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Priority to CN201680026137.1A priority Critical patent/CN107531952B/zh
Priority to JP2017557467A priority patent/JP6905472B2/ja
Publication of WO2016177327A1 publication Critical patent/WO2016177327A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a chloroprene rubber composition
  • a chloroprene rubber composition comprising: a modified polyvinyl chloride and polychloroprene obtained by chemically reacting polyvinyl chloride with a polyfunctional nucleophile Co-crosslinking.
  • the present invention relates to a vulcanized molded product obtained by vulcanization molding the chloroprene rubber composition, and various rubber products such as a mechanical belt, a vibration-proof rubber, and a rubber tire using the vulcanized molded product.
  • chloroprene rubber is excellent in the balance of physical properties such as mechanical properties, weather resistance, and flame retardancy, and is easy to process, it is widely used as an industrial rubber component such as various automotive parts, belts, hoses, and anti-vibration rubber. Raw materials. Polyvinyl chloride is also widely used as an industrial material which is excellent in inexpensiveness, mechanical properties, and weather resistance.
  • chloroprene rubber and the polyvinyl chloride have similar solubility parameter values and are high-polarity polymers, it is desirable to use chloroprene by adding polyvinyl chloride to the chloroprene rubber.
  • a rubber composition having improved oil resistance, chemical resistance, weather resistance, fire resistance and the like can be obtained.
  • the crystallinity of the chloroprene rubber may become an obstacle, resulting in the inability of these compounds to be uniformly mixed. Therefore, techniques for making chloroprene rubber compatible with polyvinyl chloride have been studied.
  • Non-Patent Document 1 As a technique for uniformly mixing a chloroprene rubber and polyvinyl chloride, a method is known in which a specific compound is added to a mixture of a chloroprene rubber and a polyvinyl chloride, and at a specific temperature. The kneading is performed a plurality of times (see Non-Patent Document 1).
  • Non-Patent Document 1 Japanese Rubber Association, Vol. 52, No. 4, pp. 70-76 (1979)
  • Patent Document 1 Japanese Patent Laid-Open No. Hei 10-287750
  • Polyvinyl chloride can be compatible with chloroprene rubber by the above method.
  • the obtained product has insufficient oil resistance and it is necessary to further improve oil resistance.
  • a chloroprene rubber composition which does not impair the mechanical properties evaluated by the tensile test using the dumbbell test piece and further improves the oil resistance and heat resistance.
  • various types of rubber products such as a vulcanized molded product of the chloroprene rubber composition and a mechanical belt, an anti-vibration rubber, and a vehicle tire using the vulcanized molded product are also proposed.
  • the present inventors have succeeded in obtaining a tool that does not damage the machine by performing various studies on the type of the drug used to obtain the co-crosslinked body of polyvinyl chloride and polychloroprene, and the operating conditions or steps.
  • the chloroprene rubber composition having characteristics and improved oil resistance has completed the present invention.
  • the present invention relates to a chloroprene rubber composition
  • a chloroprene rubber composition comprising: a modified polyvinyl chloride and a polychlorinated compound obtained by chemically reacting polyvinyl chloride and a polyfunctional nucleophile; A co-crosslinked body of butadiene.
  • the co-crosslinked body of the modified polyvinyl chloride and polychloroprene is preferably a co-crosslinked body composed of 5 to 45 parts by mass of modified polyvinyl chloride and 95 to 55 parts by mass of polychloroprene.
  • the polyfunctional nucleophile is preferably at least one selected from the group consisting of thiol compounds.
  • the modified polyvinyl chloride is preferably a material obtained by chemically reacting polyvinyl chloride with a polyfunctional nucleophilic reagent at 140 to 160 ° C, and the co-crosslinked body of the modified polyvinyl chloride and polychloroprene is preferably A material obtained by co-crosslinking modified polyvinyl chloride and polychloroprene at 120 to 140 °C.
  • the polyvinyl chloride is preferably a polyvinyl chloride having a softening temperature of 80 to 160 ° C.
  • the polyfunctional nucleophilic agent in the modified polyvinyl chloride is preferably 0.1 to 1.5% by mass in 100% by mass of the polyvinyl chloride.
  • the chloroprene rubber composition can be formed into a vulcanized molded body by vulcanization molding.
  • Examples of specific products using a vulcanized molded article include a mechanical belt, an anti-vibration rubber, a rubber tire, a wiper blade, a sponge, a hose, a wire and cable coating, a rubber lining, and the like.
  • the chloroprene rubber composition comprises: (1) a co-crosslinked body of a modified polyvinyl chloride and (2) polychloroprene.
  • the modified polyvinyl chloride is a compound obtained by chemically bonding a polyfunctional nucleophile to polyvinyl chloride by mixing a polyfunctional nucleophile and polyvinyl chloride and heating.
  • Multifunctional nucleophiles are used to promote co-crosslinking of polyvinyl chloride with polychloroprene.
  • a polyfunctional nucleophile is added only to polyvinyl chloride and polychloroprene, cross-linking of polychloroprene is carried out without co-crosslinking of polyvinyl chloride and polychloroprene. Therefore, by chemically reacting the polyfunctional nucleophilic reagent with polyvinyl chloride in advance, it is introduced into the polyvinyl chloride as a crosslinking point, and the polychloroprene is crosslinked with the crosslinking point, thereby promoting the polymerization of polyvinyl chloride and poly Co-crosslinking of chloroprene.
  • the polyfunctional nucleophile is a compound having a plurality of nucleophilic functional groups, and a known polyfunctional nucleophile can be used.
  • a polyfunctional nucleophile there is a thiol compound, specifically, as a thiol a compound comprising thiocyanuric acid, 2,5-dimercapto-1,3,4-thiadiazole, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, bis(fluorenyl) Methyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis( ⁇ -mercaptopropionate), 1,1,3,3-tetra(mercaptomethylthio)
  • propane the polyiso(thio)cyanate compound is m-xylylene diisocyanate, bis(isocyanatomethyl)norbornane, di(isocyano
  • polyfunctional nucleophiles may be used singly or in combination of a plurality of reagents. Further, a polymer obtained by polymerization using three to ten of the above polyfunctional nucleophilic reagents may also be used.
  • the amount of the polyfunctional nucleophilic agent added is in the range of 0.1 to 1.5% by mass based on the total mass of the polyvinyl chloride, the balance between the oil resistance and the mechanical strength of the obtained chloroprene rubber composition is improved.
