JPWO2008114706A1 - Polyether-based multi-component copolymer, cross-linkable rubber composition containing the same, and automotive rubber parts comprising the cross-linked product - Google Patents

Abstract

The present invention provides a crosslinked product of a polyether copolymer that can be used as a rubber having all of excellent heat resistance, oil resistance, fuel oil resistance, and low temperature characteristics, with little or no halogen-containing compound, and The copolymer is provided. 60 to 99.8 mol% of structural units represented by the following general formula (I), 0 to 39.8 mol% of structural units represented by the following general formula (II), and a structure derived from a crosslinkable oxirane monomer A polyether multi-component copolymer having 0.2 to 10 mol% of units. In the formula, R 1 is an alkyl group having 1 to 6 carbon atoms, R 2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group or —CH 2 O—R 3, and R 3 is an alkyl group having 1 to 6 carbon atoms or a phenyl group. means. [Chemical 1]

Description

  The present invention relates to a polyether multi-component copolymer mainly comprising a structural unit having a cyano group in the side chain, a crosslinking rubber composition containing the copolymer, a crosslinked product obtained by crosslinking this, and further from the crosslinked product. This relates to automotive rubber parts.

  Polyether polymers can have various properties by selecting the type of oxirane compound that is the raw material, so rubber parts for automobiles, rubber parts for electrical and electronic equipment, civil engineering, and construction It is used as a polymer material in a wide range of fields such as rubber materials for industrial use, various industrial rubber members, polymers for various plastic blends, and polymer solid electrolytes.

Since the crosslinked product of the polyether copolymer having a cyano group has excellent ionic conductivity, it has an epoxy resin composition for a polymer solid electrolyte (see Patent Document 1) and has excellent dielectric properties. Therefore, the use as a high dielectric resin composition (see Patent Document 2) is known.
Japanese Patent Application Laid-Open No. 11-121036 JP, 2002-179767, A With regard to application to rubber materials, in particular, as a rubber composition having excellent cold resistance (see Patent Document 3 and Non-Patent Document 1), propylene oxide-cyanoethyl glycidyl ether-allyl glycidyl. Although a crosslinked product of an ether terpolymer has been proposed, these are not used for automobile parts because of their poor heat resistance, oil resistance, fuel oil resistance, and the like. U.S. Pat. No. 3,410,810 J. Macromol. Sci. Chem., A7, 1483 (1973) Epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-ethylene oxide, generally called epichlorohydrin rubber -Crosslinked products of allyl glycidyl ether terpolymers have excellent heat resistance, oil resistance, fuel oil resistance, ozone resistance, low temperature characteristics, semiconductive characteristics, etc. Widely used as a rubber member for electrical and electronic equipment.

  On the other hand, as part of countermeasures against environmental problems in recent years, there has been an active movement to avoid using polymer materials containing a large amount of halogen as much as possible. However, a polyether polymer rubber that can be substituted for epichlorohydrin rubber and whose cross-linked product has excellent heat resistance, oil resistance, fuel oil resistance, and low temperature characteristics has not yet been found. Currently.

On the other hand, various polyether polymer rubbers produced with little or no halogen-containing compound such as epichlorohydrin have been proposed. For example, ethylene oxide and oxirane copolymerizable therewith are proposed. Monomers are copolymerized, and the resulting copolymer is used for rubber parts of OA equipment (see, for example, Patent Document 4), water-swellable sealing material (see, for example, Patent Document 5), polymer solid It has been proposed to use it as an electrolyte (see, for example, Patent Document 6).
JP 2002-105246 A JP 2002-194202 A However, the polyether polymers described in these documents have performances that can be used only in the above specific fields, and are polyether copolymers that incorporate a specific oxirane monomer. There is no description or suggestion that the polymer has various properties such as excellent heat resistance, oil resistance, fuel oil resistance, and low temperature characteristics.

  In view of the above environmental problems in recent years, the object of the present invention is to provide various properties such as excellent heat resistance, oil resistance, fuel oil resistance, low temperature characteristics and the like, using little or no halogen-containing compound such as epichlorohydrin. An object of the present invention is to provide a crosslinked product of a polyether copolymer that can be used as a rubber having both properties.

  As a result of various studies to solve the above problems, the present inventors used an oxirane monomer having a cyano group in the side chain, and the monomer and a crosslinkable oxirane monomer having a crosslinkable functional group. A multi-component copolymer having a specific composition obtained by copolymerizing a monomer and, if necessary, an alkylene oxide in a substantially random manner is crosslinked to provide excellent heat resistance, oil resistance, fuel oil resistance, low temperature characteristics, etc. As a result, the present invention was completed.

