WO2019017470A1 - クロロプレン系重合体及びその製造方法 - Google Patents
クロロプレン系重合体及びその製造方法 Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L15/02—Rubber derivatives containing halogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F36/16—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
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- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F236/16—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
- C08F236/18—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
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- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/14—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
- C08F36/16—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen
- C08F36/18—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen containing chlorine
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- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
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- 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
- C08L11/02—Latex
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J111/00—Adhesives based on homopolymers or copolymers of chloroprene
- C09J111/02—Latex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J115/00—Adhesives based on rubber derivatives
- C09J115/02—Rubber derivatives containing halogen
Definitions
- the present invention relates to a chloroprene polymer having a number average molecular weight Mn of 1.5 to 300,000 and having a functional group of a specific structure.
- Chloroprene rubber is a general-purpose rubber used for various applications because it is excellent in heat resistance, weather resistance, ozone resistance, chemical resistance, flame resistance and the like.
- the molecular weight of polychloroprene is controlled by varying chain transfer agents such as mercaptans and xanthogen disulfides.
- chain transfer agents such as mercaptans and xanthogen disulfides.
- chloroprene rubber is produced by radical emulsion polymerization, usable chain transfer agents are limited, and terminal functional groups that greatly affect rubber physical properties can not be easily changed.
- the present invention provides a chloroprene-based polymer capable of obtaining an industrially usable vulcanized rubber having a sufficient molecular weight and excellent in fatigue resistance and an adhesive excellent in layer separation resistance.
- the main purpose is
- the present invention provides a chloroprene polymer having a number average molecular weight Mn of 15,000 to 300,000 and having a functional group represented by the following general formula (1) or (2).
- R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group .
- the chloroprene polymer may have a functional group of the structure represented by the above general formula (1).
- the chloroprene polymer may have a molecular weight distribution Mw / Mn of 1.5 to 5.0, which is the ratio of the weight average molecular weight Mw to the number average molecular weight Mn.
- the chloroprene polymer may be a homopolymer of a chloroprene monomer.
- the chloroprene polymer may be a statistical copolymer comprising a chloroprene monomer and a monomer copolymerizable with the chloroprene monomer.
- the monomer copolymerizable with the chloroprene monomer is 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, acrylic acid, acrylic acid ester, methacrylic acid, methacrylic acid ester And at least one selected from the group consisting of acrylamides, unsaturated nitriles and aromatic vinyl compounds.
- the present invention is a production method for obtaining the above-mentioned chloroprene polymer,
- a chain transfer agent represented by the following general formula (3) or (4) is added to 100 parts by mass of the total monomers, and the substance amount of the total monomers and the chain transfer agent at the start of polymerization
- a solution (A) having a ratio [M] 0 / [CTA] of 5/1 to 500/1, and an aqueous solution (B) 500 to 5000 parts by mass of an emulsifier of 0.1 to 10% by mass are mixed and emulsified
- radical polymerization is performed, and when the polymerization rate reaches 20 to 50%, 100 to 5000 parts by mass of chloroprene monomer alone, or chloroprene monomer and monomer copolymerizable with chloroprene monomer are added.
- R 2 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group
- R 3 to 5 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted saturated, unsaturated or aromatic carbon ring, a substituted or unsubstituted Indicates a saturated, unsaturated or aromatic heterocycle, an organometallic species, or any polymer chain
- the final polymerization rate after the additional addition may be 50% or more.
- the method for producing the chloroprene polymer may be one to which a chain transfer agent represented by the above general formula (3) is added
- the present invention also provides a composition comprising the above chloroprene polymer.
- the composition may further contain at least one selected from the group consisting of natural rubber, isoprene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, butadiene rubber, styrene butadiene rubber and ethylene propylene rubber.
- the present invention also provides an adhesive composition comprising the composition.
- the present invention also provides an adhesive comprising the adhesive composition.
- the adhesive composition or the adhesive may have a layer separation resistance of 8 weeks or more.
- the present invention also provides a vulcanized rubber comprising the above composition.
- the vulcanized rubber may be free of cracks at one million times of the dematcher flex fatigue test.
- the present invention provides a vibration-proof rubber, belt, parts for overhead vehicles, seismic isolation rubber, hoses, wipers, dipped products, seal parts, boots, rubber-coated cloths, rubber rolls or sponge products using the vulcanized rubber.
- the present invention is a latex comprising the above chloroprene polymer.
- the latex may be for an adhesive or for a vulcanized rubber.
- a chloroprene-based polymer capable of obtaining an industrially usable vulcanized rubber having a sufficient molecular weight and excellent in fatigue resistance and an adhesive excellent in layer separation resistance. sell.
- the present invention can provide a vulcanized rubber excellent in durability and fatigue resistance and an adhesive excellent in layer separation resistance.
- FIG. 1 is a diagram showing 1 H-NMR spectrum of the chloroprene polymer obtained in Example 1.
- Chloroprene polymer The chloroprene polymer of the present embodiment is mainly composed of 2-chloro-1,3-butadiene (hereinafter referred to as “chloroprene”), and is represented by the following general formula (1) or (2) Have a functional group of
- R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group.
- the functional group having the structure represented by the general formula (1) is introduced into the chloroprene polymer by performing radical polymerization in the presence of a chain transfer agent [CTA] represented by the following general formula (3) .
- the functional group having the structure represented by the general formula (2) is introduced into the chloroprene polymer by performing radical polymerization in the presence of a chain transfer agent [CTA] represented by the following general formula (4) .
- R 2 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group.
- R 3 to 5 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted saturated, unsaturated or aromatic carbocyclic ring, a substituted or unsubstituted saturated group , Unsaturated or aromatic heterocycle, organometallic species, or any polymer chain is shown.
- the chain transfer agent [CTA] represented by the above general formula (3) is not particularly limited and general compounds can be used, and examples thereof include dithiocarbamates and dithioesters.
- benzyl 1-pyrrole carbodithioate (conventional name: benzyl 1-pyrrole dithiocarbamate), 1-benzyl-N, N-dimethyl-4-aminodithiobenzoate, 1-benzyl-4-methoxydithiobenzoate, 1-phenylethylimidazole carbodithioate (conventional name: 1-phenylethylimidazole dithiocarbamate), benzyl-1- (2-pyrrolidinone) carbodithioate (conventional name: benzyl-1- (2-pyrrolidinone) dithiocarbamate), Benzyl phthalimidyl carbodithioate, (conventional name: benzyl phthalimidyl dithiocarbamate), 2-cyanoprop
- benzyl 1-pyrrole carbodithioate 1-phenylethylimidazole carbodithioate, 3-chloro-2-butenylpyrrole dithiocarbamate, 1H-pyrrole-1-carbodithioic acid-phenylenebismethylene ester, Benzyl dithiobenzoate is used, and particularly preferably benzyl 1-pyrrole carbodithioate is used.
- the chain transfer agent [CTA] represented by the above general formula (4) is not particularly limited, and a general compound can be used.
- a general compound can be used.
- 2-cyano-2-propyldodecyltrithiocarbonate Dibenzyltrithiocarbonate, butylbenzyltrithiocarbonate, 2-[[(butylthio) thioxomethyl] thio] propionic acid, 2-[[(dodecylthio) thioxomethyl] thio] propionic acid, 2-[[(butylthio)] Thioxomethyl] thio] succinic acid, 2-[[(dodecylthio) thioxomethyl] thio] succinic acid, 2-[[(dodecylthio) thioxomethyl] thio] -2-methylpropionic acid, 2,2 '-[carbonothioyl bis ( Thio)] bis [2-methylpropionic acid], 2-
- the general formula (1) is preferably a structure represented by the following general formula (5).
- the functional group of the structure represented by the above general formula (5) is introduced into a chloroprene polymer by performing radical polymerization in the presence of benzyl 1-pyrrole carbodioate (conventional name: benzylpyrrole dithiocarbamate) Can do
- the chloroprene polymer of the present embodiment has a number average molecular weight Mn of 150,000 to 300,000.