  • the amount of the polyfunctional nucleophilic agent added is in the range of 0.1 to 1.5% by mass based on the total mass of the polyvinyl chloride, the balance between the oil resistance and the mechanical strength of the obtained chloroprene rubber composition is improved.
  • the amount of the polyfunctional nucleophilic agent added is in the range of 0.1 to 1.5% by mass based on the total mass of the polyvinyl chloride, the balance between the oil resistance and the mechanical strength of the obtained chloroprene rubber composition is improved.
  • the amount of the polyfunctional nucleophilic agent added is in the range of 0.1 to 1.5% by mass based on the total mass of the polyvinyl chloride, the balance between the oil resistance and the mechanical strength of the obtained chloroprene rubber composition is improved.
  • the polyvinyl chloride a commercially available polyvinyl chloride having a molecular weight, a molecular weight distribution, a chemical modification, a type of an additive such as a plasticizer contained in the polyvinyl chloride, or an added amount can be used as long as the effect of the present invention is not impaired.
  • the softening temperature of the polyvinyl chloride is preferably in the range of 80 to 160 °C. When the softening temperature of the polyvinyl chloride is less than 80 ° C, when the modified polyvinyl chloride and the polychloroprene are co-crosslinked, the modified polyvinyl chloride is thermally softened, and the intended chloroprene may not be obtained.
  • An olefin rubber composition An olefin rubber composition.
  • the softening temperature of the polyvinyl chloride exceeds 160 ° C
  • the reaction temperature of the polyfunctional nucleophilic reagent and the polyvinyl chloride must exceed 160 ° C. Therefore, the number of crosslinking points introduced into the obtained modified polyvinyl chloride is reduced, and the intended chloroprene rubber composition may not be obtained.
  • a polyfunctional nucleophile may be mixed and heated with polyvinyl chloride. Specifically, the polyvinyl chloride is kneaded at a temperature equal to or higher than the softening temperature of the polyvinyl chloride by using a kraft mixer such as a well-known Banbury mixer, a kneader mixer, or an open roll. The polyfunctional nucleophilic reagent is added thereto, and kneading is continued for a predetermined period of time, whereby the polyfunctional nucleophilic reagent is chemically reacted with polyvinyl chloride to obtain a modified polyvinyl chloride.
  • a kraft mixer such as a well-known Banbury mixer, a kneader mixer, or an open roll.
  • the polyfunctional nucleophilic reagent is added thereto, and kneading is continued for a predetermined period of time, whereby the polyfunctional nucleophilic reagent is chemically reacted with polyviny
  • the obtained neoprene rubber is obtained by adjusting the kneading temperature of the kneading device to 140 to 160 °C.
  • the mechanical strength of the rubber composition is improved, so the above kneading temperature is preferred.
  • Polychloroprene is a homopolymer of chloroprene or a copolymer of chloroprene and other monomers copolymerizable with chloroprene.
  • the monomer copolymerizable with chloroprene for example, 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, styrene, acrylonitrile, methacryl Nitrile, isoprene, butadiene, and acrylic acid, methacrylic acid, and esters thereof can be used within the range that satisfies the object of the present invention.
  • any one of polychloroprene can be used as long as the effects of the present invention are not impaired.
  • the polychloroprene of the present invention is classified into a thiol modified type, a xanthogen modified type, and a sulfur modified type depending on the molecular weight modifier used.
  • the thiol-modified chloroprene rubber is obtained by using an alkyl thiol such as n-dodecyl mercaptan, t-dodecyl octyl mercaptan or octyl mercaptan in the molecular weight modifier.
  • the chloroprene rubber and the chloroprene-modified chloroprene rubber are modified chloroprene rubber obtained by using an alkylxanthogen compound in a molecular weight modifier.
  • the sulfur-modified chloroprene rubber is obtained by plasticizing a polymer obtained by copolymerizing thiuram disulfide with sulfur and a chloroprene monomer, and adjusting the viscosity to a predetermined Mooney viscosity.
  • Chloroprene rubber any one of polychloroprene can be used as long as the effects of the present invention are not impaired.
  • the modified polyvinyl chloride and the polychloroprene When the modified polyvinyl chloride and the polychloroprene are co-crosslinked, the modified polyvinyl chloride and the polychloroprene may be mixed and heated. Specifically, polychloroprene may be added to the modified polyvinyl chloride obtained by the above method, and kneading may be carried out in a range of from 120 to 140 ° C for a predetermined period of time. By adjusting the kneading temperature to this range, the mechanical strength of the obtained chloroprene rubber composition is improved, which is preferable.
  • the apparatus for kneading the modified polyvinyl chloride and the polychloroprene may be a kneading device such as a well-known Banbury mixer, a kneading mixer, or an open roll.
  • the composition ratio of the polyvinyl chloride is adjusted to 5 to 45 parts by mass, and the composition ratio of the polychloroprene is adjusted to 95 to 55 parts by mass.
  • the obtained chloroprene rubber composition is a composition based on chloroprene rubber, and the mechanical properties evaluated by the tensile test are maintained, which is preferable.
  • chloroprene rubber composition a public addition can be added to the extent that the effects of the present invention are not impaired.
  • the vulcanizing agent may be a metal monomer such as sulfur, bismuth, magnesium, zinc, calcium, strontium, barium, titanium, tin, zirconium, hafnium, vanadium, niobium, molybdenum, tungsten, niobium, selenium, iron, nickel, cobalt or ruthenium. And oxides or hydroxides of these metals.
  • these vulcanizing agents that can be added especially due to sulfur, calcium oxide or zinc oxide, iron trioxide, titanium dioxide, lead oxide, lead trioxide, cerium oxide, antimony trioxide, magnesium oxide, hydrotalcite High, so it is preferred. Further, these vulcanizing agents may be used in combination of two or more kinds.
  • the amount of the vulcanizing agent to be mixed can be added in the range of 0.1 part by mass or more to 10 parts by mass or less based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition.
  • the vulcanization accelerator is a compound added to promote the vulcanization of the chloroprene rubber composition, and is generally used in the vulcanization of chloroprene rubber, hydrazines, thiurams, thiazoles, peroxidation. Things and so on.
  • thiourea compound examples include ethylenethiourea, diethylthiourea, trimethylthiourea, triethylthiourea, and N,N'-diphenylthiourea.