The present invention includes 60 to 99.8 mol% of structural units represented by the following general formula (I), 0 to 39.8 mol% of structural units represented by the following general formula (II), and a single amount of crosslinkable oxirane. A crosslinkable rubber composition containing a polyether-based multi-component copolymer having 0.2 to 10 mol% of a structural unit derived from a body and a crosslinking agent, a crosslinkable rubber composition containing the copolymer, and an automobile comprising the crosslinked product Providing rubber parts.

[Wherein, R ¹ represents an alkyl chain having 1 to 5 carbon atoms. ]

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or —CH ₂ O—R ³ , and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. . ]
Hereinafter, the configuration of the present invention will be described in detail.

60 to 99.8 mol% of the structural unit represented by the general formula (I), 0 to 39.8 mol% of the structural unit represented by the general formula (II), and a structure derived from a crosslinkable oxirane monomer The molecular weight of the polyether-based multi-component copolymer (hereinafter abbreviated as “polyether multi-component copolymer”) having 0.2 to 10 mol% of the unit is JIS K 6300- from the viewpoint of processability of the rubber material. The Mooney viscosity (ML _{1 + 4} ) measured at 100 ° C. according to the method described in 1 is in the range of 5 to 200, preferably 10 to 100. Such a high molecular weight polyether multi-component copolymer is prepared by using a solution capable of ring-opening polymerization of an oxirane compound as a catalyst, and by a solution polymerization method, a slurry polymerization method, or the like within a temperature range of -20 to 100 ° C. Can do. As such a catalyst, for example, a catalyst system obtained by reacting organic aluminum mainly with water or phosphorus oxo acid compound or acetylacetone, and obtained by reacting water mainly with organic zinc. Examples thereof include a catalyst system and an organic tin-phosphate ester condensate catalyst system. For example, polyether multicomponent copolymers can be prepared using the organotin-phosphate ester condensate catalyst system described in US Pat. No. 3,773,694 by the present applicant.

  In addition, by such a manufacturing method, the structural unit (I) 60 to 99.8 mol%, the structural unit (II) 0 to 39.8 mol%, and the structural unit 0.2 derived from the crosslinkable oxirane monomer In order to produce a polyether multi-component copolymer having 10 mol% and having the rubber-like properties aimed by the present invention, the monomer components corresponding to these structural units are substantially randomly selected. Copolymerization is preferred.

  As the proportion of the structural unit (I) increases, the heat resistance and fuel oil resistance of the resulting crosslinked product are improved. However, if the proportion is too large, the vulcanized physical properties as a rubber material are lowered. Therefore, the proportion of the structural unit (I) is preferably 60 to 99.8 mol%, more preferably 70 to 99.8 mol%, and particularly preferably 90 to 99.6 mol%.

  Examples of the monomer constituting the structural unit (I) include cyanoalkyl glycidyl ethers such as cyanomethyl glycidyl ether, cyanoethyl glycidyl ether, and cyanopropyl glycidyl ether. Two or more of these may be used in combination. However, when a cyanoalkyl glycidyl ether having a large number of carbon atoms is used, the oil resistance and fuel oil resistance of the resulting crosslinked product of the polyether multi-component copolymer tend to decrease. The ether is cyanomethyl glycidyl ether, cyanoethyl glycidyl ether, particularly preferably cyanoethyl glycidyl ether.

  The range of the proportion of the structural unit (II) is 0 to 39.8 mol%. However, as the proportion increases, the proportion of the structural unit (I) decreases, so that the fuel oil resistance, oil resistance, and heat resistance are increased. Decreases. The proportion of the structural unit (II) is preferably 0 to 29.8 mol%, particularly preferably 0 to 9.6 mol%.

  Examples of the monomer constituting the structural unit (II) include alkylene oxides such as ethylene oxide, propylene oxide, isobutylene oxide, n-butylene oxide, methyl glycidyl ether, and styrene oxide. Two or more of these may be used in combination. However, when an alkylene oxide having a large number of carbon atoms is used, the oil resistance and fuel oil resistance of the resulting crosslinked product of the polyether multi-component copolymer tend to be lowered. Therefore, the alkylene oxide preferably used as the monomer is ethylene oxide and Propylene oxide, particularly preferably ethylene oxide.

  Crosslinkable oxirane monomers are introduced into these (co) polymers as a cross-linking site to crosslink the homopolymer of structural unit (I) or the copolymer of structural unit (I) and structural unit (II). Any oxirane monomer may be used, such as halogen-containing oxirane monomers, specific examples include epihalohydrins such as epibromohydrin and epiiodohydrin, p-chlorostyrene oxide, dibromocyanoethyl glycidyl ether, Halogen-containing oxiranes other than epihalohydrins such as m-chloromethylstyrene oxide, p-chloromethylstyrene oxide, glycidyl chloroacetate and chloromethyl glycidate, 2,3-epoxypropyl-2 ′, 3′-epoxy-2 ′ -Methyl propyl ether, metaglycidic acid glycidyl ester, glycy Diepoxy compounds having reactive functional groups in the molecule such as metaglycidyl doic acid ester, 1,2,3,4-diepoxy-2-methylbutane, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl crotonic acid, 3 And ethylenically unsaturated group-containing oxiranes such as 4-epoxy-1-butene. Two or more of these crosslinkable oxirane monomers may be used in combination.