- a chloroprene-based polymer having a number average molecular weight Mn of less than 150,000 may not be able to exhibit mechanical properties as an industrially practical vulcanized rubber. Further, in some cases, a vulcanized rubber can not be synthesized from a chloroprene polymer having a number average molecular weight Mn of more than 300,000.
- chloroprene polymers having a number average molecular weight Mn of less than 150,000 may have low mechanical properties as an adhesive, for example, low adhesion peel strength.
- the chloroprene polymer of the present embodiment preferably has a molecular weight distribution Mw / Mn of 1.5 to 5.0, which is a ratio of a weight average molecular weight Mw to the above number average molecular weight Mn, and is preferably 2.0 to 5. 0 is more preferable. It is suitable for industrial application that molecular weight distribution Mw / Mn is 1.5 or more. On the other hand, it is technically difficult to adjust the molecular weight distribution Mw / Mn to more than 5.0.
- the weight average molecular weight Mw and the number average molecular weight Mn are values measured by gel permeation chromatography (GPC), and the details of the measurement conditions are as described in the section of Examples described later.
- the chloroprene polymer of the present embodiment is a homopolymer of chloroprene, or a statistical copolymer composed of a chloroprene monomer and a monomer copolymerizable with the chloroprene monomer.
- Examples of monomers copolymerizable with chloroprene monomers include acrylic acid, methacrylic acid, methyl acrylate, butyl acrylate, acrylic acid esters such as 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, Methacrylates such as butyl methacrylate and 2-ethylhexyl methacrylate, and hydroxy (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxymethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate 2,3-Dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, butadiene, isoprene, aromatic vinyl compounds such as ethylene and styrene, unsaturated nitriles such as acrylonitrile and methacrylonitrile, acrylamide And the like.
- copolymerization is “statistical copolymerization”
- “statistical copolymer” is a copolymer having a chain of statistical monomer units obtained by statistical copolymerization.
- “statistical copolymer” is described in J. C. As described in Randall "POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method", Academic Press, New York, 1977, pages 71-78, by Bernoulli's statistical model, or by first- or second-order Markov statistical models, It means that it is a copolymer whose monomer chain distribution can be described.
- the “statistical copolymer” in the chloroprene polymer of this embodiment is composed of a binary monomer, it may be combined with the chloroprene monomer at the start of polymerization in the following Mayo-Lewis formula (I): Assuming that the ratio to a monomer other than chloroprene monomer is d [M1] / d [M2] and the chloroprene monomer is M1, the reactivity ratio r1 and r2 is r1 of 0.3 to 3000 It is preferable to obtain a statistical copolymer that the range, r2, is in the range of 10 -5 to 3.0.
- the “statistical copolymer” is a copolymer obtained by radical polymerization under coexistence of a plurality of monomers.
- the above “statistical copolymer” is a concept including substantially random copolymer.
- the chloroprene polymer of the present embodiment can be produced by the following method. That is, the chain transfer agent [CTA] represented by the above general formula (3) or (4) is added to 100 parts by mass of all monomers, and all monomers at the start of polymerization and the chain transfer agent A solution (A) having a ratio of [M] 0 / [CTA] of 5/1 to 500/1, and 500 to 5000 parts by mass of an aqueous solution (B) of 0.1 to 10% by mass of an emulsifier After mixing and emulsifying, radical polymerization is carried out, and when the polymerization rate reaches 20 to 50%, chloroprene monomer alone, or chloroprene monomer and monomer copolymerizable with chloroprene monomer 100 to 5000 mass Add the part.
- the monomer to be additionally added is preferably 250 to 3000 parts by mass.
- the monomer When the polymerization rate of the initially added monomer reaches 20 to 50%, the monomer is additionally added according to the desired molecular weight. If it is 20% or less, free radical polymerization may proceed by formation of micelles newly during polymerization, and if it is 50% or more, monomer oil droplets will disappear once, so continuous monomer supply is interrupted and side reaction May progress.
- the polymerization rate of the initially added monomer can be determined from the specific gravity of the emulsion. That is, a polymerization curve and a specific gravity calibration curve can be created by previously performing polymerization under the same conditions, sampling at three or more points, and measuring the solid content concentration and the specific gravity.
- the method of additional addition of the monomer it is preferable to cool the monomer in order to prevent thermal polymerization of the monomer.
- the means for additional addition is not particularly limited, and may be added directly into the system using a pump or the like.
- RAFT agents may be used as chain transfer agents.
- the RAFT agent is preferably a compound represented by the above general formula (3), more preferably benzyl 1-pyrrole carbodioate (sometimes described as a common name "benzylpyrrole dithiocarbamate"), 1-phenyl Ethylimidazole carbodithioate, 3-chloro-2-butenylpyrrole dithiocarbamate, 1H-pyrrole-1-carbodithioic acid-phenylenebismethylene ester, benzyl dithiobenzoate.
- benzyl 1-pyrrole carbodioate sometimes described as a common name "benzylpyrrole dithiocarbamate”
- 1-phenyl Ethylimidazole carbodithioate 1-phenyl Ethylimidazole carbodithioate
- 3-chloro-2-butenylpyrrole dithiocarbamate 1, 1H-pyrrole-1-carbodi
- RAFT agents are described in, for example, JP-A-2000-515181 and JP-A-2002-508409.
- the compound represented by the general formula (4) may be used as a chain transfer agent.
- butyl benzyl trithio carbonate, dibenzyl trithio carbonate, 2-cyano-2-propyl dodecyl trithio carbonate and the like can be mentioned.
- butyl benzyl trithio carbonate or dibenzyl trithio carbonate is preferable.
- the radical polymerization initiator is not particularly limited, and persulfates, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, azo compounds and the like can be used, but the half-life temperature is 10 hours It is preferable that it is 70 degrees C or less. When the initiator 10-hour half-life temperature is 70 ° C. or less, it is possible to generate sufficient radicals at the initial stage of polymerization to further improve the polymerization controllability.
- the emulsifier used in the emulsion polymerization is not particularly limited, but from the viewpoint of the emulsion stability, an anionic or nonionic emulsifier is preferable.
- an alkali metal rosin acid salt can be obtained by giving an appropriate strength to a film-like chloroprene polymer (chloroprene rubber) obtained by freeze-coagulation drying after completion of polymerization and giving an appropriate strength to prevent excessive shrinkage and breakage.
- Rosin acids are mixtures of resin acids, fatty acids and the like.
- resin acids include abietic acid, neoabietic acid, parastringic acid, pimaric acid, isopimaric acid, dehydroabietic acid, dihydropimaric acid, dihydroisopimaric acid, secode de hydroabietic acid, dihydroabietic acid, etc. , Oleic acid, linoleic acid etc. are included.
- the composition of these components varies depending on the difference in the method of collecting rosins classified into gum rosin, wood rosin and tall rosin, the place of production and species of pine, distillation refining and disproportionation (disproportionation) reaction, and is limited in the present invention. I will not.
- the emulsifier is preferably rosin acid sodium salt or rosin acid potassium salt, in consideration of the emulsion stability and the ease of handling.
- the concentration of the emulsifier is 0.1 to 10% by mass, more preferably 1 to 5% by mass. If the concentration is lower than 0.1% by mass, the monomer can not be emulsified sufficiently, and if it exceeds 10% by mass, there is a possibility that the precipitation can not be performed well when making the chloroprene polymer into a solid.
- the addition amount of the aqueous solution (B) of 0.1 to 10% by mass of the emulsifier is 500 to 5000 parts by mass, more preferably 600 to 4000 parts by mass with respect to 100 parts by mass of all monomers at the start of polymerization. is there.
- the amount of the aqueous solution (B) added is preferably 100 to 200 parts by mass with respect to 100 parts by mass of all the monomers including the additional monomer, in consideration of the final stability of the latex. .
- the polymerization temperature is preferably 10 to 50.degree.
- the polymerization temperature is preferably 10 to 50.degree.
- the polymerization temperature is preferably 10 to 50.degree.
- the polymerization temperature is preferably 10 to 50.degree.
- the thickening of the emulsion and the efficiency of the initiator can be further improved.
