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WO2017116145A1 - Procédé de préparation de caoutchouc de styrène-butadiène et caoutchouc de styrène-butadiène - Google Patents

Procédé de préparation de caoutchouc de styrène-butadiène et caoutchouc de styrène-butadiène Download PDF

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Publication number
WO2017116145A1
WO2017116145A1 PCT/KR2016/015423 KR2016015423W WO2017116145A1 WO 2017116145 A1 WO2017116145 A1 WO 2017116145A1 KR 2016015423 W KR2016015423 W KR 2016015423W WO 2017116145 A1 WO2017116145 A1 WO 2017116145A1
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WIPO (PCT)
Prior art keywords
styrene
butadiene rubber
thiol
weight
pentamethylheptane
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Ceased
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PCT/KR2016/015423
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English (en)
Korean (ko)
Inventor
이재민
이세은
김병윤
조인성
최우석
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LG Chem Ltd
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LG Chem Ltd
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Publication date
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Priority to EP16882097.5A priority Critical patent/EP3309184B1/fr
Priority to US15/741,538 priority patent/US10501610B2/en
Priority to CN201680043640.8A priority patent/CN107849195B/zh
Priority claimed from KR1020160181187A external-priority patent/KR101961918B1/ko
Publication of WO2017116145A1 publication Critical patent/WO2017116145A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F236/10—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 with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene

Definitions

  • the present invention relates to a method for producing styrene-butadiene rubber and styrene-butadiene rubber produced through the above, and specifically, using a molecular weight regulator including two or more components in a polymerization reaction, adding each component of the molecular weight regulator.
  • the present invention relates to a method for preparing styrene-butadiene rubber which can improve the physical properties of styrene-butadiene rubber prepared by optimizing a viewpoint, and to styrene-butadiene rubber produced thereby.
  • Emulsion polymerized styrene-butadiene rubber is the most commonly used synthetic rubber in the manufacture of tires and has properties such as flat vulcanizability, stable scorch, high processability and the like.
  • US Pat. Nos. 3,575,913 and 3,563,946 disclose that styrene-butadiene or styrene-butadiene-acrylate copolymers are prepared using potassium persulfate or azobisisobutyronitrile in emulsion.
  • Japanese Patent Laid-Open No. 1999-0077755 discloses an emulsion styrene-butadiene rubber which can be used for the production of tire treads having improved rolling resistance and treadwear properties with improved static friction properties.
  • t-dodecylmercaptan (t-DDM) is used as a molecular weight regulator, and t-dodecylmercaptan is composed of a mixture of 35 isomers due to its manufacturing mechanism.
  • t-DDM t-dodecylmercaptan
  • An object of the present invention is to prepare a styrene-butadiene rubber that can improve the physical properties of the styrene-butadiene rubber prepared by optimizing the input time of each component of the molecular weight regulator, while using a molecular weight regulator comprising two or more components. Is to provide.
  • Another object of the present invention is to provide a styrene-butadiene rubber having improved physical properties produced by the above production method.
  • SBR styrene-butadiene rubber
  • t-dodecyl mercaptan and pentamethylheptanthiol are included in a weight ratio of 70:30 to 95: 5,
  • the pentamethylheptane thiol provides a process for preparing styrene-butadiene rubber, which is introduced at a time when the polymerization exhibits a conversion of 10% to 55%.
  • the present invention is produced by the above production method, the tensile strength (TS) is 250 kg ⁇ f / cm 2 to 300 kg ⁇ f / cm 2 , the tensile elongation ( ⁇ ) is 370-400%, Provides butadiene rubber.
  • the method for producing styrene-butadiene rubber according to the present invention can improve the physical properties of the styrene-butadiene rubber produced by optimizing the input time of each component of the molecular weight regulator, while using a molecular weight regulator comprising two or more components. Therefore, the styrene-butadiene rubber produced by the above manufacturing method is improved in the properties of tensile strength, tensile elongation, etc. can be usefully used in the production of tires having environmentally friendly, wear resistance and the like.