  Especially for automotive rubber parts, heat resistance is required, so as crosslinkable oxirane monomers, halogen-containing oxiranes and diepoxy compounds having reactive functional groups in the molecule contain ethylenically unsaturated groups. Compared to oxiranes, it is preferable because of its high heat resistance.

  The crosslinkable oxirane monomer may contain a halogen. However, when the halogen-containing oxirane monomer is used as the crosslinkable oxirane monomer, the main content of the present invention is to reduce the halogen content in the polyether multi-component copolymer as much as possible when the amount used is too large. Therefore, the proportion of the halogen-containing oxirane monomer should be as low as possible. The halogen content in the polyether multi-component copolymer is preferably 7% by weight or less.

  The proportion of the structural unit derived from the crosslinkable oxirane monomer is in the range of 0.2 to 10 mol%, preferably 1 to 6 mol%. When this ratio is less than 0.2 mol%, a sufficient crosslinking density cannot be obtained when the polyether multi-component copolymer is crosslinked, and therefore a crosslinked product having sufficient physical properties cannot be obtained. On the contrary, if this ratio exceeds 10 mol%, there is a possibility of causing a so-called scorch problem and a decrease in heat resistance, which is not preferable.

 As the crosslinkable oxirane monomer, a chlorine-containing crosslinkable oxirane monomer can be used, and as the chlorine-containing crosslinkable oxirane monomer, o-chloromethylstyrene oxide, p-chlorostyrene oxide, m-chloromethylstyrene oxide can be used. And oxiranes having highly active chlorine such as p-chloromethylstyrene oxide, glycidyl chloroacetate and chloromethyl glycidate. Two or more of these crosslinkable oxirane monomers may be used in combination. Particularly preferred are o-chloromethyl styrene oxide, m-chloromethyl styrene oxide, p-chloromethyl styrene oxide, glycidyl chloroacetate and chloromethyl glycidate.

  A structural unit derived from a chlorine-containing crosslinkable oxirane monomer exhibits reactivity even if its proportion is relatively low. The proportion of the structural unit derived from the chlorine-containing crosslinkable oxirane monomer is in the range of 0.2 to 10 mol%, preferably 0.4 to 5 mol%. When this ratio is less than 0.2 mol%, a sufficient crosslinking density cannot be obtained when the polyether multi-component copolymer is crosslinked, and therefore a crosslinked product having sufficient physical properties cannot be obtained. On the contrary, if this ratio exceeds 10 mol%, there is a possibility of causing a so-called scorch problem and a decrease in heat resistance, which is not preferable.

  The proportion of the structural unit derived from the chlorine-containing crosslinkable oxirane monomer is preferably lower in order to reduce the halogen content in the polyether multi-component copolymer as much as possible, and the halogen content in the polyether multi-component copolymer The amount is preferably 1% by weight or less. The chlorine-containing crosslinkable oxirane monomer of the present invention is particularly excellent in that the halogen content in the polyether copolymer can be reduced.

  Among the crosslinkable oxirane monomers, when epihalohydrins such as epibromohydrin and epiiodohydrin are used, and as the crosslinkable oxirane monomer, a chlorine-containing crosslinkable oxirane monomer, preferably chloromethylstyrene When using oxiranes having highly active chlorine such as oxide, glycidyl chloroacetate and chloromethyl glycidate, those usually used for halogen-containing rubbers can be blended as crosslinking agents. Examples of such crosslinking agents include amine-based crosslinking agents such as ethylenediamine, diethylenetriamine, triethylenetetramine, p-phenylenediamine, and hexamethylenediamine carbonate, and thiourea-based crosslinking agents such as ethylenethiourea, 1,3-diethylthiourea, and trimethylthiourea. 2,5-dimercapto-1,3,4-thiadiazole, thiadiazole-based crosslinking agents such as 2,5-mercapto-1,3,4-thiadiazole-5-thiobenzoate, 2,4,6-trimercapto-1 , 3,5-triazine, 1-hexylamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercaptotriazine, 1-phenylamino-3,5-dimercaptotriazine, etc. Agent, quinoxaline-2, -2,3-dimercaptoquinoxaline derivative-based crosslinking agents such as dithiocarbonate, 6-methylquinoxaline-2,3-dithiocarbonate, 5,6-dimethylquinoxaline-2,3-dithiocarbonate, pyrazine-2,3-dithio 2,3-Dimercaptopyrazine derivatives such as carbonate, 5-methyl-2,3-dimercaptopyrazine, 5,6-dimethyl-2,3-dimercaptopyrazine, 5-methylpyrazine-2,3-dithiocarbonate Examples of the crosslinking agent include bisphenol-based crosslinking agents such as bisphenol A, bisphenol AF, and bisphenol S. In addition, sulfur, an active sulfur-releasing organic vulcanizing agent, and ammonium benzoate.