- the boiling point of chloroprene is about 59 ° C.
- by setting the polymerization temperature to 50 ° C. or less even if heat is generated due to abnormal polymerization or the like, heat rejection does not catch up and the situation of bumping of the reaction solution is avoided. can do.
- With regard to the living property by setting the temperature to 50 ° C. or less, there is an advantage that it is not necessary to consider the influence of hydrolysis of the chain transfer agent and evaporation of the monomer.
- the final polymerization rate of all the monomers after the addition of the monomer is preferably 95% or less from the viewpoint of preventing side reaction, and more preferably 85% or less from the viewpoint of further improving the durability and fatigue properties.
- the final polymerization rate of all the monomers after additional addition of the monomers is preferably 50% or more from the viewpoint of increasing the molecular weight to obtain sufficient mechanical properties as a vulcanized rubber. Further, the final polymerization rate is more preferably 50 to 75% from the viewpoint of productivity.
- a polymerization inhibitor is added to stop the polymerization reaction to stop the polymerization. Just do it.
- a polymerization inhibitor commonly used inhibitors can be used, and it is not particularly limited.
- oil-soluble polymerization inhibitor thiodiphenylamine, 4-tert-butyl catechol, 2,2-methylene bis Examples include -4-methyl-6-tert-butylphenol and diethylhydroxylamine which is a water-soluble polymerization inhibitor.
- Unreacted monomers may be removed by, for example, a steam stripping method. Thereafter, the pH is adjusted, and chloroprene rubber is obtained through the conventional processes such as freeze coagulation, water washing and hot air drying.
- a chloroprene polymer having high molecular weight, excellent vulcanized rubber physical properties and high adhesive peel strength by the emulsion polymerization method using a radical polymerization initiator and a specific chain transfer agent according to the present embodiment as described above Can be produced industrially advantageously.
- Latex> contains the above-mentioned chloroprene polymer, and is preferably for adhesive or vulcanized rubber. Details of the adhesive and the vulcanized rubber will be described later.
- composition of the present embodiment contains the above-mentioned chloroprene polymer, and is preferably an adhesive composition or a rubber composition.
- the adhesive composition of the present embodiment is preferably a solvent-based adhesive composition.
- the solvent-based adhesive composition can contain a solvent in addition to the above-mentioned chloroprene-based polymer.
- the solvent is not an aromatic solvent such as toluene, xylene or ethylbenzene which causes sick house syndrome but a non-aromatic solvent such as n-hexane, cyclohexane, methylcyclohexane, acetone, methyl ethyl ketone, ethyl acetate or butyl acetate.
- the chloroprene polymer is dissolved only with a mixture of poor solvents having poor solubility of chloroprene rubber alone.
- the amount of the solvent used may be appropriately adjusted depending on the application and type of the adhesive, and is not particularly limited, but adjustment as the solid content concentration of chloroprene rubber is 10 to 30% by mass makes it possible as an adhesive It is preferable because the heat resistant adhesive strength and the initial adhesive strength are well balanced.
- the adhesive composition may contain, in addition to the solvent, a metal oxide, a tackifying resin and an antiaging agent. By adding these additives to the adhesive, it is possible to improve the initial adhesive strength, the normal adhesive strength, the spray coatability and the like of the obtained adhesive.
- metal oxide for example, zinc oxide (zinc white), aluminum oxide, titanium oxide, magnesium oxide or the like can be used.
- tackifying resin for example, a phenolic resin, a rosin resin, a coumarone resin, a petroleum resin or the like can be used.
- anti-aging agents include, for example, 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,6-di- t-Butyl-4-methylphenol, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], thiodiethylene bis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N'-hexane-1,6-diylbis-3- (3,5 -Di-t-butyl-4-hydroxyphenylpropionamide), 3,5-bis (1,1-dimethylethyl) -4-hydroxyalkyl ester, [ ⁇ 3,5-bis (1,1
- the adhesive composition may further contain a formaldehyde catcher, a filler and the like according to the desired physical properties.
- formaldehyde catcher for example, pyrrolidine, piperidine, piperazine, morpholine, melamine, dicyandiamide, urea, ethylene urea, 4,5-dimethoxyethylene urea, propylene urea, 5-methylpropylene urea, 5-hydroxypropylene urea, 5-hydroxypropylene urea, Methoxypropyleneurea, oxalylurea (parabanic acid), hydrazobenzothiazole, semicarbazide, thiosemicarbazide can be used.
- Formaldehyde catchers can capture formaldehyde, a harmful volatile substance.
- the filler talc, calcium carbonate, clay, smectite, silica, hydrotalcite, mica and the like can be used.
- an ultraviolet absorber such as benzotriazole or a light stabilizer such as hindered amine may be added to the adhesive composition.
- the adhesive composition of the present embodiment further comprises at least one raw rubber selected from the group consisting of natural rubber, isoprene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, butadiene rubber, styrene butadiene rubber and ethylene propylene rubber ( It may contain uncrosslinked or unvulcanized rubber).
- a manufacturing method of adhesive composition after dissolving an alkyl phenol resin and magnesium oxide (MgO) in an organic solvent and leaving it to stand at 25 ° C for 20 hours, chloroprene rubber, metal oxide, anti-aging agent, etc.
- MgO magnesium oxide
- the manufacturing means is not particularly limited, and known machines and devices may be used.
- the adhesive composition of this embodiment is used as a raw material of an adhesive.
- an adhesive can be obtained by further adding other additives to the adhesive composition, or mixing the adhesive composition with another adhesive composition.
- the adhesive is suitably used for bonding or bonding of paper, wood, cloth, leather, jersey, leather, rubber, plastic, foam, pottery, glass, mortar, cement-based material, ceramic, metal, etc. be able to.
- the adhesive composition of the present embodiment or an adhesive using the same has high stability and resistance to delamination of 8 weeks or more.
- the rubber composition containing the above-mentioned chloroprene polymer is used for the production of a crosslinked rubber or a vulcanized rubber by crosslinking or vulcanization.
- the rubber composition of the present embodiment is suitably used for the production of a vulcanized rubber.
- the raw materials other than the chloroprene-based polymer are not particularly limited, and can be appropriately selected according to the purpose and application.
- Raw materials that can be contained in the rubber composition include, for example, vulcanizing agents, vulcanization accelerators, fillers or reinforcing agents, plasticizers, processing aids and lubricants, antiaging agents, and silane coupling agents. .
- vulcanizable agents sulfur, thiourea-based, guanidine-based, thiuram-based and thiazole-based organic vulcanizing agents generally used for vulcanizing chloroprene rubber can be used, but thiourea-based ones are preferable.
- thiourea-type vulcanizing agents include ethylenethiourea, diethylthiourea, trimethylthiourea, triethylthiourea, N, N'-diphenylthiourea and the like, with preference given to trimethylthiourea and ethylenethiourea.
- a vulcanizing agent such as a mixture of 3-methylthiazolidinethione-2-thiazole and phenylenedimaleimide, dimethylammonium hydrogen isophthalate or 1,2-dimercapto-1,3,4-thiadiazole derivative. It can.
- a vulcanizing agent such as a mixture of 3-methylthiazolidinethione-2-thiazole and phenylenedimaleimide, dimethylammonium hydrogen isophthalate or 1,2-dimercapto-1,3,4-thiadiazole derivative.
- Oxides and hydroxides can be used as vulcanizing agents.
- these vulcanizing agents that can be added calcium oxide, zinc oxide, antimony dioxide, antimony trioxide and magnesium oxide are particularly preferable because of their high vulcanization effect.
- these vulcanizing agents may use 2 or more types together.
- the vulcanizing agent is preferably added in a range of 0.1 parts by mass or more and 10 parts by mass or less in total with respect to 100 parts by mass of the rubber component in the rubber composition of the present embodiment.
- a filler or a reinforcing agent is added to adjust the hardness of the rubber or to improve the mechanical strength, and is not particularly limited.
- carbon black, silica, clay, talc, calcium carbonate may be mentioned.
