WO2021071273A1 - Procédé de fabrication d'un caoutchouc à base de nitrile, caoutchouc à base de nitrile fabriqué selon le procédé, et composition de caoutchouc le comprenant - Google Patents

Procédé de fabrication d'un caoutchouc à base de nitrile, caoutchouc à base de nitrile fabriqué selon le procédé, et composition de caoutchouc le comprenant Download PDF

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WO2021071273A1
WO2021071273A1 PCT/KR2020/013720 KR2020013720W WO2021071273A1 WO 2021071273 A1 WO2021071273 A1 WO 2021071273A1 KR 2020013720 W KR2020013720 W KR 2020013720W WO 2021071273 A1 WO2021071273 A1 WO 2021071273A1
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Prior art keywords
nitrile
emulsifier
rubber
based rubber
mixture
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PCT/KR2020/013720
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English (en)
Korean (ko)
Inventor
이재민
김병윤
손성민
이세은
최우석
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주식회사 엘지화학
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Priority claimed from KR1020200126181A external-priority patent/KR102536743B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2021539444A priority Critical patent/JP7299987B2/ja
Priority to US17/422,254 priority patent/US20220089801A1/en
Priority to EP20874984.6A priority patent/EP3892656B1/fr
Priority to CN202080008786.5A priority patent/CN113272342B/zh
Publication of WO2021071273A1 publication Critical patent/WO2021071273A1/fr

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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
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F236/12—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 nitriles
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/14—Treatment of polymer emulsions
    • C08F6/18—Increasing the size of the dispersed particles
    • 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
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • the present invention relates to a method for producing a nitrile-based rubber having a low residual emulsifier content and excellent mechanical properties, a nitrile-based rubber prepared therefrom, and a rubber composition comprising the nitrile-based rubber.
  • nitrile rubber is a polymer prepared by copolymerizing an ⁇ , ⁇ -unsaturated nitrile monomer such as acrylonitrile (ACN) with a conjugated diene monomer such as butadiene, and is a repeat derived from ⁇ , ⁇ -unsaturated nitrile monomer.
  • ACN acrylonitrile
  • butadiene conjugated diene monomer
  • nitrile rubber is a polymer prepared by copolymerizing an ⁇ , ⁇ -unsaturated nitrile monomer such as acrylonitrile (ACN) with a conjugated diene monomer such as butadiene, and is a repeat derived from ⁇ , ⁇ -unsaturated nitrile monomer.
  • the vulcanization properties of the nitrile rubber may vary depending on the content of the repeating unit derived from the ⁇ , ⁇ -unsaturated nitrile monomer contained in the rubber.
  • the ⁇ , ⁇ -unsaturated nitrile monomer As the content of acrylonitrile increases, resistance to hydrocarbon fuels and petroleum fluids increases, and heat resistance, ozone resistance, abrasion resistance, tensile strength, hardness and density increase, but low temperature flexibility, repulsion elasticity, and gas permeability decrease. There is this.
  • nitrile-based rubbers are low nitrile rubbers having an ⁇ , ⁇ -unsaturated nitrile-based monomer content of 18-20 wt%, mid-low nitrile rubbers having 28-29 wt%, and heavy nitrile-based rubbers having 33-34 wt%, 38- It is classified into 39% by weight of high nitrile rubber and 45 to 48% by weight of ultra-high nitrile rubber.
  • high nitrile rubber and ultra-high nitrile rubber are fields that require resistance to hydrocarbons with a high aromatic content such as gasoline.
  • heavy nitrile rubber is used for oils with low aromatic content or swelling of rubber products
  • medium-low nitrile rubber and low nitrile rubber are liquids with insignificant swelling effect such as paraffin oil or polyalphaolefin. It is mainly used in the manufacture of foam insulation materials and hoses that require low temperature properties such as low temperature resistance.
  • these nitrile rubbers are generally prepared by emulsion polymerization using a fatty acid or rosin containing a monocarboxyl group having 12 to 18 carbon atoms as an emulsifier at a low temperature of 5 to 15°C.