  The amount of the crosslinking agent is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the polyether multi-component copolymer. If the blending amount is less than this range, crosslinking may be insufficient. Conversely, if it exceeds this range, it is not economical.

  In addition, when halogen-substituted oxiranes other than epihalohydrins such as chloromethylstyrene oxide, glycidyl chloroacetate, chloromethyl glycidate, etc. are used as the crosslinkable oxirane monomer, In addition, sulfur, active sulfur releasing organic vulcanizing agent, ammonium benzoate and the like can be exemplified as the crosslinking agent. Even when these crosslinking agents are used, the above accelerators, retarders, and acid acceptors can be appropriately used.

  On the other hand, when the above diepoxy compounds are used as the crosslinkable oxirane monomer, examples of the crosslinking agent include alkyldithiocarbamate-based crosslinking agents such as zinc dimethyldithiocarbamate and iron dimethyldithiocarbamate, ethylenediamine, diethylenetriamine, and triethylene. Examples include amine crosslinking agents such as tetramine, p-phenylenediamine, and hexamethylenediamine carbamate, active sulfur releasing organic vulcanizing agents such as dipentamethylene thiuram tetrasulfide, ammonium benzoate, isocyanuric acid, and ammonium salts of organic acids. . Also in this case, a crosslinking accelerator and a retarder can be appropriately used. Examples of the accelerator include imidazoles and onium salts, and examples of the retarder include phthalic anhydride.

  Furthermore, when using ethylenically unsaturated group-containing oxiranes such as allyl glycidyl ether and glycidyl methacrylate as the crosslinkable oxirane monomer, it is possible to blend those usually used in diene rubbers as the crosslinking agent. it can. Examples of such crosslinking agents include sulfur-based crosslinking (vulcanization) agents such as sulfur, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and morpholine disulfide, and quinone dioximes such as parabenzoquinone dioxime and benzoylquinone dioxime. Resin-based crosslinking agents such as oxime-based crosslinking agent, polymethylolphenol, alkylphenol formaldehyde resin, bromated alkylphenol formaldehyde resin, dicumyl peroxide, 1,3-bis (ter-butylperoxyisopropyl) benzene, n-butyl-4 , 4-bis (ter-butylperoxy) valerate, 2,5-dimethyl-2,5-di (ter-butylperoxy) hexane and other organic peroxide crosslinking agents. These crosslinking agents and vulcanization accelerators, vulcanization acceleration assistants, crosslinking assistants and retarders known for diene rubbers can be used in combination as appropriate.

  Further, known accelerators (that is, vulcanization accelerators), retarders and the like which are usually used together with these crosslinking agents can also be used in the production of the polyether multi-component copolymer. Examples of accelerators include sulfur, thiuramsphides, morpholine sulfides, amines, weak acid salts of amines, basic silica, quaternary ammonium salts, quaternary phosphonium salts, polyfunctional vinyl compounds, mercaptobenzothiazoles, Examples thereof include sulfenamides and dimethylthiocarbonates.

  Examples of the retarder include N- (cyclohexylthio) phthalimide, organic zinc compound, acidic silica, sulfonamide compound and the like. The compounding quantity of an accelerator or a retarder is 0-10 weight part with respect to 100 weight part of a polyether multicomponent copolymer, Preferably it is 0.1-5 weight part.

  In addition, it is also preferable to combine the said crosslinking agent and acid acceptor. Examples of the acid acceptor used in this case include magnesium oxide, magnesium hydroxide, aluminum hydroxide, barium hydroxide, sodium carbonate, magnesium carbonate, barium carbonate, quicklime, slaked lime, calcium carbonate, calcium silicate, sodium stearate, Potassium stearate, calcium stearate, zinc stearate, calcium phthalate, calcium phosphite, zinc white, tin oxide, lisage, red lead, lead white, dibasic lead phthalate, dibasic lead carbonate, tin stearate, base Lead phosphite, basic tin phosphite, basic lead sulfite, tribasic lead sulfate, zeolites, aluminophosphate type molecular sieve, layered silicate, synthetic hydrotalcite, Li-Al inclusion compound Etc. The compounding quantity of an acid acceptor is 0-30 weight part with respect to 100 weight part of a polyether multicomponent copolymer, Preferably it is 0.1-10 weight part.

  In the polyether multi-component copolymer, additives other than those usually used in the art, for example, lubricants, fillers, reinforcing agents, plasticizers, anti-aging agents, processing aids, flame retardants, foaming agents , Foaming aids, conductive agents, antistatic agents, pigments, tackifiers and the like can be blended as necessary. Furthermore, it is also possible to perform blending with rubber, resin and the like, which is usually performed in the technical field.