- Be Other inorganic fillers include, but not particularly limited to, alumina (Al 2 O 3 ) such as ⁇ -alumina and ⁇ -alumina, alumina monohydrate such as boehmite and diaspore (Al 2 O 3 ⁇ H 2 O ), Aluminum hydroxide such as gibbsite and bayerite [Al (OH) 3 ], aluminum carbonate [Al 2 (CO 3 ) 2 ], magnesium hydroxide [Mg (OH) 2 ], magnesium carbonate (MgCO 3 ), talc (3MgO ⁇ 4SiO 2 ⁇ H 2 O), attapulgite (5MgO ⁇ 8SiO 2 ⁇ 9H 2 O), titanium white (TiO 2 ), titanium black (TiO 2 n-1 ), calcium oxide
- the filler and the reinforcing agent may be used alone or in combination of two or more.
- the compounding amount of the filler and the reinforcing agent may be adjusted according to the physical properties required for the rubber composition and the crosslinked rubber or vulcanized rubber obtained from the rubber composition, and is not particularly limited. It can be generally added in a range of 15 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the rubber component in the rubber composition of the embodiment.
- the plasticizer is not particularly limited as long as it is a plasticizer compatible with the rubber, but, for example, vegetable oil such as rapeseed oil, linseed oil, castor oil, coconut oil, phthalate plasticizer, DUP (diundecyl phthalate), DOS ( Dioctyl sebacate), DOA (dioctyl adipate), ester plasticizers, ether plasticizers, thioether plasticizers, thioether plasticizers, aroma oils, naphthenic oils, lubricating oils, processing oils, paraffins, liquid paraffin, vaseline, petroleum There are petroleum-based plasticizers such as asphalt and the like, and one or more may be used according to the properties required for the rubber composition and the crosslinked rubber or vulcanized rubber obtained from the rubber composition. Although there is no limitation in particular in the compounding quantity of a plasticizer, it can be usually compounded in a total of 5 mass parts or more and 50 mass parts or less with respect to 100 mass parts of rubber
- processing aids and lubricants include fatty acids such as stearic acid, paraffinic processing aids such as polyethylene, and fatty acid amides.
- the processing aid and the lubricant may be used alone or in combination of two or more.
- the addition amount thereof is not particularly limited, but in general, the total amount is 0.5 parts by mass to 5 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition of the present embodiment.
- primary antioxidants to improve heat resistance
- added primary antioxidants used for ordinary rubber applications which capture radicals to prevent auto-oxidation, and secondary antioxidants to render hydroperoxide harmless can do.
- Those antioxidants are preferably added in a proportion of 0.1 to 10 parts by mass with respect to 100 parts by mass of the rubber component in the rubber composition, and more preferably 2 to 5 parts by mass It is the following range.
- These anti-aging agents can be used alone or in combination of two or more.
- primary anti-aging agents include phenolic anti-aging agents, amine anti-aging agents, acrylate anti-aging agents, imidazole anti-aging agents, metal salts of carbamates and waxes.
- next antiaging agent examples include phosphorus antiaging agents, sulfur antiaging agents, and imidazole antiaging agents.
- anti-aging agents include, but are not limited to, N-phenyl-1-naphthylamine, alkylated diphenylamine, octylated diphenylamine, 4,4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, p- (p -Toluenesulfonylamide) diphenylamine, N, N'-di-2-naphthyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N -Phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2
- a silane coupling agent may be further added.
- the silane coupling agent may be added when the rubber composition is kneaded, or may be added in the form of surface treatment of the filler or the reinforcing agent in advance.
- the silane coupling agent may be used alone or in combination of two or more.
- bis- (3-triethoxysilylpropyl) tetrasulfide bis- (3-trimethoxinylpropyl) tetrasulfide, bis- (3-methyldimethoxysilylpropyl) ) Tetrasulfide, bis- (2-triethoxysilylethyl) tetrasulfide, bis- (3-triethoxysilylpropyl) disulfide, bis- (3-trimethoxysilylpropyl) disulfide, bis- (3-triethoxysilylpropyl) ) Trisulfide, 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethoxysilane, 2-hexanoylthiopropyltriethoxys
- the rubber composition of the present embodiment is at least one raw rubber (unfinished rubber) selected from the group consisting of natural rubber, isoprene rubber, butyl rubber, nitrile rubber, hydrogenated nitrile rubber, butadiene rubber, styrene butadiene rubber and ethylene propylene rubber. It may contain crosslinked or unvulcanized rubber).
- the rubber composition of the present embodiment is preferably used as a vulcanized rubber for practical use by vulcanization. Vulcanization may be carried out by a known method, but it is generally carried out at a vulcanization temperature of 120 to 230 ° C. using a thiourea-based vulcanizing agent.
- the vulcanized rubber obtained by vulcanizing the above composition can exhibit high mechanical properties of 20 MPa in tensile strength and 350% or more in breaking elongation in a tensile test based on JIS K6251.
- the vulcanized rubber obtained by vulcanizing the above-mentioned rubber composition exhibits high durability fatigue. Specifically, it exhibits a bending fatigue characteristic that there is no crack even after repeating a dematcher bending fatigue test based on JIS K6260 one million times. The details of the measurement conditions of the dematcher flex fatigue test are as described in the section of Examples described later.
- the vulcanized rubber obtained by vulcanizing the above rubber composition has excellent durability and is capable of dramatically improving the product life, and is useful for various products.
- the above-mentioned vulcanized rubber is suitably used particularly for anti-vibration rubbers, belts, parts for overhead vehicles, seismic isolation rubbers, hoses, wipers, immersion products, sealing parts, boots, rubberized fabrics, rubber rolls or sponge products.
- the method for producing a product containing the above rubber composition is not particularly limited as long as the above rubber composition is compounded.
- the rubber composition may be used as it is or after being vulcanized.
- Example 1 In a polymer can with an inner volume of 10 liters, 480 g of chloroprene monomer, 5.2 g of benzyl 1-pyrrole carbodioate (common name: benzyl pyrrole dithiocarbamate), 4000 g of pure water, potassium disproportionated rosin acid (manufactured by Harima Chemicals, Ltd.) 160 g, sodium hydroxide 9.2 g, and sodium salt of ⁇ -naphthalenesulfonic acid formalin condensate (trade name Demol N: manufactured by Kao Corporation) 20 g were added.
- a polymerization initiator 0.60 g of potassium persulfate was added, and polymerization was performed at a polymerization temperature of 35 ° C. in a nitrogen stream.
- the polymerization rate of the initial monomer reaches 30%
- 3520 g of chloroprene monomer is additionally added over 2 hours
- the polymerization terminator diethylhydroxyamine use The polymerization was terminated by adding 0.02 parts by mass of 100 parts by mass of the chloroprene monomer.
- the pH of the chloroprene latex containing chloroprene polymer was adjusted to 7.0 using dilute acetic acid.
- a solid chloroprene-based polymer (chloroprene rubber) was obtained by a freeze-coagulation-drying method.
- the freeze-coagulation-drying method specifically, latex is poured on a metal plate cooled to -20.degree. C. and freeze-coagulated to break the emulsion, and the resulting sheet is washed with water and then dried at 130.degree. C. for 15 minutes Thus, a solid chloroprene polymer was obtained.
- the number-average molecular weight Mn, mass-average molecular weight Mw, and molecular weight distribution (Mw / Mn) of the obtained chloroprene-based polymer and the polymer or copolymer obtained by sampling on the way are the sample adjustment concentration 0 in THF .1 mass%, and then measured by TOSOH HLC-8320 GPC (in terms of standard polystyrene).
- the sample pump pressure is 8.0 to 9.5 MPa
- the flow rate is 1 mL / min
- it flows out at 40 ° C and detected by a differential refractometer did.
- Efflux time and molecular weight were measured using a calibration curve prepared by measuring a total of 9 standard polystyrene samples having known molecular weights as listed below.
- Example 2 A procedure similar to that of Example 1 is repeated except that 5.0 g of benzyl 1-pyrrole carbodioate (common name: benzylpyrrole dithiocarbamate) of Example 1 is changed to 0.58 g of potassium persulfate. Obtained chloroprene rubber.