  • an emulsifier In addition to being added as an impurity, most of them remain as impurities in the nitrile-based rubber, resulting in a problem that the mechanical properties of the nitrile-based rubber produced by emulsion polymerization are deteriorated and the glass transition temperature range is widened, and this causes the application of the nitrile-based rubber. There is a problem that the field is limited and processing is difficult.
  • the present invention was devised to solve the problem of the technology behind the present invention, and an object of the present invention is to provide a method for producing a nitrile-based rubber having a low residual emulsifier content and excellent mechanical properties.
  • an object of the present invention is to provide a nitrile-based rubber having a low residual emulsifier content prepared by the above production method.
  • an object of the present invention is to provide a rubber composition comprising the nitrile-based rubber.
  • the present invention comprises the step (S1) of polymerizing a monomer mixture comprising an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer in the presence of an emulsifier mixture.
  • the emulsifier mixture comprises a first emulsifier containing a sulfosuccinate ester-based compound and a second emulsifier containing a fatty acid having 12 to 18 carbon atoms or a rosin acid containing a monocarboxy group, and the first emulsifier and It provides a method for producing a nitrile-based rubber containing a second emulsifier in a weight ratio of 2:1 to 6:1.
  • the present invention is prepared by the above production method, and the residual emulsifier content is 1.2% by weight or less, and the emulsifier is a fatty acid or rosin acid having 12 to 18 carbon atoms including a sulfosuccinate ester compound and a monocarboxy group. Provides a nitrile rubber.
  • the present invention provides a nitrile-based rubber composition comprising the nitrile-based rubber.
  • the manufacturing method according to the present invention while emulsion polymerization is easily performed with a reduced amount of emulsifier, the content of impurities derived from the emulsifier is reduced, so that a nitrile-based rubber having excellent mechanical properties can be prepared.
  • the nitrile-based rubber according to the present invention may have a very small amount of residual emulsifier, as it is prepared by the above manufacturing method, thereby having excellent mechanical properties.
  • the present invention provides a method for producing a nitrile-based rubber capable of producing a nitrile-based rubber having excellent mechanical properties due to a low content of a residual emulsifier.
  • the manufacturing method of the nitrile-based rubber comprises the step (S1) of polymerizing a monomer mixture including an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer in the presence of an emulsifier mixture
  • the emulsifier mixture comprises a first emulsifier containing a sulfosuccinate ester-based compound and a second emulsifier containing a fatty acid having 12 to 18 carbon atoms or a rosin acid containing a monocarboxy group, wherein the first emulsifier and the second emulsifier It is characterized in that it comprises a weight ratio of 2:1 to 6:1.
  • nitrile rubber is prepared through emulsion polymerization using an emulsifier such as a fatty acid having 12 to 18 carbon atoms or rosin acid containing a monocarboxyl group, and at this time, 2 to 3 parts by weight based on 100 parts by weight of a monomer for smooth emulsion polymerization.
  • Negative emulsifiers are used, and the above emulsifiers are not removed during post-treatment such as coagulation after polymerization, and most of them remain as impurities in the nitrile-based rubber, thereby causing deterioration in properties such as mechanical properties and vulcanization properties of the nitrile-based rubber. There is a problem.
  • a first emulsifier containing a sulfosuccinate ester-based compound as an emulsifier and a second emulsifier containing a fatty acid having 12 to 18 carbon atoms or a rosin acid containing a monocarboxyl group are mixed in a specific ratio.
  • one emulsifier mixture not only can the emulsion polymerization be sufficiently smooth with the amount of the emulsifier used less than the usual amount of emulsifier, but most of them are removed in the post-treatment process to significantly reduce the residual emulsifier content, and thus, the mechanical properties and vulcanization properties are excellent.
  • a nitrile-based rubber having a low emulsifier content can be prepared.
  • the step (S1) is a step of polymerizing a monomer mixture including an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer to prepare a nitrile-based rubber.