  • hydrazine 1,3-diphenylfluorene, di-o-tolyl oxime, di-m-toluene oxime, di-p-toluene oxime, 1-o-tolylbiguanide, 1-m-toluobiguanide, 1-p-toluene bismuth, Di-o-tolyl sulfonium salt of dicatechol borate, di-toluene sulfonium salt of di-catechol borate, di-p-toluene salt of di- catechol borate, hydrochloric acid Bismuth, cerium nitrate, cerium carbonate, cerium phosphate, cerium sulfamate, formyl hydrazide, acetohydrazide, chloroacetyl hydrazine, 1,2-n-diacetyl hydrazine, 1,3-n-diacetyl hydra
  • thiura compound there are tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, and tetrasulfide tetrasulfide.
  • Kethiram tetrabenzylthiuram disulfide, tetra-2-ethylhexylthiuram disulfide, and the like.
  • thiazole compound there are 2-mercaptobenzothiazole, benzothiazole disulfide, di-2-benzothiazole disulfide, 2-mercaptobenzothiazole zinc salt, 2-morpholinyl dithiobenzothiazole, N-cyclohexyl-2-benzothiazole sulfenamide, N,N-dicyclohexyl-2-benzothiazole sulfenamide, 1-(N,N-diethylthiocarbamoylphenyl)- 1,3-benzothiazole and the like.
  • peroxide examples include dicumyl peroxide, valerate peroxide, alkyl peroxide, substituted alkyl aromatic peroxide, and the like.
  • vulcanization accelerator 3-methyltetrahydrothiazole-2-thione, a mixture of thiadiazole and phenylene bismaleimide, or diammonium isophthalate or 1, can also be used.
  • a vulcanization accelerator such as 2-dimercapto-1,3,4-thiadiazole derivative.
  • vulcanization accelerators may be used in combination of two or more of the above-exemplified compounds. These vulcanization accelerators may be added in an amount of 0.5 to 5 parts by mass based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition of the present invention.
  • the vulcanization aid is a compound added to increase the efficiency of the vulcanization accelerator, and may be a fatty acid such as stearic acid or zinc stearate or a metal salt thereof.
  • a peroxide it is preferred to use at least one compound selected from a difunctional ester compound or a trifunctional ester compound. Specifically, trimethylolpropane, ethylene glycol dimethacrylate, triallyl isocyanate, or phenylene bismaleimide can be used.
  • vulcanization aids may be added in an amount of 0.5 to 5 parts by mass based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition of the present invention.
  • the anti-aging agent is used to suppress the decrease in Shore hardness, elongation at break, compression set, and heat resistance when the vulcanized molded article or the anti-vibration rubber of the obtained chloroprene rubber composition is heated.
  • the added compounds include phenolic antioxidants, amine antioxidants, acrylate antioxidants, metal carbamates, and waxes. These primary antioxidants can be used alone or in combination. Among these compounds, 4,4'-bis(?,?-dimethylbenzyl)diphenylamine or octylated diphenylamine of an amine antioxidant is preferred because it has a large effect of improving heat resistance.
  • the compounding amount of the primary antioxidant may be 0.1 to 10 parts by mass based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition of the present invention.
  • the secondary antioxidant is for suppressing a decrease in Shore hardness, elongation at break, and compression set at the time of heating the vulcanized molded product of the obtained chloroprene rubber composition or the vibration-proof rubber thereof, and
  • Examples of the compound to be added to improve heat resistance include a phosphorus antioxidant, a sulfur antioxidant, and an imidazole antioxidant. These secondary antioxidants may be used alone or in combination.
  • the amount of the secondary antioxidant may be 0.1 to 10 parts by mass based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition of the present invention.
  • the plasticizer is a compound added to plasticize the obtained chloroprene rubber composition, and is vegetable oil such as rapeseed oil, vegetable oil such as linseed oil, castor oil, coconut oil, phthalate plasticizer, DUP. (ceadecyl phthalate), DOS (dioctyl sebacate), DOA (dioctyl adipate), ester plasticizer, ether ester plasticizer, thioether Plasticizers such as plasticizers, aromatic oils, naphthenic oils, lubricating oils, processing oils, paraffin waxes, liquid paraffin, petroleum jelly, petroleum asphalt, etc. Depending on the characteristics required for the chloroprene rubber composition, one type or a combination of a plurality can be used.
  • the amount of the plasticizer blended can be 5 to 50 parts by mass based on 100 parts by mass of the total of the polyvinyl chloride and the polychloroprene in the chloroprene rubber composition of the present invention.
  • the processing aid is a compound added to improve the processing characteristics such as easy peeling of the chloroprene rubber composition from a roll, a molding die, a screw of an extruder, or the like.
  • a fatty acid such as stearic acid or a wax processing aid such as polyethylene, a fatty acid amide, or the like
  • a total of polyvinyl chloride and polychloroprene in the chloroprene rubber composition of the present invention 100 parts by mass can be added until the processing aid reaches 0.5 to 5 parts by mass.
  • fillers or reinforcing agents can also be added to the chloroprene rubber composition within the range not impairing the object of the present invention.
  • the filler or reinforcing agent include carbon black, silica, clay, talc, calcium carbonate, and the like. These fillers and reinforcing agents may be used in combination of two or more kinds depending on the purpose of use. 100 parts by mass relative to the polyvinyl chloride and polychloroprene in the chloroprene rubber composition, The amount of these fillers and reinforcing agents added can be 1 to 100 parts by mass.
  • the vulcanized molded product is a molded body obtained by subjecting a chloroprene rubber composition obtained by the above method to vulcanization molding.
  • the vulcanized molded body may be a molded body obtained by molding a chloroprene rubber composition into various desired shapes and then vulcanized; or the chloroprene rubber composition may be vulcanized in advance and then molded into each A molded body obtained in a shape.
  • a method of molding a chloroprene rubber composition or a vulcanized rubber includes conventional methods such as press molding, extrusion molding, and calender molding. These methods may be carried out by a method used in the usual rubber industry.
  • vulcanization can be carried out by general steam vulcanization or UHF vulcanization.
  • Steam vulcanization is a method of vulcanizing a vulcanized chloroprene rubber composition by applying pressure and temperature to steam as a heat medium
  • UHF vulcanization is a method of irradiating a chloroprene rubber composition with a microwave to vulcanize it.
  • the mold temperature can be raised to the vulcanization temperature and vulcanized in a state where the chloroprene rubber composition is held inside the molding die.
  • the vulcanization temperature can be appropriately set depending on the ratio of the chloroprene rubber composition or the type of the vulcanizing agent, and is usually preferably in the range of 140 to 220 ° C, more preferably 150 to 180 ° C.
  • the vulcanized molded body is used as a mechanical belt, an anti-vibration rubber, a rubber tire, a blade for a wiper, a sponge, a hose, a wire and cable, and a rubber lining.