  • Example 1 is a graph showing the M H value with time in the manufacturing method of Example 3 and Comparative Example 1.
  • SBR styrene-butadiene rubber
  • the styrene monomer may be at least one selected from styrene, monochlorostyrene, methyl styrene, ⁇ -methyl styrene, divinylbenzene, p-tert-styrene, and dimethyl styrene.
  • the styrene-based monomer may be 10% to 60% by weight of the total amount of the monomers, specifically, may be 15 to 50% by weight.
  • the styrene-based monomer is less than 10% by weight, mechanical properties including tensile properties of the produced styrene-butadiene rubber may be lowered, and when it exceeds 60% by weight, the elasticity and abrasion resistance of the produced styrene-butadiene rubber may be reduced. Can be.
  • the butadiene monomer is composed of 1,3-butadiene, 1,4-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene It may be one or more.
  • the butadiene-based monomer may be 40% to 90% by weight of the total amount of the monomer, specifically, may be 50% to 85% by weight. If the butadiene-based monomer is less than 40% by weight, there may be a problem that the elasticity and wear resistance of the produced styrene-butadiene rubber is lowered, and when it exceeds 90% by weight, mechanical properties including tensile properties of the produced styrene-butadiene rubber This can be degraded.
  • the structure of the butadiene unit in the copolymer of the styrene-butadiene rubber produced may have one or more structures selected from the group consisting of trans, cis, and vinyl groups.
  • molecular weight modifiers including t-dodecylmercaptan and pentamethylheptane thiol (PMHT)
  • the molecular weight modifier includes t-dodecyl mercaptan and pentamethylheptane thiol (PMHT), and the t-dodecyl mercaptan and pentamethylheptane thiol are included in a weight ratio of 70:30 to 95: 5.
  • PMHT pentamethylheptane thiol
  • the t-dodecyl mercaptan may be prepared according to the following scheme, and will include at least 35 isomers in the preparation method.
  • R ⁇ 1> -R ⁇ 4> is an alkyl group each independently, and the sum of carbon number of said R ⁇ 1> -R ⁇ 4> is 10.
  • the pentamethylheptanethiol is 2,2,4,4,6-pentamethylheptan-4-thiol, 2,4,4,6,6-pentamethylheptan-2-thiol, 2,3 It may include one or more selected from the group consisting of 4,6,6-pentamethylheptan-2-thiol, and 2,3,4,6,6-pentamethylheptan-3-thiol.
  • the pentamethylheptane thiol may include 65 mol% or more of 2,2,4,4,6-pentamethylheptan-4-thiol based on the total moles of pentamethylheptane thiol.
  • the pentamethylheptane thiol may be prepared according to the following scheme, and in the preparation method, 65 mol% of 2,2,4,4,6-pentamethylheptan-4-thiol based on the total number of moles of the pentamethylheptane thiol It may include more.
  • the molecular weight modifier used in the method for preparing styrene-butadiene rubber of the present invention includes the pentamethylheptane thiol such that the t-dodecyl mercaptan and pentamethylheptane thiol satisfy a weight ratio of 70:30 to 95: 5,
  • the pentamethylheptane thiol may include 65 mol% or more of the 2,2,4,4,6-pentamethylheptan-4-thiol with respect to the total mole number of the pentamethylheptane thiol, 2,
  • the single isomer of 2,4,4,6-pentamethylheptane-4-thiol occupies the largest fraction, allowing the styrene-butadiene rubbers to be produced to have even physical properties, thus the tensile strength of the styrene-butadiene rubbers And tensile elongation can be increased.
  • the t-dodecyl mercaptan and pentamethylheptanthiol are weight ratios greater than 70: less than 30 to less than 95: more than 5, more specifically weight ratios greater than 80:20 to less than 95: more than 5, more specifically 80 It may be included in a weight ratio of: 20 to 90:10.