  In order to produce a rubber product by crosslinking the polyether multi-component copolymer, a polyether multi-component is appropriately used by using a mixing means conventionally used in the field of polymer processing, for example, a mixing roll, a Banbury mixer, various kneaders and the like. A crosslinker and other compounding agents are blended into the copolymer to crosslink the polyether multi-component copolymer. The temperature and time required for crosslinking are appropriately set depending on the crosslinkable oxirane compound, the crosslinking agent, etc. used in the production of the polyether multi-component copolymer. Usually, the temperature is 100 to 250 ° C., and the time is 0.5 to 300 minutes. Is in range. As a method of cross-linking molding, methods such as compression molding using a mold, injection molding, steam can, air bath, infrared ray, or heating using microwaves can be appropriately used.

  The cross-linked product of the polyether multi-component copolymer thus obtained can be used in all fields where polyether rubbers typified by epichlorohydrin rubbers are used. For example, it is useful as a rubber material for various fuel-based laminated hoses for automobiles, air-based laminated hoses, tubes, belts, diaphragms, seals and the like, and rubber materials for general industrial equipment and devices. In particular, it can be suitably applied to rubber parts for automobiles by taking advantage of the excellent heat resistance and oil resistance of the polyether multi-component copolymer.

  Furthermore, since the polyether multi-component copolymer of the present invention contains almost no halogen atoms due to its chemical structure, it is possible to reduce environmental pollution such as generation of halogen-containing gas due to combustion.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples without departing from the gist thereof.

Production of Polymerization Catalyst A three-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 10 g of tributyltin chloride and 35 g of tributyl phosphate, and these were heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream. The distillate was distilled off, and a condensate solid at room temperature was obtained as a residue. Thereafter, this was used as a polymerization catalyst in Examples and Comparative Examples.

Analysis of Polymer The copolymer composition of the polyether multi-component copolymer obtained in the examples was determined by ¹ H-NMR spectrum. The Mooney viscosity (ML _{1 + 4} ) of the polyether multi-component copolymer was measured at 100 ° C. using an L rotor according to the method described in JIS K 6300.

Production Example 1 of Polyether Multielement Copolymer
The inside of a stainless steel reactor with a jacket having a capacity of 5 L was purged with nitrogen. While the polymerization rate was monitored by gas chromatography, it was added successively. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C.

  After removing the polymer from the reactor by decantation, it was dried at 80 ° C. for 8 hours under reduced pressure to obtain 197 g of a polyether multi-component copolymer. The copolymer composition of this polyether multi-element copolymer was 65 mol% cyanoethyl glycidyl ether units, 33 mol% ethylene oxide units, and 2 mol% epibromohydrin units. The Mooney viscosity measured at 100 ° C. was 53, and the halogen content was 1.6 wt%.

Example 2
Charge during polymerization and its amount, polymerization catalyst 18 g, cyanoethyl glycidyl ether 267 g, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether 18 g, ethylene oxide 15 g, toluene 2700 g Except for the above, 224 g of a polyether multi-component copolymer was obtained in the same procedure as in Example 1.

  The copolymer composition of this polyether multi-component copolymer is as follows: cyanoethyl glycidyl ether unit 80 mol%, ethylene oxide unit mol 16%, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether unit 4 Mol%. The Mooney viscosity measured at 100 ° C. was 46.

Example 3
Polyether multi-component copolymer in the same procedure as in Example 1 except that the amount charged in polymerization and its amount, 18 g of polymerization catalyst, 278 g of cyanoethyl glycidyl ether, 16 g of epibromohydrin, 6 g of propylene oxide and 2700 g of toluene were changed. 182 g was obtained.

  The copolymer composition of this polyether multi-component copolymer was 90 mol% of cyanoethyl glycidyl ether units, 5% of propylene oxide units, and 5 mol% of epibromohydrin units. The Mooney viscosity measured at 100 ° C. was 43 and the halogen content was 1.6 wt%.

Example 4
The inside of a jacketed stainless steel reactor with an internal volume of 5 L was purged with nitrogen, charged with 18 g of the polymerization catalyst, 285 g of cyanoethyl glycidyl ether, 15 g of epibromohydrin, and 2700 g of toluene as a solvent, and the polymerization rate was monitored by gas chromatography. did. The polymerization reaction was stopped by adding 1 g of methanol after 4 hours while maintaining the reaction temperature at 20 ° C.

  After taking out the polymer from the reactor by decantation, it was dried under reduced pressure at 80 ° C. for 8 hours to obtain 182 g of a polyether multi-component copolymer. The copolymer composition of this polyether multi-component copolymer was 95 mol% of cyanoethyl glycidyl ether units and 5 mol% of epibromohydrin units. The Mooney viscosity measured at 100 ° C. was 47, and the halogen content was 3.1 wt%.