  • a monomer mixture containing an ⁇ , ⁇ -unsaturated nitrile-based monomer and a conjugated diene-based monomer is emulsified. It can be carried out by polymerization.
  • the emulsifier mixture may include the first emulsifier and the second emulsifier in a weight ratio of 2:1 to 6:1, specifically in a weight ratio of 4:1 to 6:1, and emulsion polymerization within this range
  • the content of the residual emulsifier which remains in the nitrile-based rubber and acts as an impurity, can be significantly reduced.
  • the ratio of the first emulsifier in the emulsifier mixture is increased, the residual emulsifier content in the prepared nitrile rubber may be further reduced, but the conversion rate or emulsification performance decreases due to poor emulsion polymerization, resulting in lower productivity.
  • the emulsifier mixture is used in an amount of 1.0 to 1.5 parts by weight, specifically, or 1.0 to 1.3 parts by weight, based on 100 parts by weight of the monomer mixture. While the emulsion polymerization can be performed smoothly within this range, the content of the residual emulsifier in the prepared nitrile-based rubber may be a very small amount. Specifically, when the amount of the emulsifier mixture is less than 1.5 parts by weight, the amount of the residual emulsifier can be minimized, and improvement of all mechanical properties can be expected through this, and at the same time, a decrease in polymerization productivity can be prevented.
  • the first emulsifier containing a sulfosuccinate ester compound may be the sulfosuccinate ester compound itself or a solution in which a sulfosuccinate ester compound is dissolved in the solvent.
  • the sulfosuccinate ester-based compound may be a compound represented by the following Formula 1 or an alkali metal salt thereof.
  • R and R' are each independently an alkyl group having 1 to 20 carbon atoms.
  • R and R' may each independently be an alkyl group having 3 to 10 carbon atoms.
  • the sulfosuccinate ester compound may be an alkali metal salt of the compound represented by Formula 1, wherein the alkali metal may be sodium, and more specifically, the sulfosuccinate ester compound is It may be dihexyl sulfosuccinate sodium salt.
  • the sulfosuccinate ester-based compound When the sulfosuccinate ester-based compound is included in the emulsifier mixture, the content of the emulsifier remaining in the rubber is reduced in the post-treatment process of coagulation and drying after polymerization, and even if a small amount of the emulsifier mixture is added, emulsification Due to its excellent properties, the vulcanization properties and mechanical properties are remarkably excellent.
  • the second emulsifier containing a fatty acid having 12 to 18 carbon atoms or a rosin acid containing a monocarboxylic group may be the fatty acid or rosin acid itself, or may be in the form of a metal salt thereof, and a fatty acid or rosin in the solvent It may be a solution in which an acid is dissolved.
  • the monomer mixture comprises an ⁇ , ⁇ -unsaturated nitrile monomer and a conjugated diene monomer in a weight ratio of 15:85 to 45:55, specifically 18:82 to 45:55, or 18:82 to 35:65 days In this range, a nitrile-based rubber having excellent flexibility, oil resistance and tensile strength can be prepared.
  • the ⁇ , ⁇ -unsaturated nitrile-based monomer may be one or more selected from the group consisting of acrylonitrile, methacrylonitrile, ⁇ -chloronitrile and ⁇ -cyanoethylacrylonitrile, specifically acrylonitrile. It can be nitrile.
  • the conjugated diene-based monomer is one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and isoprene It may be more than one, specifically, it may be 1,3-butadiene.
  • the emulsion polymerization may further use a polymerization initiator, and the polymerization initiator may be one or more selected from the group consisting of inorganic peroxides, organic peroxides, and nitrogen-based compounds as radical initiators.
  • the inorganic peroxide may be one or more selected from the group consisting of sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide, and specifically, may be ammonium persulfate.
  • the organic peroxide is di-isobutyl hydroperoxide, t-butyl peroxide, cumene hydroperoxide, p-mentane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide.
  • Isobutyl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3,5,5-trimethylhexanol peroxide, and t-butyl peroxy may be one or more selected from the group consisting of isobutylate, specific As may be p-mentane hydroperoxide.