  • modified polyvinyl chloride C All of the conditions were the same as those of the modified polyvinyl chloride C except that the time for kneading the polyvinyl chloride and the respective additives was 8 minutes and 16 minutes, respectively, and modified polyvinyl chlorides F and G were obtained.
  • Example 1 100 parts by mass of the co-crosslinked body A obtained by the above method, 5 parts by mass of zinc oxide (manufactured by Mitsui Metals, Inc.), and 0.5 parts by mass of ethylenethiourea (product name: Accel 22S, Kawaguchi Chemical Industry Co., Ltd.) 0.5 parts by mass of stearic acid (manufactured by China National Pharmaceutical Group Chemical Reagent Co., Ltd.), which was kneaded at 40 ° C for 5 minutes using two open rolls of 4 inches in diameter, thereby obtaining Example 1 A chloroprene rubber composition.
  • Example 1 The chloroprene rubber composition of Example 1 obtained by the above method was subjected to press vulcanization under the conditions of 160 ° C ⁇ 20 minutes and a pressure of 0.8 MPa to prepare a vulcanized molded product sheet having a thickness of 2.0 mm.
  • the test piece was cut out from the vulcanized molded body sheet, and immediately after the test piece was produced, according to JIS K6251 was subjected to mechanical strength test (tensile strength, elongation at break, measurement of 100% tensile modulus). Specifically, the test piece was cut out from the vulcanized molded product sheet using a dumbbell No.
  • the cut test piece was immersed in an ASTM No. 3 oil at 100 ° C for 70 hours, and then subjected to an immersion test in accordance with JIS K6258, and subjected to an oil resistance test (volume change rate, weight change rate).
  • the mechanical strength of the vulcanized molded article obtained by using the chloroprene rubber composition is qualified if the tensile strength is 7.5 MPa or more, the elongation at break is 220% or more, and the tensile modulus at 100% is 0.2 MPa. .
  • the volume change rate is 80% or less and the weight change rate is 100% or less, the oil resistance is acceptable.
  • Table 3 The results obtained are shown in Table 3.
  • Example 1 All of the conditions were the same as those of Example 1 except that the co-crosslinked body A was replaced with the co-crosslinked bodies B to Q, respectively, and the chloroprene rubbers of Examples 2 to 12 and Comparative Examples 1 to 5 were produced.
  • the composition was evaluated under the same conditions as in Example 1. The evaluation results are shown in Table 3.
  • Comparative Example 1 since the kneading temperature was low, the modified polyvinyl chloride and the polychloroprene were not uniformly dispersed, and the chloroprene rubber composition could not be obtained.