  • the molecular weight modifier may include 2,2,4,4,6-pentamethylheptan-4-thiol 5 mol% or more relative to the total mole number of the molecular weight regulator, specifically 5 mol% to 50 mol% Can be.
  • the composition may include 0.01 to 2 parts by weight of the molecular weight modifier, based on 100 parts by weight of the composition, specifically 0.05 to 2 parts by weight, and more specifically 0.1 to 1 parts by weight. can do.
  • the average molecular weight of the styrene-butadiene rubber can be adjusted according to the amount of the molecular weight modifier used.
  • the styrene-butadiene rubber prepared when the molecular weight modifier is used in a small amount close to 0.01 parts by weight based on 100 parts by weight of the composition has a high molecular weight.
  • the styrene-butadiene rubber produced may have a low molecular weight when used in large quantities close to 2 parts by weight.
  • the content of the molecular weight modifier is less than 0.01 parts by weight, a problem may occur in the gel, when the content of more than 2 parts by weight, the physical properties of the produced styrene-butadiene rubber may be lowered.
  • a styrene monomer in the method for producing styrene-butadiene rubber of the present invention 2) butadiene monomers; And 3) a molecular weight modifier comprising t-dodecylmercaptan and pentamethylheptanthiol (PMHT) can be radically polymerized in an emulsion state.
  • PMHT pentamethylheptanthiol
  • the radical polymerization may be performed at a temperature of 5 ° C to 90 ° C, specifically 10 ° C to 50 ° C, for 2 hours to 72 hours, and specifically for 4 hours to 48 hours.
  • the temperature of the radical polymerization is less than 5 °C, it is difficult to reach the activity of the reaction, if it exceeds 90 °C, a gel can be formed.
  • t-dodecylmercaptan and pentamethylheptane thiol (PMHT) included in the molecular weight regulator may be separately added according to the progress of the polymerization reaction, and specifically, the t- Dodecylmercaptan may be added at the beginning of the reaction, and the pentamethylheptane thiol (PMHT) may be added after the polymerization reaction has started.
  • the pentamethylheptane thiol may be added at the time when the polymerization shows a conversion rate of 10% to 55%, and specifically the pentamethylheptane thiol (PMHT) may show a conversion rate of 15% to 50% of the polymerization. It may be added at the time indicated, and more specifically may be added at the time when the polymerization shows a conversion of 15% to 45%.
  • the styrene-butadiene rubbers produced according to the use of a single isomer, such as a large amount of a single isomer of 4,4,6-pentamethylheptan-4-thiol, have even physical properties, and thus the tensile strength and tensile elongation of the styrene-butadiene rubber. It is possible to exhibit a high physical property improvement effect, such as increased physical properties.
  • the composition may further include an acrylonitrile monomer in addition to the 1) styrene monomer and 2) butadiene monomer.
  • the acrylonitrile monomer may be at least one selected from methacrylonitrile, etaacrylonitrile, ⁇ -chloronitrile, ⁇ -cyanoethylacrylonitrile, and crotononitrile.
  • the acrylonitrile monomer may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total amount of the monomers.
  • the styrene-butadiene copolymer may express hydrophilicity, and when the amount is 10 parts by weight or less, the elasticity may be lowered, or the problem may be prevented from increasing in strength to a problem in processability.
  • composition may further include a radical initiator, an emulsifier, a polymerization terminator and the like as necessary.
  • the radical initiators include inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium peroxide, potassium perphosphate, hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide organic, such as t-butylcumyl peroxide, acetyl peroxide, isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, t-butyl peroxy isobutylate Nitrogen compounds such as peroxides, azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, azobis isobutane (butyl acid) methyl.
  • the polymerization initiator can be used alone or in combination of two or more
  • the radical initiator may be used in an amount of 0.01 to 3 parts by weight, specifically 0.02 to 1 part by weight, and more specifically 0.05 to 0.5 part by weight, based on 100 parts by weight of the total composition.