- Example 3 Example 1 except that 3.2 g of benzyl 1-pyrrole carbodioate (common name: benzyl pyrrole dithiocarbamate) of Example 1 was changed to 0.37 g of potassium persulfate, and the final polymerization rate was 80%.
- the chloroprene rubber of Example 3 was obtained by the same procedure as in.
- Example 4 The experiment was carried out except that 5.52 g of butylbenzyltrithiocarbonate was added instead of benzyl 1-pyrrole carbodioate (common name: benzylpyrrole dithiocarbamate) of Example 1, and potassium persulfate was changed to 0.64 g.
- the chloroprene rubber of Example 4 was obtained by the same procedure as Example 1.
- Example 5 Example 1 except that 6 g of dibenzyl trithiocarbonate was added instead of bebenzyl 1-pyrrole carbodioate (common name: benzyl pyrrole dithiocarbamate) of Example 1, and potassium persulfate was changed to 0.69 g.
- the chloroprene rubber of Example 5 was obtained by the same procedure as in.
- Example 6 The chloroprene of Example 6 was carried out in the same manner as Example 1, except that the initial chloroprene monomer of Example 1 was changed to 400 g, the additional chloroprene monomer was changed to 3600 g, and the final polymerization rate was changed to 65%. I got a rubber.
- Example 7 The chloroprene rubber of Example 7 was obtained in the same manner as in Example 1 except that the final polymerization rate of Example 1 was changed to 95%.
- Example 8 The monomer to be charged in the initial stage of Example 1 is 380 g of chloroprene monomer and 200 g of 2,3-dichloro-1,3-butadiene monomer, and the monomer to be additionally added is 3400 g of chloroprene monomer, benzyl 1
- the procedure is the same as in Example 1 except that 4.8 g of pyrrolecarbodithioate (conventional name: benzylpyrrole dithiocarbamate), 0.56 g of potassium persulfate, and the final conversion rate to 65%.
- the chloroprene rubber of Example 8 was obtained.
- Example 9 The monomer charged in the initial stage of Example 1 is 320 g of chloroprene monomer and 600 g of styrene monomer, the monomer to be additionally added is 3600 g of chloroprene monomer, and the final polymerization rate is changed to 85%,
- the chloroprene rubber of Example 9 was obtained by the same procedure as Example 1.
- Example 10 The monomer to be charged in the initial stage of Example 1 is 320 g of chloroprene monomer, 160 g of 2,3-dichloro-1,3-butadiene monomer is 480 g and styrene monomer 480 g, and the monomer to be additionally added is chloroprene alone.
- the chloroprene rubber of Example 10 was obtained in the same manner as in Example 1 except that 3040 g of the monomer was used and the final polymerization rate was changed to 85%.
- Example 11 The same as Example 1 except that the monomer charged in the initial stage of Example 1 was changed to 320 g of chloroprene monomer and 800 g of n-butyl acrylate monomer, and the monomer to be additionally added was changed to 2980 g of chloroprene monomer.
- the chloroprene rubber of Example 11 was obtained by the following procedure.
- Example 12 According to the same procedure as in Example 1, except that the monomers charged in the initial stage of Example 1 were 600 g of chloroprene monomer and 1200 g of acrylonitrile monomer, and the monomer to be additionally added was changed to 2200 g of chloroprene monomer. The chloroprene rubber of Example 12 was obtained.
- Comparative Example 1 In a polymer can with an internal volume of 10 liters, 4000 g of chloroprene monomer, 16 g of diethylxanthogen disulfide, 4000 g of pure water, 160 g of disproportionated potassium rosinate (manufactured by Harima Chemicals), 9.2 g of sodium hydroxide, ⁇ -naphthalenesulfonic acid 20 g of sodium salt of formalin condensation product (Demol N: manufactured by Kao Corporation) was added. A 2% aqueous solution of potassium persulfate was added as a polymerization initiator, and polymerization was performed at a polymerization temperature of 35 ° C. under a nitrogen stream.
- chloroprene latex was adjusted to 7.0 using dilute acetic acid. Then, chloroprene rubber was obtained by the freeze-coagulation-drying method.
- Comparative Example 2 A chloroprene rubber of Comparative Example 2 was obtained by the same procedure as Comparative Example 1 except that the diethyl xanthogen disulfide of Comparative Example 1 was changed to 8.8 g of dodecyl mercaptan.
- Comparative Example 3 The chloroprene rubber of Comparative Example 3 was obtained in the same manner as in Example 1 except that the final polymerization rate of Example 1 was changed to 47%.
- Comparative Example 4 When 3.2 g of benzyl 1-pyrrole carbodioate (common name: benzyl pyrrole dithiocarbamate) of Example 1 was changed to 0.37 g of potassium persulfate and the polymerization rate of the initial monomer reached 80% Thus, the chloroprene rubber of Comparative Example 4 was obtained by the same procedure as in Example 1 except that the chloroprene monomer was additionally added.
- the polymerization rate from the polymerization start to a certain time was calculated from the dry weight (solid content concentration) by heating the chloroprene rubber latex with heating and air. Specifically, it was calculated from the following formula (III).
- the solid concentration was obtained by heating 2 g of the sampled emulsion polymerization liquid at 130 ° C. to remove the solvent (water), volatile chemicals and raw materials, and removing volatiles from weight change before and after heating It is the density
- concentration (mass%) of solid content was calculated from the polymerization recipe.
- the total charged amount is the total amount of the raw materials, reagents, and solvent (water) charged in the polymerizer from the polymerization start to a certain time.
- the evaporation residue represents the weight of the chemical and raw materials charged from the polymerization start to a certain time, which does not volatilize under the condition of 130 ° C. and remains as a solid with the polymer.
- the amount of charged monomers is the sum of the amount of monomers initially charged to the polymerizer and the amount of monomers added from the start of polymerization to a certain time.
- monomer preparation amount is the total amount of these.
- Polymerization rate [%] ⁇ (total charge amount [g] ⁇ solid content concentration [mass%] / 100) ⁇ (evaporation residue [g]) ⁇ / monomer charge amount [g] ⁇ 100. III)
- Test pieces of a vulcanized sheet having a thickness of 2 mm were produced from the obtained vulcanized rubber, and a tensile test was conducted based on JIS K6251 to measure the tensile strength (MPa) and the elongation at break (%) of the vulcanized rubber.
- the vulcanized rubber obtained from the chloroprene rubber of the example was superior in the endurance fatigue property to the comparative example. Further, the tensile strength and the elongation at break of the vulcanized rubber of the example were comparable or slightly higher than those of the comparative example, and the hardness of the vulcanized rubber of the example was equivalent to that of the comparative example. From these results, it was confirmed that the chloroprene rubber of the present invention can improve the endurance fatigue properties of the vulcanized rubber without affecting the physical properties of the rubber.
- the adhesive obtained from the chloroprene rubber of the example was superior in delamination resistance to the comparative example.
- the normal-state adhesive peel strength, heat-resistant adhesive peel strength and softening point of the vulcanized rubber of the example were equal to those of the comparative example. From these results, it was confirmed that the chloroprene rubber of the present invention can improve the layer separation resistance of the adhesive without affecting the adhesion properties.
- the chloroprene rubbers of Comparative Examples 1 and 2 did not have a functional group of the structure represented by the above general formula (1) or (2).
- the chloroprene rubber of Comparative Example 3 had a number average molecular weight of less than 150,000.
- the vulcanized rubbers obtained from these comparative examples were inferior in endurance fatigue resistance, and the adhesive had low delamination resistance.
- the chloroprene rubber of Comparative Example 4 having a number average molecular weight of more than 300,000 has a high viscosity, so that the composition becomes hard to form a uniform molded product, and can not be processed into a vulcanized rubber.
- the adhesive of Comparative Example 4 had low resistance to delamination.
- R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group .
- R 1 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group .
- the monomer copolymerizable with the chloroprene monomer is 2,3-dichloro-1,3-butadiene, 1-chloro-1,3-butadiene, acrylic acid, acrylic ester, methacrylic acid,
- the chloroprene polymer according to [5] which is at least one selected from the group consisting of methacrylic acid esters, acrylamides, unsaturated nitriles and aromatic vinyl compounds.