Example 5
237 g of a polyether multi-component copolymer was obtained in the same manner as in Example 4 except that the amount of the charge and the amount thereof during polymerization were changed to 18 g of polymerization catalyst, 285 g of cyanoethyl glycidyl ether, 15 g of allyl glycidyl ether, and 2700 g of toluene.

  The copolymer composition of this polyether multi-component copolymer was 95 mol% of cyanoethyl glycidyl ether units and 5 mol% of allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 55.

Example 6
The procedure was carried out except that the polymerization charge and amount thereof were changed to 18 g of polymerization catalyst, 280 g of cyanoethyl glycidyl ether, 20 g of 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, and 2700 g of toluene. In the same procedure as in Example 4, 213 g of a polyether multi-component copolymer was obtained.

  The copolymer composition of this polyether multi-element copolymer was 95 mol% of cyanoethyl glycidyl ether units and 5 mol% of 2,3-epoxypropyl-2 ', 3'-epoxy-2'-methylpropyl ether units. The Mooney viscosity measured at 100 ° C. was 45.

Example 7
The inside of a jacketed stainless steel reactor with an internal volume of 10 L was purged with nitrogen, charged with 14 g of the condensate catalyst, 1,000 g of cyanoethyl glycidyl ether, 50 g of glycidyl chloroacetate, and 2500 g of toluene as a solvent, and the polymerization rate was gas chromatographed. Followed by graphy. The polymerization reaction was stopped by adding 1 g of methanol after 8 hours while maintaining the reaction temperature at 60 ° C.

  After removing the polymer from the reactor by decantation, it was dried at 80 ° C. under reduced pressure for 8 hours to obtain 920 g of a polyether multi-component copolymer. The copolymer composition of this polyether multi-element copolymer was 96 mol% of cyanoethyl glycidyl ether units and 4 mol% of glycidyl chloroacetate units. The Mooney viscosity measured at 100 ° C. was 38, and the chlorine content was 1.1%.

Example 8
940 g of a polyether multi-component copolymer was obtained in the same procedure as in Example 7 except that the amount of the charged product and the amount thereof were changed to 14 g of condensate catalyst, 1,000 g of cyanoethyl glycidyl ether, and 19 g of glycidyl chloroacetate.

  The copolymer composition of this polyether multi-element copolymer was 98.5 mol% of cyanoethyl glycidyl ether units and 1.5 mol% of glycidyl chloroacetate units. The Mooney viscosity measured at 100 ° C. was 39, and the chlorine content was 0.41%.

Example 9
870 g of a polyether multi-component copolymer was obtained in the same procedure as in Example 7, except that the amount of the charged product and the amount thereof were changed to 14 g of condensate catalyst, 1,000 g of cyanoethyl glycidyl ether, and 9 g of glycidyl chloroacetate.

  The copolymer composition of this polyether multi-component copolymer was 99.3 mol% of cyanoethyl glycidyl ether units and 0.7 mol% of glycidyl chloroacetate units. The Mooney viscosity measured at 100 ° C. was 47, and the chlorine content was 0.21%.

Example 10
The inside of a jacketed stainless steel reactor with an internal volume of 10 L was purged with nitrogen, charged with 18 g of the condensate catalyst, 1,000 g of cyanoethyl glycidyl ether, 38 g of p-chloromethylstyrene oxide, and 2500 g of toluene as a solvent, and the polymerization rate Was followed by gas chromatography. The polymerization reaction was stopped by adding 1 g of methanol after 6 hours while maintaining the reaction temperature at 60 ° C.

  After removing the polymer from the reactor by decantation, it was dried at 80 ° C. under reduced pressure for 8 hours to obtain 782 g of a polyether multi-component copolymer. The copolymer composition of this polyether multi-component copolymer was 97 mol% of cyanoethyl glycidyl ether units and 3 mol% of p-chloromethylstyrene oxide units. The Mooney viscosity measured at 100 ° C. was 47, and the chlorine content was 0.82%.

Comparative Example 1
168 g of the polyether multi-component copolymer in the same procedure as in Example 1 except that the amount charged in the polymerization and the amount thereof were changed to 18 g of polymerization catalyst, 215 g of cyanoethyl glycidyl ether, 20 g of allyl glycidyl ether, 65 g of propylene oxide and 2700 g of toluene. Got.

  The copolymer composition of this polyether multi-element copolymer was 55 mol% of cyanoethyl glycidyl ether units, 40% of propylene oxide units, and 5 mol% of allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 31.

Comparative Example 2
Charge 232 g of the polyether multi-component copolymer in the same procedure as in Example 1 except that the amount of the charged product and the amount thereof were changed to 18 g of polymerization catalyst, 197 g of cyanoethyl glycidyl ether, 25 g of allyl glycidyl ether, 78 g of ethylene oxide, and 2700 g of toluene. Obtained.