  • the nitrogen-based compound may be one or more selected from the group consisting of azobis isobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, and methyl azobis isobutyrate. , Specifically, it may be azobis isobutyronitrile.
  • the polymerization initiator may be used in an amount of 0.01 parts by weight to 2 parts by weight, or 0.03 parts by weight to 1 part by weight based on 100 parts by weight of the monomer mixture, and a nitrile rubber having an appropriate viscosity and excellent viscoelastic properties by controlling the polymerization degree within this range Can be manufactured.
  • the polymerization can be carried out in a temperature range of 5°C to 90°C, or 5°C to 50°C, and if necessary, a molecular weight modifier, a chelating agent, an oxidation-reducing agent, a dispersant, a pH adjuster, a deoxidant, an anti-aging agent, and At least one additive selected from the group consisting of oxygen trapping agents may further be used.
  • the manufacturing method according to an embodiment of the present invention may further perform a coagulation and drying step after the polymerization in step (S1).
  • the nitrile-based rubber prepared by the polymerization may be in the state of a nitrile-based rubber latex, and the agglomeration is for agglomeration of the nitrile-based rubber latex, and salt agglomeration by treating the latex with an aqueous inorganic salt solution and forming a nitrile-based rubber latex aggregate It may be a forming step.
  • the salt agglomeration is to remove impurities (remaining emulsifier, etc.) from the nitrile rubber latex and obtain a nitrile rubber latex aggregate. After heating, the nitrile-based rubber latex may be added and stirred for 10 minutes to 1 hour.
  • the inorganic salt aqueous solution is a mixture of inorganic salt and distilled water, but is not particularly limited, may be a pH of 2 to 11, and the inorganic salt is selected from the group consisting of potassium chloride, sodium chloride, manganese chloride, calcium chloride, magnesium sulfate, and aluminum sulfate. It may be one or more, specifically, it may be calcium chloride.
  • the drying is to remove moisture from the nitrile-based rubber latex aggregate produced by the agglomeration to obtain a nitrile-based rubber powder, and may be performed by applying heat of 80°C to 130°C, or 80°C to 110°C. Within this range, it is possible to appropriately adjust the amount of water remaining without causing thermal deformation.
  • the present invention provides a nitrile-based rubber manufactured by the above manufacturing method.
  • the nitrile-based rubber according to an embodiment of the present invention is prepared by the above manufacturing method, and the residual emulsifier content is 0.1 to 1.2% by weight, 0.1 to 0.9% by weight, 0.1 to 0.7% by weight, or 0.2 to 0.7% by weight.
  • the residual emulsifier may be a fatty acid having 12 to 18 carbon atoms including a sulfosuccinate ester-based compound and a monocarboxyl group, or a rosin acid or a residual material derived therefrom.
  • nitrile-based rubber is prepared by emulsion polymerization using 2 to 3 parts by weight of an emulsifier based on 100 parts by weight of a monomer, and the total amount of the emulsifier used is present as impurities in the prepared nitrile-based rubber, so the residual emulsifier content in the rubber.
  • the nitrile-based rubber according to the present invention has the effect of significantly reducing the content of the emulsifier remaining in the rubber by being prepared by the above production method using the emulsifier mixture as described above.
  • the present invention provides a nitrile-based rubber composition comprising the nitrile-based rubber.
  • the nitrile-based rubber composition according to the present invention includes the nitrile-based rubber as a raw material rubber, and if necessary, at least one additive selected from the group consisting of a vulcanizing agent, a vulcanization accelerator, a dispersant, a reinforcing filler, and a dissolution accelerator It may further include.
  • the vulcanizing agent is powdered sulfur, sublimated sulfur, precipitated sulfur, surface-treated sulfur, insoluble sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, N,N'-dityro-bis(hexahydro-2H-a Zepinone) and polysulfide.
  • the vulcanization accelerator may be at least one selected from the group consisting of zinc oxide, N-tert-butyl-2-benzothiazolesulfenamide (TBBS), and tetramethylthiuram monosulfite (TMTM).