- a solution (A) having a ratio [M] 0 / [CTA] of 5/1 to 500/1, and an aqueous solution (B) 500 to 5000 parts by mass of an emulsifier of 0.1 to 10% by mass are mixed and emulsified After that, radical polymerization is performed, and when the polymerization rate reaches 20 to 50%, 100 to 5000 parts by mass of chloroprene monomer alone, or chloroprene monomer and monomer copolymerizable with chloroprene monomer are added.
- R 2 represents hydrogen, chlorine, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclyl group
- R 3 to 5 each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted saturated, unsaturated or aromatic carbon ring, a substituted or unsubstituted Indicates a saturated, unsaturated or aromatic heterocycle, an organometallic species, or any polymer chain
- a latex comprising the chloroprene polymer according to any one of the above [1] to [6].
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Abstract
Description
前記クロロプレン系重合体は、上記一般式(1)で表される構造の官能基を有してもよい。
前記クロロプレン系重合体は、重量平均分子量Mwと前記数平均分子量Mnとの比である分子量分布Mw/Mnが1.5~5.0であってもよい。
前記クロロプレン系重合体は、クロロプレン単量体の単独重合体であってもよい。
前記クロロプレン系重合体は、クロロプレン単量体及び該クロロプレン単量体と共重合可能な単量体からなる統計的共重合体であってもよい。
前記クロロプレン単量体と共重合可能な単量体が、2,3-ジクロロ-1,3-ブタジエン、1-クロロ-1,3-ブタジエン、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリルアミド、不飽和ニトリル及び芳香族ビニル化合物からなる群より選択される少なくとも1種であってもよい。
全単量体100質量部に対し、下記一般式(3)又は(4)で表される連鎖移動剤を添加して、重合開始時における前記全単量体と前記連鎖移動剤との物質量の比[M]0/[CTA]を5/1~500/1とした溶液(A)と、乳化剤0.1~10質量%の水溶液(B)500~5000質量部と、を混合し乳化した後、ラジカル重合を行い、重合率20~50%に到達した時に、クロロプレン単量体単独、又はクロロプレン単量体及びクロロプレン単量体と共重合可能な単量体100~5000質量部を追添加する、クロロプレン系重合体の製造方法を提供する。
前記クロロプレン系重合体の製造方法において、前記追添加後の最終重合率は50%以上であってもよい。
前記クロロプレン系重合体の製造方法は、上記一般式(3)で表される連鎖移動剤を添加するものであってもよい。
前記組成物は、更に、天然ゴム、イソプレンゴム、ブチルゴム、ニトリルゴム、水素化ニトリルゴム、ブタジエンゴム、スチレンブタジエンゴム及びエチレンプロピレンゴムからなる群より選択される少なくとも1種を含んでもよい。
また、本発明は、前記組成物を含む接着剤組成物を提供する。
また、本発明は、前記接着剤組成物を含む接着剤を提供する。
前記接着剤組成物又は前記接着剤は、耐層分離性が8週間以上であってもよい。
また、本発明は、前記組成物を含む加硫ゴムを提供する。
前記加硫ゴムは、デマッチャ屈曲疲労試験を100万回実施した時点で亀裂がないものであってもよい。
また、本発明は、前記加硫ゴムを使用した防振ゴム、ベルト、オーバヘッドビークル向け部品、免震ゴム、ホース、ワイパー、浸漬製品、シール部品、ブーツ、ゴム引布、ゴムロール又はスポンジ製品を提供する。
また、本発明は、前記クロロプレン系重合体を含むラテックス。
前記ラテックスは、接着剤用又は加硫ゴム用であってもよい。
本実施形態のクロロプレン系重合体は、2-クロロ-1,3-ブタジエン(以下、「クロロプレン」という。)を主成分とするものであり、下記一般式(1)又は(2)で表される構造の官能基を有する。
(理論分子量)=MW(M)×[M]T/[CTA]×重合率+MW(CTA)・・・(II)
MW(M):単量体の平均分子量(単量体1の分子量×モル分率+単量体2の分子量×単量体のモル分率)
[M]T:全単量体の物質量
[CTA]:連鎖移動剤の物質量
MW(CTA):連鎖移動剤の分子量
本実施形態のラテックスは、上記クロロプレン系重合体を含み、好ましくは接着剤用又は加硫ゴム用である。接着剤及び加硫ゴムの詳細については、後述する。
本実施形態の組成物は、上記クロロプレン系重合体を含み、好ましくは接着剤組成物又はゴム組成物である。
内容積10リットルの重合缶に、クロロプレン単量体480g、ベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)5.2g、純水4000g、不均化ロジン酸カリウム(ハリマ化成社製)160g、水酸化ナトリウム9.2g、β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩(商品名デモールN:花王社製)20gを添加した。重合開始剤として過硫酸カリウム0.60gを添加し、重合温度35℃にて窒素気流下で重合を行った。初期単量体の重合率30%となった時点で、クロロプレン単量体3520gを2時間かけて追添加し、最終重合率が70%となった時点で重合停止剤であるジエチルヒドロキシアミン(使用したクロロプレン単量体100質量部に対し0.02質量部)を加えて重合を停止させた。減圧蒸留して未反応の単量体を除去した後、希酢酸を用いて、クロロプレン系重合体を含むクロロプレンラテックスのpHを7.0に調整した。そして、凍結凝固乾燥法により、固形状のクロロプレン系重合体(クロロプレンゴム)を得た。凍結凝固乾燥法では、具体的には、-20℃に冷やした金属板上にラテックスを注ぎ、凍結凝固させることで乳化破壊し、得られたシートを水洗した後、130℃で15分間乾燥させることにより、固体状のクロロプレン系重合体を得た。
得られたクロロプレン系重合体、及び、途中のサンプリングで得られた重合体又は共重合体の数平均分子量Mn、質量平均分子量Mw、及び分子量分布(Mw/Mn)は、THFでサンプル調整濃度0.1質量%とした後、TOSOH HLC-8320GPCにより測定した(標準ポリスチレン換算)。その際、プレカラムとしてTSKガードカラムHHR-H、分析カラムとしてHSKgelGMHHR-H3本を使用し、サンプルポンプ圧8.0~9.5MPa、流量1mL/min、40℃で流出させ、示差屈折計で検出した。流出時間と分子量は、以下にあげる分子量既知の標準ポリスチレンサンプル計9点を測定して作成した校正曲線を用いた。(Mw=8.42×106、1.09×106、7.06×105、4.27×105、1.90×105、9.64×104、3.79×104、1.74×104、2.63×103)
得られたクロロプレン系重合体の連鎖移動剤[CTA]由来の官能基の分析は以下のように行った。得られたクロロプレン系重合体をベンゼンとメタノールで精製し、再度凍結乾燥して測定用試料を得た。クロロプレン系重合体30mgを重クロロホルム1mlに溶解し、JEOL製ECX400(400MHz)を使用し、30℃で1H-NMRを測定した。実施例1で得られたクロロプレン系重合体の1H-NMRスペクトルを図1に示す。用いた連鎖移動剤[CTA](ベンジル1-ピロールカルボジチオエート)由来のピーク(図1中、a及びbで示すピーク)が明瞭に観察された。同定された官能基の構造は、下記表に示した。
実施例1のベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)を5.0g、過硫酸カリウムを0.58gに変更した以外は、実施例1と同様の手順により実施例2のクロロプレンゴムを得た。