  The copolymer composition of this polyether multi-component copolymer was 40 mol% of cyanoethyl glycidyl ether units, 55% of ethylene oxide units, and 5 mol% of allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 58.

Comparative Example 3
151 g of a polyether multi-component copolymer in the same procedure as in Example 1 except that the amount and amount of the charge during polymerization were changed to 18 g of polymerization catalyst, 127 g of cyanoethyl glycidyl ether, 25 g of allyl glycidyl ether, 148 g of propylene oxide, and 2700 g of toluene. Got.

  The copolymer composition of this polyether multi-component copolymer was 25 mol% of cyanoethyl glycidyl ether units, 70% of propylene oxide units, and 5 mol% of allyl glycidyl ether units. The Mooney viscosity measured at 100 ° C. was 32.

Comparative Example 4
286 g of a polyether multi-component copolymer was obtained in the same procedure as in Example 1 except that the amount charged in the polymerization and the amount thereof were changed to 18 g of polymerization catalyst, 207 g of epichlorohydrin, 93 g of ethylene oxide, and 2700 g of hexane.

  The copolymer composition of this polyether multi-element copolymer was 52 mol% of epichlorohydrin units and 48% of ethylene oxide units. The Mooney viscosity measured at 100 ° C. was 52 and the halogen content was 26 wt%.

Comparative Example 5
875 g of a polyether polymer was obtained in the same procedure as in Example 7 except that the amount of the charged product and the amount thereof were changed to 14 g of condensate catalyst, 1,000 g of cyanoethyl glycidyl ether, and 2500 g of toluene.

  The copolymer composition of this polyether polymer was 100 mol% of cyanoethyl glycidyl ether units, and the chlorine content was 0%. The Mooney viscosity measured at 100 ° C. was 46.

Examples 11-20, Comparative Examples 6-10
Preparation of a polyether multi-component copolymer cross-linked specimen A polyether multi-component cross-linked product was prepared using the following compounding agents in the ratios shown in Tables 1 and 2.

Carbon black: “Seast SO”, plasticizer manufactured by Tokai Carbon Co., Ltd .: “Adeka Sizer RS-107”, lubricant manufactured by Asahi Denka Kogyo Co., Ltd .: “Splendor R-300”, anti-aging agent manufactured by Kao Corporation: “Nauguard 445” ”, Acid acceptor manufactured by Crompton Co., Ltd. 1: synthetic hydrotalcite“ DHT-4A ”, acid acceptor manufactured by Kyowa Chemical Industry Co., Ltd. 2: magnesium oxide,“ Kyowa Mag 150 ”, zinc flower manufactured by Kyowa Chemical Industry Co., Ltd .: vulcanized Accelerating aid,
Sulfur: Vulcanizing agent, Vulcanization accelerator ETU: Vulcanizing agent, Ethylenethiourea DM: Vulcanization accelerator, “Noxeller DM”, manufactured by Ouchi Shinsei Chemical Co., Ltd. TS: Vulcanization accelerator, “Noxeller TS”, large Inner Emerging Chemical Co., Ltd. SS: Vulcanization retarder, “Noctizer SS”, Ouchi Emerging Chemical Co., Ltd. TRA: Vulcanizing agent, “Noxeller TRA”, Ouchi Emerging Chemical Co., Ltd. vulcanizing agent 1: 6- Methylquinoxaline-2,3-dithiocarbonate “Daisonette XL-21S” Other compounding agent manufactured by Daiso Corporation: stearic acid, sodium stearate Examples 1 to 6 in a 1 liter kneader set at 120 ° C. 100 parts by weight of the polyether multi-component copolymers obtained in Examples 7 to 10, Comparative Examples 1 to 4 and Comparative Example 5 were masticated for 1 minute, respectively, and then the A kneading compound shown in Tables 1 to 4 was added thereto. table 1 to 5 were blended in amounts shown in Table 4. After kneading these for 5 minutes, the obtained kneaded material was taken out from the kneader and formed into a sheet with a 7 inch roll set at 70 ° C. to prepare an A-kneaded rubber sheet.

  Next, using a 7-inch roll set at a temperature of 70 ° C., the B kneading compound shown in Tables 1 to 4 is added to the A kneaded rubber sheet in the compounding amounts shown in Tables 1 to 4, and the whole is kneaded for about 5 minutes. By doing so, a B-kneaded roll rubber sheet was produced.

The B-kneaded roll rubber sheet was heated and pressed with a press set at 170 ° C. for 15 minutes to form a 2 mm thick crosslinked rubber sheet. This was punched into a desired shape with a punching die to obtain a dumbbell-shaped No. 3 test piece shown in JIS K 6251. For Examples 11 to 14, 16 to 20, and Comparative Example 9, a test piece was obtained after heat treatment (so-called secondary vulcanization) for 2 hours in an oven set at a temperature of 150 ° C. with a 2 mm thick crosslinked rubber sheet. .