  • radical initiator When the radical initiator is used in an amount of 0.01 parts by weight or more based on 100 parts by weight of the total composition, sufficient polymerization may be achieved, and when used in an amount of 3 parts by weight or less, a polymer having a desired molecular weight may be more appropriately produced.
  • the emulsifier may be an anion, a cation, a nonionic surfactant, or the like, and specifically, may be at least one selected from a metal salt and an ammonium salt.
  • Specific examples of the emulsifier include at least one selected from alkyl sulfate metal salts, alkyl allyl sulfonic acid metal salts, alkyl phosphate metal salts, alkyl sulfate ammonium salts, alkyl allyl sulfonic acid ammonium salts, alkyl aryl sulfonic acid ammonium salts, allyl sulfonic acid ammonium salts and alkyl phosphate ammonium salts. And, more specifically, at least one selected from dodecylbenzene sulfonic acid, rosin acid, fatty acid, lauryl sulfonic acid, and hexadecylsulfonic acid.
  • the alkyl (allyl) and aryl (aryl) may each independently have 5 to 20 carbon atoms, if the carbon number is less than 5, there may be a problem in the role of dispersant, 20 carbon atoms If exceeded, the hydrophilicity of the styrene-butadiene copolymer may be lowered.
  • the emulsifier may be used in an amount of 0.1 to 10 parts by weight, specifically 0.5 to 10 parts by weight, based on 100 parts by weight of the total composition.
  • emulsifier is less than 0.1 parts by weight, micelles may not be formed, and if it exceeds 10 parts by weight, a microemulsion may be formed to generate low molecules.
  • polymerization terminator examples include diethyl hydroxyamine, N-isopropylhydroxyamine, monoethylhydroxyamine, sodium dimethyldithiocarbamate, and the like.
  • the polymerization terminator may be 0.01 parts by weight to 2 parts by weight with respect to 100 parts by weight of the total composition, and when less than 0.01 parts by weight, a reaction stopping effect may be insufficient and a gel may be generated.
  • the polymerization terminator is harmful to the human body is preferably used in less than 2 parts by weight, and when used in excess, may cause problems of odor caused by the unreacted polymerization terminator.
  • the method for producing styrene-butadiene rubber according to an example of the present invention may be based on the emulsion polymerization method commonly used in the art, except for the method of adding the above-described molecular weight regulator, 1) a styrene monomer and 2) Mixing of the butadiene monomer and the t-dodecyl mercaptan in the molecular weight regulator is not particularly limited and may be added to the polymerization reactor at the same time, or each component may be added to the polymerization reactor continuously.
  • the styrene-butadiene rubber prepared according to the method for preparing styrene-butadiene rubber is washed and removed to remove impurities (residue emulsifier, flocculant, etc.) from the coagulum of the produced styrene-butadiene copolymer and to obtain styrene-butadiene rubber.
  • the drying step can be further roughened.
  • the styrene-butadiene rubber prepared according to the polymerization method of the styrene-butadiene rubber of the present invention has a tensile strength (TS) of 250 kg ⁇ f / cm 2 to 300 kg ⁇ f / cm 2 and a tensile elongation ( ⁇ ) of 370 to May be 400%.
  • TS tensile strength
  • ⁇ tensile elongation
  • the styrene-butadiene rubber may have a 300% modulus value of 190 to 200.
  • the styrene-butadiene copolymer may have a weight average molecular weight of 200,000 g / mol to 3,000,000 g / mol, and specifically 500,000 g / mol to 2,000,000 g / mol.
  • weight average molecular weight is less than 200,000 g / mol may cause a problem of deterioration of physical properties, and if the weight average molecular weight exceeds 3,000,000 g / mol, it may occur a problem difficult to process due to high gel generation and hardness.