実施例1のベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)を3.2g、過硫酸カリウムを0.37gに変更し、最終重合率を80%とした以外は、実施例1と同様の手順により実施例3のクロロプレンゴムを得た。
実施例1のベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)の代わりにブチルベンジルトリチオカルボネートを5.52g添加し、過硫酸カリウムを0.64gに変更した以外は、実施例1と同様の手順により実施例4のクロロプレンゴムを得た。
実施例1のベベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)の代わりにジベンジルトリチオカルボネートを6g添加し、過硫酸カリウムを0.69gに変更した以外は、実施例1と同様の手順により実施例5のクロロプレンゴムを得た。
実施例1の初期のクロロプレン単量体を400gに、追添加するクロロプレン単量体を3600gとし、最終重合率を65%に変更した以外は、実施例1と同様の手順により実施例6のクロロプレンゴムを得た。
実施例1の最終重合率を95%に変更した以外は、実施例1と同様の手順により実施例7のクロロプレンゴムを得た。
実施例1の初期に仕込む単量体をクロロプレン単量体380g及び2,3-ジクロロ-1,3-ブタジエン単量体200gとし、追添加する単量体をクロロプレン単量体3400gとし、ベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)を4.8gとし、過硫酸カリウムを0.56gとし、最終重合率を65%に変更した以外は、実施例1と同様の手順により実施例8のクロロプレンゴムを得た。
実施例1の初期に仕込む単量体をクロロプレン単量体320g及びスチレン単量体600gとし、追添加する単量体をクロロプレン単量体3600gとし、最終重合率を85%に変更した以外は、実施例1と同様の手順により実施例9のクロロプレンゴムを得た。
実施例1の初期に仕込む単量体をクロロプレン単量体320g、2,3-ジクロロ-1,3-ブタジエン単量体を160g及びスチレン単量体480gとし、追添加する単量体をクロロプレン単量体3040gとし、最終重合率を85%に変更した以外は、実施例1と同様の手順により実施例10のクロロプレンゴムを得た。
実施例1の初期に仕込む単量体をクロロプレン単量体320g及びn-ブチルアクリレート単量体800gとし、追添加する単量体をクロロプレン単量体2980gに変更した以外は、実施例1と同様の手順により実施例11のクロロプレンゴムを得た。
実施例1の初期に仕込む単量体をクロロプレン単量体600g及びアクリロニトリ単量体1200gとし、追添加する単量体をクロロプレン単量体2200gに変更した以外は、実施例1と同様の手順により実施例12のクロロプレンゴムを得た。
内容積10リットルの重合缶に、クロロプレン単量体4000g、ジエチルキサントゲンジスルフィド16g、純水4000g、不均化ロジン酸カリウム(ハリマ化成社製)160g、水酸化ナトリウム9.2g、β-ナフタレンスルホン酸ホルマリン縮合物のナトリウム塩(デモールN:花王社製)20gを添加した。重合開始剤として2%過硫酸カリウム水溶液を添加し、重合温度35℃にて窒素気流下で重合を行った。重合率が70%となった時点で重合停止剤であるジエチルヒドロキシアミンを加えて重合を停止させた。減圧蒸留して未反応の単量体を除去した後、希酢酸を用いて、クロロプレン系重合体(クロロプレンラテックス)のpHを7.0に調整した。そして、凍結凝固乾燥法により、クロロプレンゴムを得た。
比較例1のジエチルキサントゲンジスルフィドをドデシルメルカプタン8.8gに変更した以外は、比較例1と同様の手順により比較例2のクロロプレンゴムを得た。
実施例1の最終重合率を47%に変更した以外は、実施例1と同様の手順により比較例3のクロロプレンゴムを得た。
実施例1のベンジル1-ピロールカルボジチオエート(慣用名:ベンジルピロールジチオカルバメート)を3.2g、過硫酸カリウムを0.37gに変更し、初期単量体の重合率が80%となった時点で、クロロプレン単量体を追添加した以外は、実施例1と同様の手順により比較例4のクロロプレンゴムを得た。
重合開始からある時刻までの重合率は、クロロプレンゴムラテックスを加熱風乾することで乾燥重量(固形分濃度)から算出した。具体的には、以下の式(III)より計算した。式(III)中、固形分濃度は、サンプリングした乳化重合液2gを130℃中で加熱して溶媒(水)、揮発性薬品、及び原料を除き、加熱前後の重量変化から揮発分を除いた固形分の濃度(質量%)である。総仕込み量及び蒸発残分は重合処方より計算した。総仕込み量とは、重合開始からある時刻までに重合缶に仕込んだ原料、試薬、溶媒(水)の総量である。蒸発残分とは、重合開始からある時刻までに仕込んだ薬品及び原料のうち、130℃の条件下で揮発せずに重合体と共に固形分として残留する薬品の重量を表す。単量体仕込み量は、重合缶に初期に仕込んだ単量体及び重合開始からある時刻までに分添した単量体の量の合計である。なお、クロロプレン単量体と他の単量体との共重合の場合は、単量体仕込み量はこれらの合計量である。
2,3-ジクロロ-1,3-ブタジエン、スチレン、及びn-ブチルアクリレートの各ユニットの共重合体中の含量は、1H-NMR測定による公知の方法により求めた。アクリロニトリルユニットの含量は、化学分析により求めた窒素原子の含有量から算出した。
クロロプレンゴムについて、JIS K6300に準拠し、100℃におけるムーニー粘度を測定した。
上記クロロプレンゴム100質量部に、ステアリン酸1質量部、オクチル化ジフェニルアミン2質量部、酸化マグネシウム4質量部、カーボンブラック(SRF)40質量部、酸化亜鉛5.0質量部を添加して、8インチロールを用いて混合し、160℃で20分間プレス架橋して加硫ゴムを作製した。
得られた加硫ゴムから厚さ2mmの加硫シートのテストピースを作製し、JIS K6251に基づいて引張試験を行い、加硫ゴムの引張強度(MPa)及び破断伸び(%)を測定した。
得られた加硫ゴムについて、JIS K6253に基づいて試験を行い、硬度を測定した。
得られた加硫ゴムについて、JIS K6260のデマッチャ屈曲疲労試験に準拠して、ストローク58mm、速度300±10rpmの条件下で、亀裂が発生した時点における屈曲試験の回数(単位:万回)を確認することにより、耐久疲労性を評価した。測定は200万回まで実施した。100万回超を合格とした。200万回で亀裂が発生しなかったサンプルについては、表中に200万回と記載した。
アルキルフェノール樹脂(タマノル526:荒川化学工業社製)50質量部と酸化マグネシウム(キョウワマグ#150:協和化学工業社製)3質量部をシクロヘキサン100質量部に溶解させて、室温下、16時間キレート化反応させた。次に、そのシクロヘキサン溶液に対して、クロロプレンゴム100質量部、酸化マグネシウム3質量部、酸化亜鉛質量1部、シクロヘキサン90質量部、メチルエチルケトン190質量部を加え、クロロプレンゴムが完全に溶解するまで混合攪拌し、接着剤を得た。
接着剤を作成後、ブルックフィールド型粘度計を用いて25℃における粘度を測定した。
接着剤をガラス製容器に入れ、遮光下、23℃の恒温水槽中に貯蔵した。8週間にわたり接着剤の外観観察を実施し、接着剤成分の分離が見られた週を記録し、6週間以上を合格とした。
帆布(25mm×150mm)2枚それぞれに、実施例及び比較例の各接着剤を3000g/m2塗布した。その後、オープンタイムを30分として、ハンドローラーで5往復した。そして、セットタイム1日後の初期強度と、10日後の常態強度を50mm/minの引張強度で測定した。
帆布(25mm×150mm)2枚それぞれに、実施例及び比較例の各接着剤を3000g/m2塗布した。その後、オープンタイムを30分として、ハンドローラーで5往復した。そして、セットタイム10日後の被着体を、80℃の恒温槽付きの引張試験機で50mm/minの条件で剥離強度を測定した。
帆布(25mm×150mm)2枚それぞれに、実施例及び比較例の各接着剤を3000g/m2塗布した。その後、オープンタイムを30分として、ハンドローラーで5往復した。そして、セットタイム10日後の試験体を、500gの重りを吊り下げた状態で試験装置内にセットし、試験装置内を38℃雰囲気下で15分間保持後、5分間に2℃の割合で昇温し、重りが落下する温度を測定した。
〔1〕数平均分子量Mnが15~30万であり、下記一般式(1)又は(2)で表される構造の官能基を有するクロロプレン系重合体。
〔2〕上記一般式(1)で表される構造の官能基を有する、〔1〕に記載のクロロプレン系重合体。