  • Comparative Example 2 since the kneading temperature was high, a part of the modified polyvinyl chloride and polychloroprene was vulcanized, and a part became a powdery neoprene rubber. Gum composition. Therefore, no evaluation was made for Comparative Example 1 and Comparative Example 2.
  • the chloroprene rubber composition of the present invention can provide a chloroprene rubber composition which does not impair the mechanical properties evaluated by the tensile test and further improves the oil resistance and heat resistance. Sulfide.

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Abstract

本发明提供一种包含聚氯乙烯与聚氯丁二烯进行共交联而得到的反应物的氯丁二烯橡胶组合物，所述氯丁二烯橡胶组合物能够得到不损害机械特性、并使耐油耐热性提高的硫化成型体。所述氯丁二烯橡胶组合物包含：使聚氯乙烯和多官能亲核试剂进行化学反应而得到的改性聚氯乙烯与聚氯丁二烯的共交联体。改性聚氯乙烯与聚氯丁二烯的共交联体优选为，由5～45质量份的改性聚氯乙烯和95～55质量份的聚氯丁二烯组成的共交联体。多官能亲核试剂优选为从硫醇化合物中选出的至少一种。

Description

氯丁二烯橡胶组合物、硫化成型体及其用途
本申请要求在2015年5月04日提交中国专利局、申请号为201510221849.6、发明名称为“氯丁二烯橡胶组合物、硫化成型体及其用途”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及一种氯丁二烯橡胶组合物，该氯丁二烯橡胶组合物包含：使聚氯乙烯和多官能亲核试剂进行化学反应而得到的改性聚氯乙烯与聚氯丁二烯的共交联体。并且，本发明还涉及将该氯丁二烯橡胶组合物进行硫化成型而得到的硫化成型体、以及使用了该硫化成型体的机械用皮带、防振橡胶、橡胶轮胎等各种橡胶制品。
背景技术
由于氯丁二烯橡胶在机械特性、耐候性、阻燃性等物性平衡的方面优异且容易加工，所以被广泛用作各种汽车用部件、皮带、软管、防振橡胶等工业用橡胶部件的原材料。聚氯乙烯也被广泛用作廉价且机械物性或耐候性等优异的工业用材料。
由于氯丁二烯橡胶与聚氯乙烯的溶解度参数值相近、且均为极性高的高分子，因此通过在氯丁二烯橡胶中加入聚氯乙烯，由此可以期望在使采用氯丁二烯橡胶的各种制品的成本下降的同时，可得到一种耐油性、耐化学性、耐候性、耐火性等都提高的橡胶组合物。然而，实际上氯丁二烯橡胶的结晶性会成为障碍，导致这些化合物无法均匀混合。因此，人们研究了使氯丁二烯橡胶与聚氯乙烯相溶的技术。
作为用于使氯丁二烯橡胶与聚氯乙烯均匀混合的技术，已知有如下的方法：在氯丁二烯橡胶和聚氯乙烯的混合物中添加特定的化合物、并在特定温 度下进行多次混炼(参照非专利文献1)。
另外，还已知使用过的农业用聚氯乙烯和天然橡胶(或合成橡胶)能够在特定温度下进行良好的混合(参照专利文献1)。
现有技术文献
非专利文献
非专利文献1：日本橡胶协会志，第52卷，第4号，70～76页(1979年)
专利文献
专利文献1：日本特开平10-287750号公报
发明内容
发明所要解决的课题
通过上述方法能够使聚氯乙烯与氯丁二烯橡胶相溶。但是，所得的制品的耐油性不充分，需要进一步提高耐油性。
因此，在本发明中，以提供不损害用哑铃试验片的拉伸试验来评价的机械特性、并使耐油耐热性进一步提高的氯丁二烯橡胶组合物为课题。并且，还以提供该氯丁二烯橡胶组合物的硫化成型体、以及使用了该硫化成型体的机械用皮带、防振橡胶、车辆用轮胎等各种橡胶制品为课题。
用于解决课题的方法
本发明人为了解决上述课题，通过对用于得到聚氯乙烯与聚氯丁二烯的共交联体的药剂种类、以及操作条件或步骤等进行各种研究，成功地得到了不会损害机械特性、并使耐油性提高的氯丁二烯橡胶组合物，从而完成了本发明。
即、本发明涉及一种氯丁二烯橡胶组合物，所述氯丁二烯橡胶组合物包含：使聚氯乙烯和多官能亲核试剂进行化学反应而得到的改性聚氯乙烯与聚氯丁二烯的共交联体。
改性聚氯乙烯与聚氯丁二烯的共交联体优选为，由5～45质量份的改性聚氯乙烯和95～55质量份的聚氯丁二烯组成的共交联体。
多官能亲核试剂优选为，从硫醇化合物中选出的至少一种。
改性聚氯乙烯优选为，使聚氯乙烯与多官能亲核试剂在140～160℃下进行化学反应而得到的物质，改性聚氯乙烯与聚氯丁二烯的共交联体优选为，使改性聚氯乙烯与聚氯丁二烯在120～140℃下进行共交联而得到的物质。
聚氯乙烯优选为软化温度是80～160℃的聚氯乙烯，在100质量％的聚氯乙烯中，改性聚氯乙烯中的多官能亲核试剂优选为0.1～1.5质量％。
氯丁二烯橡胶组合物通过硫化成型，能够制成硫化成型体。
作为使用了硫化成型体的具体制品的例子，有机械用皮带、防振橡胶、橡胶轮胎、雨刷用叶片、海绵、软管、电线电缆包覆、橡胶衬里等。
发明效果
通过实施本发明，可以得到形成硫化成型体的不损害用拉伸试验来评价的机械特性、且耐油性比以往更高的氯丁二烯橡胶组合物以及使用了该氯丁二烯橡胶组合物的硫化成型体。
具体实施方式
＜氯丁二烯橡胶组合物＞
氯丁二烯橡胶组合物包含：(1)改性聚氯乙烯与(2)聚氯丁二烯的共交联体。
(1)改性聚氯乙烯
改性聚氯乙烯是指，通过混合多官能亲核试剂和聚氯乙烯并进行加热，使多官能亲核试剂与聚氯乙烯进行化学键合而得到的化合物。
多官能亲核试剂用于促进聚氯乙烯与聚氯丁二烯的共交联。仅仅在聚氯乙烯和聚氯丁二烯中添加多官能亲核试剂时，会进行聚氯丁二烯的交联，而不会进行聚氯乙烯与聚氯丁二烯的共交联。因此，通过预先使多官能亲核试剂与聚氯乙烯进行化学反应而作为交联点导入聚氯乙烯中，聚氯丁二烯与该交联点交联，由此能够促进聚氯乙烯与聚氯丁二烯的共交联。