  • Pentamethylheptane thiol (TIB-TDM, Chevron Phillips, 2,2) containing 65 mol% or more of 2,2,4,4,6-pentamethylheptan-4-thiol as a molecular weight regulator when the conversion rate reaches 15% 65 parts by weight of 4,4,6-pentamethylheptan-4-thiol and 35 parts by weight of the remaining isomers were added 0.05 parts by weight (10 parts by weight of 0.5 parts by weight of the total amount of the molecular weight regulator). It was. The polymerization was terminated at the conversion point of 63%, and the reaction time was 7 hours.
  • Example 1 a styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the pentamethylheptanthiol was added at the time when the conversion rate reached 30%.
  • Example 1 styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the pentamethylheptanthiol was added at the time when the conversion rate reached 45%.
  • Example 1 styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the pentamethylheptanthiol was added at a time when the conversion rate reached 50%.
  • Example 1 0.4 parts by weight of t-dodecyl mercaptan (Isu Chemical) as a molecular weight regulator (95 parts by weight of 0.5 parts by weight of total molecular weight regulator), and 0.025 parts by weight of the pentamethylheptane thiol (total weight) Styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the molecular weight regulator was added in an amount of 0.5 parts by weight (5% by weight).
  • t-dodecyl mercaptan Isu Chemical
  • Example 1 0.35 parts by weight of t-dodecyl mercaptan (Isu Chemical) as a molecular weight regulator (70% by weight of 0.5 parts by weight of the total molecular weight regulator), and 0.15 parts by weight of the pentamethylheptane thiol (total weight) Styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the content of the molecular weight modifier was 0.5 parts by weight (30% by weight).
  • Example 1 a styrene-butadiene rubber was prepared in the same manner as in Example 1, except that only 0.5 part by weight of t-dodecyl mercaptan was added as the molecular weight regulator and the pentamethylheptane thiol was not added. .
  • Example 1 0.3 parts by weight of t-dodecyl mercaptan (Isu Chemical) as a molecular weight regulator (60 parts by weight of 0.5 parts by weight of the total molecular weight regulator), 0.2 parts by weight of the pentamethylheptane thiol (total molecular weight regulator) Styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the amount was added in an amount of 0.5 parts by weight (40% by weight).
  • t-dodecyl mercaptan Isu Chemical
  • pentamethylheptane thiol total molecular weight regulator
  • Example 1 a styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the pentamethylheptanthiol was added at a time when the conversion rate reached 60%.
  • Example 1 a styrene-butadiene rubber was prepared in the same manner as in Example 1, except that the pentamethylheptanthiol was added at a conversion rate of 5%.
  • Mooney viscosity was measured by using a Mooney viscometer (MV2000, Alpha Technologies, Inc.) at a temperature of 125 ° C. with a large rotor and reading and reading 4 minutes after the start of the rotor.
  • M H and M L The difference between M H and M L was recorded by measuring the M L (minimum torque) and M H (maximum torque) values with MDR, Ts ⁇ 1 (time to 1% vulcanization), Ts ⁇ 2 (2% The time required until vulcanization), Tc'50 (50% cure time) and Tc'90 (90% cure time) were measured. In this case, Tc'90 means the vulcanization speed.
  • Figure 1 shows the M H value over time of Example 3 and Comparative Example 1.
  • Elongation (e%) measured the elongation of the vulcanizate after vulcanizing each of the nitrile copolymer rubbers at 145 ° C. for 45 minutes.
  • Tensile strength (TS, kg, f / cm 2 ) measured the tensile strength of 300% vulcanizate after vulcanizing each of the nitrile copolymer rubber at 145 °C.
  • PMHT pentamethylheptane thiol
  • MV Mooney viscosity
  • c-MV Mooney viscosity after vulcanization
  • MDR Moving Die Rheometer
  • 300% M represents 300% modulus and the dosage represents weight percent of the total molecular weight modifier dosage.