Performance Test A tensile test was performed on each test piece obtained in Examples and Comparative Examples according to the method described in JIS K 6251.

  The aging test of the vulcanized rubber was conducted by the cell oven method according to JIS K 6257 and under the conditions described in Tables 5-8.

  Fuel oil resistance was evaluated according to the method of JIS K 6258 using test fuel oil C under the conditions described in Tables 5-8.

  The evaluation of the low temperature property was performed by measuring the impact embrittlement temperature described in JIS K 6261.

These test results are shown in Tables 5 to 8.

  Evaluation of each polyether multi-component copolymer crosslinked product obtained in Examples and Comparative Examples is as follows.

 In Table 1, the cross-linked products of Examples 11 to 16 were prepared with little or no halogen-containing compound such as epibromohydrin (Examples 1 to 6). Low or zero. And as the crosslinked product of Examples 11-16 is understood from the performance test result of Table 5 and Table 7, the crosslinked product (Comparative Example 9) of the comparative example 4 manufactured using epichlorohydrin rubber | gum, and In comparison, the heat resistance and fuel oil resistance are more excellent.

  The crosslinked products of Comparative Examples 1 to 3 (Comparative Examples 6 to 8) using polyether multi-component copolymers in which the proportion of the structural unit (I) having a cyano group in the side chain departs from the scope of the present invention are low temperature characteristics. Although it is excellent in heat resistance, it is inferior in heat resistance and oil resistance.

 The crosslinked products of Examples 17 to 20 in Table 2 were produced in a very small amount of a halogen-containing compound as compared with Comparative Example 9 which is a crosslinked product using epichlorohydrin rubber. And the crosslinked material of Examples 17-20 has the performance in which heat resistance and fuel oil resistance were more excellent compared with the comparative example 9, so that the performance test result of Table 6, Table 8 may show. . The crosslinked product of Comparative Example 10 was not vulcanized because it did not have a structural unit derived from a chlorine-containing crosslinkable oxirane monomer.

  The polyether-based multi-component copolymer is configured as described above, and the cross-linked product has excellent heat resistance, oil resistance, fuel oil resistance, and low temperature characteristics. Therefore, the copolymer can be widely applied in the field where polyether rubber typified by epichlorohydrin rubber is used. For example, various fuel laminated hoses for automobiles, air laminated Rubber materials such as hoses, tubes, belts, diaphragms, seals, rubber parts for electrical and electronic equipment, semiconductive rubber parts such as charging rolls and transfer rolls used in office automation equipment, rubber for general industrial equipment and devices Useful as a material. In particular, it is expected to be applied to rubber parts for automobiles by taking advantage of the excellent heat resistance and oil resistance of the polyether multi-component copolymer.

Claims (11)

60 to 99.8 mol% of structural units represented by the following general formula (I), 0 to 39.8 mol% of structural units represented by the following general formula (II), and a structure derived from a crosslinkable oxirane monomer A polyether multi-component copolymer having 0.2 to 10 mol% of units.

[Wherein, R ¹ represents an alkyl chain having 1 to 5 carbon atoms. ]

[Wherein R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a phenyl group, or —CH ₂ O—R ³ , and R ³ represents an alkyl group having 1 to 6 carbon atoms or a phenyl group. . ]   The polyether multi-component copolymer according to claim 1, wherein the crosslinkable oxirane monomer is a halogen-containing crosslinkable oxirane monomer or a diepoxy compound having a reactive functional group in the molecule.   The polyether multi-component copolymer according to claim 2, wherein the halogen-containing crosslinkable oxirane monomer is a chlorine-containing crosslinkable oxirane monomer.   The polyether multi-component copolymer according to claim 3, wherein the chlorine-containing crosslinkable oxirane monomer is chloromethylstyrene oxide, glycidyl chloroacetate or chloromethyl glycidate.  The polyether multi-component copolymer according to any one of claims 1 to 4, wherein the halogen content in the polyether multi-component copolymer is 7% by weight or less.   The polyether multicomponent copolymer according to any one of claims 1 to 5, wherein the structural unit represented by the general formula (I) is in the range of 90 to 99.6 mol%.   The polyether multi-component copolymer according to any one of claims 1 to 6, wherein the structural unit represented by the general formula (II) is an ethylene oxide unit. The polyether multi-component copolymer according to any one of claims 1 to 7, wherein the Mooney viscosity (ML _{1 + 4} ) measured at 100 ° C is in the range of ₅ to 200.  A rubber composition for cross-linking comprising the polyether multi-component copolymer according to claim 1 and a cross-linking agent.   A crosslinked product obtained by crosslinking the crosslinking rubber composition according to claim 9.   An automotive rubber part comprising the cross-linked product according to claim 10.