〔3〕重量平均分子量Mwと前記数平均分子量Mnとの比である分子量分布Mw/Mnが1.5~5.0である〔1〕又は〔2〕に記載のクロロプレン系重合体。
〔4〕クロロプレン単量体の単独重合体である〔1〕~〔3〕のいずれか1つに記載のクロロプレン系重合体。
〔5〕クロロプレン単量体及び該クロロプレン単量体と共重合可能な単量体からなる統計的共重合体である〔1〕~〔3〕のいずれか1つに記載のクロロプレン系重合体。
〔6〕前記クロロプレン単量体と共重合可能な単量体が、2,3-ジクロロ-1,3-ブタジエン、1-クロロ-1,3-ブタジエン、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリルアミド、不飽和ニトリル及び芳香族ビニル化合物からなる群より選択される少なくとも1種である〔5〕に記載のクロロプレン系重合体。
〔7〕前記〔1〕~〔6〕のいずれか1つに記載のクロロプレン系重合体を得るための製造方法であり、
全単量体100質量部に対し、下記一般式(3)又は(4)で表される連鎖移動剤を添加して、重合開始時における前記全単量体と前記連鎖移動剤との物質量の比[M]0/[CTA]を5/1~500/1とした溶液(A)と、乳化剤0.1~10質量%の水溶液(B)500~5000質量部と、を混合し乳化した後、ラジカル重合を行い、重合率20~50%に到達した時に、クロロプレン単量体単独、又はクロロプレン単量体及びクロロプレン単量体と共重合可能な単量体100~5000質量部を追添加する、クロロプレン系重合体の製造方法。
〔8〕前記追添加後の最終重合率が50%以上である、〔7〕に記載のクロロプレン系重合体の製造方法。
〔9〕上記一般式(3)で表される連鎖移動剤を添加する、〔7〕又は〔8〕に記載のクロロプレン系重合体の製造方法。
〔10〕前記〔1〕~〔6〕のいずれか1つに記載のクロロプレン系重合体を含む組成物。
〔11〕更に、天然ゴム、イソプレンゴム、ブチルゴム、ニトリルゴム、水素化ニトリルゴム、ブタジエンゴム、スチレンブタジエンゴム及びエチレンプロピレンゴムからなる群より選択される少なくとも1種を含む〔10〕に記載の組成物。
〔12〕前記〔10〕又は〔11〕に記載の組成物を含む接着剤組成物。
〔13〕前記〔12〕に記載の接着剤組成物を含む接着剤。
〔14〕耐層分離性が8週間以上である〔12〕に記載の接着剤組成物又は〔13〕に記載の接着剤。
〔15〕前記〔10〕又は〔11〕に記載の組成物を含む加硫ゴム。
〔16〕デマッチャ屈曲疲労試験を100万回実施した時点で亀裂がない〔15〕に記載の加硫ゴム。
〔17〕前記〔15〕又は〔16〕に記載の加硫ゴムを使用した防振ゴム、ベルト、オーバヘッドビークル向け部品、免震ゴム、ホース、ワイパー、浸漬製品、シール部品、ブーツ、ゴム引布、ゴムロール又はスポンジ製品。
〔18〕前記〔1〕~〔6〕のいずれか1つに記載のクロロプレン系重合体を含むラテックス。
〔19〕接着剤用又は加硫ゴム用である〔18〕に記載のラテックス。
Claims (19)
- 上記一般式(1)で表される構造の官能基を有する、請求項1に記載のクロロプレン系重合体。
- 重量平均分子量Mwと前記数平均分子量Mnとの比である分子量分布Mw/Mnが1.5~5.0である請求項1又は2に記載のクロロプレン系重合体。
- クロロプレン単量体の単独重合体である請求項1~3のいずれか一項に記載のクロロプレン系重合体。
- クロロプレン単量体及び該クロロプレン単量体と共重合可能な単量体からなる統計的共重合体である請求項1~3のいずれか一項に記載のクロロプレン系重合体。
- 前記クロロプレン単量体と共重合可能な単量体が、2,3-ジクロロ-1,3-ブタジエン、1-クロロ-1,3-ブタジエン、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステル、アクリルアミド、不飽和ニトリル及び芳香族ビニル化合物からなる群より選択される少なくとも1種である請求項5に記載のクロロプレン系重合体。
- 請求項1~6のいずれか一項に記載のクロロプレン系重合体を得るための製造方法であり、
全単量体100質量部に対し、下記一般式(3)又は(4)で表される連鎖移動剤を添加して、重合開始時における前記全単量体と前記連鎖移動剤との物質量の比[M]0/[CTA]を5/1~500/1とした溶液(A)と、乳化剤0.1~10質量%の水溶液(B)500~5000質量部と、を混合し乳化した後、ラジカル重合を行い、重合率20~50%に到達した時に、クロロプレン単量体単独、又はクロロプレン単量体及びクロロプレン単量体と共重合可能な単量体100~5000質量部を追添加する、クロロプレン系重合体の製造方法。
- 前記追添加後の最終重合率が50%以上である、請求項7に記載のクロロプレン系重合体の製造方法。
- 上記一般式(3)で表される連鎖移動剤を添加する、請求項7又は8に記載のクロロプレン系重合体の製造方法。
- 請求項1~6のいずれか一項に記載のクロロプレン系重合体を含む組成物。
- 更に、天然ゴム、イソプレンゴム、ブチルゴム、ニトリルゴム、水素化ニトリルゴム、ブタジエンゴム、スチレンブタジエンゴム及びエチレンプロピレンゴムからなる群より選択される少なくとも1種を含む請求項10に記載の組成物。
- 請求項10又は11に記載の組成物を含む接着剤組成物。
- 請求項12に記載の接着剤組成物を含む接着剤。
- 耐層分離性が8週間以上である請求項12に記載の接着剤組成物又は請求項13に記載の接着剤。
- 請求項10又は11に記載の組成物を含む加硫ゴム。
- デマッチャ屈曲疲労試験を100万回実施した時点で亀裂がない請求項15に記載の加硫ゴム。
- 請求項15又は16に記載の加硫ゴムを使用した防振ゴム、ベルト、オーバヘッドビークル向け部品、免震ゴム、ホース、ワイパー、浸漬製品、シール部品、ブーツ、ゴム引布、ゴムロール又はスポンジ製品。
- 請求項1~6のいずれか一項に記載のクロロプレン系重合体を含むラテックス。
- 接着剤用又は加硫ゴム用である請求項18に記載のラテックス。
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US16/631,594 US11254807B2 (en) | 2017-07-21 | 2018-07-20 | Chloroprene polymer and production method therefor |
JP2019530612A JP6998958B2 (ja) | 2017-07-21 | 2018-07-20 | クロロプレン系重合体及びその製造方法 |
EP18834681.1A EP3656795B1 (en) | 2017-07-21 | 2018-07-20 | Production method of chloroprene polymer |
KR1020207004578A KR102507940B1 (ko) | 2017-07-21 | 2018-07-20 | 클로로프렌계 중합체 및 그의 제조 방법 |
CN201880048231.6A CN110945037B (zh) | 2017-07-21 | 2018-07-20 | 氯丁二烯系聚合物和其制造方法 |
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EP3783040A4 (en) * | 2018-08-31 | 2021-07-07 | Denka Company Limited | COPOLYMER OF CHLOROPRENE MONOMER AND UNSATURATED NITRILE COMPOUND, COMPOSITION WITH COPOLYMER, VULCANIZATION MOLDED BODY AND USE OF THE VULCANIZED MOLDED BODY |
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KR102507940B1 (ko) | 2023-03-08 |
KR20200032718A (ko) | 2020-03-26 |
CN110945037B (zh) | 2022-11-11 |
US11254807B2 (en) | 2022-02-22 |
US20200165421A1 (en) | 2020-05-28 |
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EP3656795A1 (en) | 2020-05-27 |
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CN110945037A (zh) | 2020-03-31 |
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