  • the styrene-butadiene rubber prepared according to Comparative Example 1 did not use the pentamethylheptanedol as a molecular weight regulator, it was confirmed that showed a low modulus.
  • the method for preparing styrene-butadiene rubber of Example 3 includes pentamethylheptane thiol as the molecular weight regulator, the M H (maximum torque) value of the styrene-butadiene rubber produced is the molecular weight regulator. It can be seen that it is higher than the styrene-butadiene rubber prepared by the preparation method according to Comparative Example 1 that does not contain pentamethylheptane thiol.

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Abstract

La présente invention concerne un procédé de préparation d'un caoutchouc de styrène-butadiène et un caoutchouc de styrène-butadiène ainsi préparé, le procédé permettant d'améliorer les propriétés physiques du caoutchouc de styrène-butadiène préparé, tout en utilisant un agent d'ajustement du poids moléculaire contenant deux ingrédients ou plus dans une réaction de polymérisation, par l'optimisation du temps de charge de chaque ingrédient de l'agent d'ajustement du poids moléculaire. Le caoutchouc de styrène-butadiène préparé par le procédé de préparation de la présente invention présente des propriétés améliorées, telles que la résistance à la traction et l'allongement à la traction, et peut ainsi être utilisé avantageusement dans la fabrication d'un pneu présentant des caractéristiques écologiques, une résistance à l'usure, etc.
PCT/KR2016/015423 2015-12-28 2016-12-28 Procédé de préparation de caoutchouc de styrène-butadiène et caoutchouc de styrène-butadiène Ceased WO2017116145A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP16882097.5A EP3309184B1 (fr) 2015-12-28 2016-12-28 Procédé de préparation de caoutchouc de styrène-butadiène et caoutchouc de styrène-butadiène
US15/741,538 US10501610B2 (en) 2015-12-28 2016-12-28 Method for preparing styrene-butadiene rubber and styrene-butadiene rubber
CN201680043640.8A CN107849195B (zh) 2015-12-28 2016-12-28 丁苯橡胶的制备方法和丁苯橡胶

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KR10-2015-0187671 2015-12-28
KR20150187671 2015-12-28
KR10-2016-0181187 2016-12-28
KR1020160181187A KR101961918B1 (ko) 2015-12-28 2016-12-28 스티렌-부타디엔 고무의 제조방법 및 스티렌-부타디엔 고무

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807941A (en) * 1994-08-29 1998-09-15 Nippon Zeon Co., Ltd. Unsaturated nitrile-conjugated diene copolymer process for producing same and vulcanizable rubber composition
US6342559B1 (en) * 1998-03-31 2002-01-29 Zeon Corporation Conjugated diene rubber, process for producing the same, and rubber composition
US6642315B2 (en) * 2000-08-01 2003-11-04 The Yokohama Rubber Co., Ltd. Rubber composition and crosslinked rubber
US6649724B2 (en) * 2000-06-07 2003-11-18 Zeon Corporation Conjugated diene rubber gel, rubber compositions containing the same and process for production of conjugated diene rubber
KR101484380B1 (ko) * 2009-12-23 2015-01-19 스타이런 유럽 게엠베하 냄새가 적은 공중합체 라텍스의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5807941A (en) * 1994-08-29 1998-09-15 Nippon Zeon Co., Ltd. Unsaturated nitrile-conjugated diene copolymer process for producing same and vulcanizable rubber composition
US6342559B1 (en) * 1998-03-31 2002-01-29 Zeon Corporation Conjugated diene rubber, process for producing the same, and rubber composition
US6649724B2 (en) * 2000-06-07 2003-11-18 Zeon Corporation Conjugated diene rubber gel, rubber compositions containing the same and process for production of conjugated diene rubber
US6642315B2 (en) * 2000-08-01 2003-11-04 The Yokohama Rubber Co., Ltd. Rubber composition and crosslinked rubber
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