多官能亲核试剂是具有多个亲核性官能团的化合物，可以使用公知的多官能亲核试剂。作为多官能亲核试剂，有硫醇化合物，具体而言，作为硫醇 化合物，包含从硫氰尿酸、2,5-二巯基-1,3,4-噻二唑、1,2-双[(2-巯基乙基)硫代]-3-巯基丙烷、双(巯基甲基)-3,6,9-三硫杂-1,11-十一烷二硫醇、季戊四醇四(β-巯基丙酸酯)、1,1,3,3-四(巯基甲硫基)丙烷中选出的一种或两种以上的化合物，聚异(硫)氰酸酯化合物有间苯二甲基二异氰酸酯、二(异氰酸根合甲基)降冰片烷、二(异氰酸根合甲基)环己烷、六亚甲基二异氰酸酯、二环己基甲烷二异氰酸酯。
这些多官能亲核试剂可以单独使用，也可以并用多种试剂。另外，还可以使用3个～10个上述多官能亲核试剂进行聚合而得到的聚合物。
若相对于聚氯乙烯的总质量，多官能亲核试剂的添加量在0.1～1.5质量％的范围，则由于使所得的氯丁二烯橡胶组合物的耐油性与机械强度的平衡提高，因此优选。
聚氯乙烯可以使用一般市场上出售的聚氯乙烯，其分子量、分子量分布、化学改性、在聚氯乙烯中所含的增塑剂等添加剂的种类或添加量，只要不妨碍本发明的效果就没有特别限定。聚氯乙烯的软化温度优选在80～160℃的范围。若聚氯乙烯的软化温度不足80℃，则在使改性聚氯乙烯与聚氯丁二烯进行共交联时，改性聚氯乙烯发生热软化，有时会无法得到作为目标的氯丁二烯橡胶组合物。
若聚氯乙烯的软化温度超过160℃，则多官能亲核试剂与聚氯乙烯的反应温度必然会超过160℃。因此，向所得的改性聚氯乙烯中导入的交联点的数目减少，可能会无法得到作为目标的氯丁二烯橡胶组合物。
为了得到改性聚氯乙烯，只要将多官能亲核试剂与聚氯乙烯进行混合、加热即可。具体而言，通过使用公知的班伯里混合机、捏合混合机(kneader mixer)、开放式辊等混炼装置，在设定成聚氯乙烯的软化温度以上的温度下混炼了聚氯乙烯，向其中添加多官能亲核试剂，并且在规定时间内继续进行混炼，由此使多官能亲核试剂与聚氯乙烯进行化学反应，从而得到改性聚氯乙烯。
由于将混炼装置的混炼温度调节至140～160℃，而使所得的氯丁二烯橡 胶组合物的机械强度提高，因此优选上述混炼温度。
(2)聚氯丁二烯
聚氯丁二烯是氯丁二烯的均聚物、或者氯丁二烯和能够与氯丁二烯共聚的其他单体的共聚物。作为能够与氯丁二烯共聚的单体，例如有2,3-二氯-1,3-丁二烯、1-氯-1,3-丁二烯、苯乙烯、丙烯腈、甲基丙烯腈、异戊二烯、丁二烯、以及丙烯酸、甲基丙烯酸及它们的酯类等，可以在满足本发明目的的范围内使用。在本发明中，只要不妨碍本发明的效果，则能够使用任意一种聚氯丁二烯。
根据所使用的分子量调节剂，将本发明的聚氯丁二烯分为硫醇改性型、黄原改性型、硫改性型。硫醇改性型的氯丁二烯橡胶是在分子量调节剂中使用正十二烷基硫醇、叔十二烷基辛基硫醇、辛基硫醇等烷基硫醇类而得到的改性氯丁二烯橡胶，黄原改性型的氯丁二烯橡胶是在分子量调节剂中使用烷基黄原化合物而得到的改性氯丁二烯橡胶。另外，硫改性型的氯丁二烯橡胶是用二硫化秋兰姆对硫与氯丁二烯类单体共聚后的聚合物进行增塑，并调节至规定的门尼粘度而得到的改性氯丁二烯橡胶。在本发明中，只要不妨碍本发明的效果，则能够使用任意一种聚氯丁二烯。
在使改性聚氯乙烯与聚氯丁二烯共交联时，只要对改性聚氯乙烯和聚氯丁二烯进行混合并加热即可。具体而言，只要在通过上述方法得到的改性聚氯乙烯中加入聚氯丁二烯，在120～140℃的范围并在规定时间内进行混炼即可。通过将混炼温度调节至该范围，而使所得的氯丁二烯橡胶组合物的机械强度提高，因此优选。对改性聚氯乙烯和聚氯丁二烯进行混炼的装置，只要使用公知的班伯里混合机、捏合混合机、开放式辊等混炼装置即可。
在改性聚氯乙烯与聚氯丁二烯的共交联体中，若聚氯乙烯的组成比调节至5～45质量份、聚氯丁二烯的组成比调节至95～55质量份的范围，则所得的氯丁二烯橡胶组合物成为以氯丁二烯橡胶为基质的组合物，用拉伸试验来评价的机械特性得以维持，因此优选。
在不损害本发明效果的范围内，在氯丁二烯橡胶组合物中还可以添加公 知的硫化剂、硫化促进剂、硫化助剂、一次防老剂、二次防老剂、增塑剂、加工助剂。
硫化剂可以使用硫、铍、镁、锌、钙、钡、锗、钛、锡、锆、锑、钒、铋、钼、钨、碲、硒、铁、镍、钴、锇等金属单体、以及这些金属的氧化物或氢氧化物。在这些能够添加的硫化剂中，特别是由于硫、氧化钙或氧化锌、三氧化铁、二氧化钛、氧化铅、四氧化三铅、二氧化锑、三氧化锑、氧化镁、水滑石的硫化效果高，因此优选。另外，这些硫化剂可以并用两种以上。相对于在氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，硫化剂的混合量在0.1质量份以上至10质量份以下的范围内能够进行添加。
硫化促进剂是为了促进氯丁二烯橡胶组合物的硫化而添加的化合物，有一般被用于氯丁二烯橡胶硫化中的硫脲类、胍类、秋兰姆类、噻唑类、过氧化物等。
作为硫脲类化合物，有乙撑硫脲、二乙基硫脲、三甲基硫脲、三乙基硫脲、N,N’-二苯基硫脲等。
作为胍类化合物，有胍、1,3-二苯基胍、二邻甲苯胍、二间甲苯胍、二对甲苯胍、1-邻甲苯双胍、1-间甲苯双胍、1-对甲苯双胍、二邻苯二酚硼酸酯(dicatechol borate)的二邻甲苯胍盐、二邻苯二酚硼酸酯的二间甲苯胍盐、二邻苯二酚硼酸酯的二对甲苯胍盐、盐酸胍、硝酸胍、碳酸胍、磷酸胍、氨基磺酸胍、甲酰胍、乙酰胍、氯乙酰胍、1,2-正二乙酰胍、1,3-正二乙酰胍、1,3-正二丙酰胍、马尿酰胍、苯磺酰胍等。
作为秋兰姆类化合物，有二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、二硫化四丁基秋兰姆、四硫化双五亚甲基秋兰姆、一硫化四甲基秋兰姆、二硫化四苄基秋兰姆、二硫化四-2-乙基己基秋兰姆等。
作为噻唑类化合物，有2-巯基苯并噻唑、二硫化苯并噻唑、二硫化二-2-苯并噻唑、2-巯基苯并噻唑锌盐、2-吗啉基二硫代苯并噻唑、N-环己基-2-苯并噻唑次磺酰胺、N,N-二环己基-2-苯并噻唑次磺酰胺、1-(N,N-二乙基硫代氨甲酰苯基)-1,3-苯并噻唑等。
作为过氧化物，有二枯基过氧化物、戊酸酯过氧化物、烷基过氧化物、取代烷基芳香族过氧化物等。
作为其他的硫化促进剂，还能够使用3-甲基四氢噻唑-2-硫酮、噻二唑与亚苯基双马来酰亚胺的混合物、间苯二甲酸氢二甲铵或1,2-二巯基-1,3,4-噻二唑衍生物等硫化促进剂。
这些硫化促进剂可以并用两种以上的上述列举的化合物。相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，这些硫化促进剂的添加量可以是0.5～5质量份。
硫化助剂是为了提高硫化促进剂的效率而添加的化合物，有硬脂酸、硬脂酸锌等脂肪酸或其金属盐。在使用过氧化物的情况下，优选并用从二官能度酯化合物或三官能度酯化合物中选出的至少一种化合物。具体而言，可使用三羟甲基丙烷、乙二醇二甲基丙烯酸酯、三烯丙基异氰酸酯、亚苯基双马来酰亚胺。
相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，这些硫化助剂的添加量可以是0.5～5质量份。
一次防老剂是为了抑制在对所得的氯丁二烯橡胶组合物的硫化成型体或其防振橡胶进行加热时的肖氏硬度、断裂伸长率、压缩永久变形的下降、并提高耐热性而添加的化合物，有苯酚类防老剂、胺类防老剂、丙烯酸酯类防老剂、氨基甲酸金属盐以及蜡。这些一次防老剂可以使用一种或并用。在这些化合物中，胺类防老剂的4,4’-双(α,α-二甲基苄基)二苯胺或辛基化二苯胺由于改善耐热性的效果大因而优选。
相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，一次防老剂的混合量可以是0.1～10质量份。通过将一次防老剂的混合量设定在该范围，能够抑制所得的硫化成型体的断裂伸长率等机械物性的下降，并提高耐热性。
二次防老剂是为了抑制在对所得的氯丁二烯橡胶组合物的硫化成型体或其防振橡胶进行加热时的肖氏硬度、断裂伸长率、压缩永久变形的下降、并 提高耐热性而添加的化合物，可以列举磷类防老剂、硫类防老剂、咪唑类防老剂。这些二次防老剂可以使用一种或并用。在这些化合物中，磷类防老剂的三(壬基苯基)亚磷酸酯、三(2,4-二叔丁基苯基)亚磷酸酯、硫类防老剂的硫代二丙酸二月桂酯、3,3’-硫代二丙酸二肉豆蔻基酯、3,3’-硫代二丙酸二硬脂醇酯、咪唑类防老剂的2-巯基苯并咪唑、1-苄基-2-乙基咪唑由于改善耐热性的效果大因而优选。
相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，二次防老剂的混合量可以是0.1～10质量份。通过将二次防老剂的混合量设在该范围，能够抑制所得的硫化成型体的断裂伸长率等机械物性的下降，并提高耐热性。
增塑剂是为了增塑所得的氯丁二烯橡胶组合物而添加的化合物，有菜籽油等植物油、亚麻油、蓖麻油、椰子油等植物油、邻苯二甲酸酯类增塑剂、DUP(邻苯二甲酸二十一烷基酯)、DOS(癸二酸二辛酯)、DOA(己二酸二辛酯)、酯类增塑剂、醚酯类增塑剂、硫醚类增塑剂、芳香类油、环烷烃类油、润滑油、加工油、石蜡、液体石蜡、凡士林、石油沥青等石油类增塑剂。根据对氯丁二烯橡胶组合物所要求的特性，可以使用一种或并用多种。相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，能够将增塑剂的混合量设为5～50质量份。
加工助剂是为了提高氯丁二烯橡胶组合物从辊或成型模具、挤压机的螺杆等上容易剥离等的加工特性而添加的化合物。具体而言，有硬脂酸等脂肪酸或聚乙烯等蜡类加工助剂、脂肪酸酰胺等，相对于在本发明的氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份，能够添加加工助剂达到0.5～5质量份为止。
在不损害本发明目的的范围内，在氯丁二烯橡胶组合物中还能够添加各种填充剂或增强剂。作为填充剂或增强剂的例子，有碳黑、二氧化硅、粘土、滑石、碳酸钙等。这些填充剂、增强剂根据使用目的，可以并用两种以上。相对于在氯丁二烯橡胶组合物中的聚氯乙烯和聚氯丁二烯的总计100质量份， 能够将这些填充剂、增强剂的添加量设为1～100质量份。
＜硫化成型体＞
硫化成型体是将通过上述方法得到的氯丁二烯橡胶组合物进行硫化成型而得到的成型体。硫化成型体可以是将氯丁二烯橡胶组合物成型成所期望的各种形状后再进行硫化而得到的成型体；或者是预先将氯丁二烯橡胶组合物进行硫化、之后再成型成各种形状而得到的成型体。对氯丁二烯橡胶组合物或硫化橡胶进行成型的方法有以往的加压成型、挤压成型、压延成型等方法。这些方法只要采用在通常的橡胶工业中所用的方法即可。
关于氯丁二烯橡胶组合物的硫化，特别是虽然没有选择硫化方法，但能够通过一般的蒸汽硫化或UHF硫化进行硫化。蒸汽硫化是通过作为热介质的蒸汽对未硫化的氯丁二烯橡胶组合物施加压力和温度而使其硫化的方法，UHF硫化是对氯丁二烯橡胶组合物照射微波而使其硫化的方法。另外，在加压硫化或注射成型时，可以在成型用模具的内部保持着氯丁二烯橡胶组合物的状态下、将模具温度升高至硫化温度并进行硫化。硫化温度可以根据氯丁二烯橡胶组合物的配比或硫化剂的种类而适当设定，通常优选在140～220℃、更优选在150～180℃的范围。
具体而言，硫化成型体被用作机械用皮带、防振橡胶、橡胶轮胎、雨刷用叶片、海绵、软管、电线电缆包覆、橡胶衬里。
[实施例]
下面通过参考例、实施例进一步进行详细说明，但本发明并不能被解释为受到这些例子的限定。此外，在以下的参考例、实施例中所使用的密炼机、双辊等装置类、聚氯乙烯、聚氯丁二烯、各种药剂均通用。
＜改性聚氯乙烯A的制作＞
使用密炼机(装置名称：Labo Plastomill 75C型号100、株式会社东洋精机制作所制造)，添加20质量份的聚氯乙烯(上海氯碱化工股份有限公司制造)、0.3质量份的硫氰尿酸(黄岩东海化工有限公司制造)、4质量份的氧化镁(协和化学工业株式会社制造)，在130℃下混炼12分钟，得到了改性聚氯乙烯A。
＜改性聚氯乙烯B～E的制作＞
除了将混炼聚氯乙烯和各添加剂的温度分别设为140℃、150℃、160℃、170℃以外，所有的条件均与改性聚氯乙烯A的条件一致，得到了改性聚氯乙烯B～E。
＜改性聚氯乙烯F、G的制作＞
除了将混炼聚氯乙烯和各添加剂的时间分别设为8分钟以及16分钟以外，所有的条件均与改性聚氯乙烯C的条件一致，得到了改性聚氯乙烯F、G。
＜改性聚氯乙烯H的制作＞
除了将0.3质量份的硫氰尿酸变更为0.3质量份的2,5-二巯基-1,3,4-噻二唑(阿达玛斯试剂制)以外，所有的条件均与制作改性聚氯乙烯C的条件一致，得到了改性聚氯乙烯H。
将改性聚氯乙烯A～H中使用的多官能亲核试剂的种类、混炼温度、混炼时间汇总表示在表1中。
[表1]
  多官能亲核试剂 混炼温度(℃) 混炼时间(分钟)
改性聚氯乙烯A 硫氰尿酸 130 12
改性聚氯乙烯B 硫氰尿酸 140 12
改性聚氯乙烯C 硫氰尿酸 150 12
改性聚氯乙烯D 硫氰尿酸 160 12
改性聚氯乙烯E 硫氰尿酸 170 12
改性聚氯乙烯F 硫氰尿酸 150 8
改性聚氯乙烯G 硫氰尿酸 150 16
改性聚氯乙烯H 2,5-二巯基-1,3,4-噻二唑 150 12
＜共交联体A的制作＞
使用密炼机，混合了20质量份的改性聚氯乙烯A、80质量份的聚氯丁二烯(电气化学工业株式会社制造DCR-OM-40)，在130℃下混炼4分钟，得到了共交联体A。
＜共交联体B～H的制作＞
除了将改性聚氯乙烯A分别换成改性聚氯乙烯B～H以外，所有的条件 均与制作共交联体A的条件一致，得到了共交联体B～H。
＜共交联体I、J的制作＞
除了将改性聚氯乙烯和聚氯丁二烯的混炼温度分别设为120℃、140℃以外，所有的条件均与制作共交联体C的条件一致，得到了共交联体I、J。
＜共交联体K、L的制作＞
除了将改性聚氯乙烯C以及聚氯丁二烯的混合量分别设为5：95、45：55以外，所有的条件均与制作共交联体C的条件一致，得到了共交联体K、L。
＜共交联体M、N的制作＞
除了将改性聚氯乙烯和聚氯丁二烯的混炼温度分别设为105℃、155℃以外，所有的条件均与制作共交联体C的条件一致，得到了共交联体M、N。
＜共交联体O的制作＞
使用上述密炼机，混炼了20质量份的上述聚氯乙烯和80质量份的上述聚氯丁二烯14分钟之后，添加0.3质量份的上述硫氰尿酸、4质量份的上述氧化镁，再继续混炼4分钟，得到了共交联体O。
＜共交联体P的制作＞
除了将0.5质量份的硫氰尿酸变更为0.3质量份的2,5-二巯基-1,3,4-噻二唑(阿达玛斯试剂制)以外，所有的条件均与制作共交联体O的条件一致，得到了共交联体P。
＜共交联体Q的制作＞
除了没有添加0.5质量份的硫氰尿酸以外，所有的条件均与制作共交联体O的条件一致，得到了共交联体Q。
将共交联体A～Q的制造条件汇总表示在表2中。
[表2]
Figure PCTCN2016080989-appb-000001
＜实施例1＞
加入100质量份的通过上述方法得到的共交联体A、5质量份的氧化锌(三井金属工业株式会社制造)、0.5质量份的乙撑硫脲(产品名称：Accel 22S、川口化学工业株式会社制造)、0.5质量份的硬脂酸(中国国药集团化学试剂有限公司制造)，使用直径为4英寸的两根开放式辊在40℃下、混炼5分钟，从而得到了实施例1的氯丁二烯橡胶组合物。
＜评价＞
将通过上述方法得到的实施例1的氯丁二烯橡胶组合物在160℃×20分钟、压力为0.8MPa的条件下进行加压硫化，制作了厚2.0mm的硫化成型体薄片。从该硫化成型体薄片中剪下试验片，在制作试验片之后立即依据JIS  K6251进行机械强度试验(拉伸强度、断裂伸长率、100％拉伸弹性模量的测定)。具体而言，使用哑铃3号模从硫化成型体薄片中剪下试验片，使用全自动橡胶拉伸试验机(装置名称：AGS-H、岛津制作所制造)，在环境温度23℃、拉伸速度500mm/分钟的条件下进行测定。
另外，在ASTM No.3油中、100℃下将剪下的试验片浸渍70小时之后，依据JIS K6258进行浸渍试验，并进行耐油性试验(体积变化率、重量变化率)。关于使用氯丁二烯橡胶组合物所得到的硫化成型体的机械强度，若拉伸强度为7.5MPa以上、断裂伸长率为220％以上、100％拉伸弹性模量为0.2MPa时为合格。关于耐油性，若体积变化率为80％以下、重量变化率为100％以下时为合格。所得到的结果如表3所示。
[表3]
Figure PCTCN2016080989-appb-000002
＜实施例2～12、比较例1～5＞
除了将共交联体A分别换成共交联体B～Q以外，所有的条件均与实施例1的条件一致，制作了实施例2～12以及比较例1～5的氯丁二烯橡胶组合物，在与实施例1相同的条件下进行评价。评价结果如表3所示。在比较例1中，由于混炼温度低，因此改性聚氯乙烯和聚氯丁二烯无法均匀分散，且无法得到氯丁二烯橡胶组合物。在比较例2中，由于混炼温度高，因此改性聚氯乙烯和聚氯丁二烯的一部分发生了硫化，一部分变成了粉状的氯丁二烯橡 胶组合物。因而，对于比较例1和比较例2没有进行评价。
如表3所示，利用本发明的氯丁二烯橡胶组合物，能够得到不会损害用拉伸试验来评价的机械特性、并使耐油耐热性进一步提高的氯丁二烯橡胶组合物的硫化物。

Claims (12)

  1. 一种氯丁二烯橡胶组合物，所述氯丁二烯橡胶组合物包含：使聚氯乙烯和多官能亲核试剂进行化学反应而得到的改性聚氯乙烯与聚氯丁二烯的共交联体。
  2. 根据权利要求1所述的氯丁二烯橡胶组合物，其中，改性聚氯乙烯与聚氯丁二烯的共交联体是由5～45质量份的改性聚氯乙烯和95～55质量份的聚氯丁二烯组成的共交联体。
  3. 根据权利要求1或2所述的氯丁二烯橡胶组合物，其中，多官能亲核试剂是从硫醇化合物中选出的至少一种。
  4. 根据权利要求1或2所述的氯丁二烯橡胶组合物，其中，改性聚氯乙烯是使聚氯乙烯与多官能亲核试剂在140～160℃下进行化学反应而得到的物质。
  5. 根据权利要求1或2所述的氯丁二烯橡胶组合物，其中，改性聚氯乙烯与聚氯丁二烯的共交联体是使改性聚氯乙烯与聚氯丁二烯在120～140℃下进行共交联而得到的物质。
  6. 根据权利要求1或2所述的氯丁二烯橡胶组合物，其中，聚氯乙烯为软化温度是80～160℃的聚氯乙烯。
  7. 根据权利要求1或2所述的氯丁二烯橡胶组合物，其中，在100质量％的聚氯乙烯中，改性聚氯乙烯中的多官能亲核试剂为0.1～1.5质量％。
  8. 一种硫化成型体，所述硫化成型体是使用权利要求1或2所述的氯丁二烯橡胶组合物而得到的。
  9. 一种使用了权利要求7所述的硫化成型体的机械用皮带、防振橡胶、橡胶轮胎、雨刷用叶片、海绵、软管、电线电缆包覆、橡胶衬里。
  10. 一种氯丁二烯橡胶组合物，其包含使5～45质量份的改性聚氯乙烯与95～55质量份的聚氯丁二烯在120～140℃下进行共交联而得到的共交联体，所述改性聚氯乙烯是使软化温度为80～160℃的聚氯乙烯与作为多官能亲 核试剂的硫醇化合物在140～160℃下进行化学反应而得到的，在100质量％的所述聚氯乙烯中含有0.1～1.5质量％的所述多官能亲核试剂。
  11. 一种硫化成型体，所述硫化成型体是使用权利要求9所述的氯丁二烯橡胶组合物而得到的。
  12. 一种使用了权利要求10所述的硫化成型体的机械用皮带、防振橡胶、橡胶轮胎、雨刷用叶片、海绵、软管、电线电缆包覆、橡胶衬里。
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