  • the dispersant may be one or more selected from the group consisting of stearic acid, oleic acid, palmitic acid and (anhydrous) maleic acid.
  • the reinforcing filler may be at least one selected from the group consisting of carbon black, silica, limestone, mica, clay, and bentonite.
  • the dissolution promoter may be at least one selected from the group consisting of di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, and diisodecyl phthalate.
  • a molded article prepared from a nitrile-based rubber composition containing the nitrile-based rubber may have excellent mechanical properties, for example, after vulcanizing the rubber composition at 145°C for 45 minutes, ASTM Tensile strength measured according to D412 is 210 kg ⁇ f/cm 2 to 230 kg ⁇ f/cm 2 , elongation is 390% to 500%, and 300% modulus is 135 kg ⁇ f/cm 2 to 140 kg ⁇ f / cm 2 it may be.
  • emulsifier mixture was a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate salt (LG Household & Health Care, Elofad TL070) in a weight part of 5:1. Subsequently, the polymerization reaction was initiated at 10° C., polymerization was performed for 8 hours, and the polymerization was terminated to prepare a nitrile-based rubber latex.
  • a calcium chloride aqueous solution was added to the latex so that the prepared nitrile rubber latex and calcium chloride in the calcium chloride aqueous solution were at a weight ratio of 100:2, and then agglomerated by heating at 65°C to prepare a nitrile rubber latex aggregate, and an oven at 100°C. And dried to prepare a nitrile-based rubber.
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Household & Health Care, Elofad TL070) as an emulsifier mixture in an amount of 2:1 was used. In the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Household & Health Care, Elofad TL070) as an emulsifier mixture in an amount of 6:1
  • CYTEC, MA80 dihexyl sulfosuccinate sodium salt
  • LG Household & Health Care, Elofad TL070 potassium oleate
  • Example 1 a mixture of dioctyl sulfosuccinate sodium salt (Merck, 577-11-7) and potassium oleate (LG Life & Health, Elofad TL070) in an amount of 5:1 as an emulsifier mixture was used. Except in the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Example 1 a mixture of dibutyl sulfosuccinate sodium salt (Merck, 5144-51-4) and potassium oleate salt (LG Life & Health, Elofad TL070) in an amount of 5:1 as an emulsifier mixture was used. Except in the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Example 1 a nitrile-based rubber was prepared in the same manner as in Example 1, except that 1.2 parts by weight of potassium oleate (LG Household & Health Care, Elofad TL070) was used instead of the emulsifier mixture.
  • potassium oleate LG Household & Health Care, Elofad TL070
  • Example 1 a nitrile-based rubber was prepared in the same manner as in Example 1, except that 2.0 parts by weight of a potassium oleate salt (LG Household & Health Care, Elofad TL070) was used instead of the emulsifier mixture.
  • a potassium oleate salt LG Household & Health Care, Elofad TL070
  • Example 1 a nitrile-based rubber was prepared in the same manner as in Example 1, except that 1.2 parts by weight of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) was used instead of the emulsifier mixture.
  • CYTEC, MA80 dihexyl sulfosuccinate sodium salt
  • Example 1 a nitrile-based rubber was prepared in the same manner as in Example 1, except that 2.0 parts by weight of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) was used instead of the emulsifier mixture.
  • CYTEC, MA80 dihexyl sulfosuccinate sodium salt
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Life & Health, Elofad TL070) as an emulsifier mixture were mixed in a 1:1 part by weight, except for using In the same manner as in Example 1, a nitrile-based rubber was prepared.
  • CYTEC, MA80 dihexyl sulfosuccinate sodium salt
  • LG Life & Health Elofad TL070
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Life & Health, Elofad TL070) as an emulsifier mixture was used in an amount of 1:2. In the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Household & Health Care, Elofad TL070) as an emulsifier mixture in an amount of 1:5 was used. In the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Example 1 a mixture of dihexyl sulfosuccinate sodium salt (CYTEC, MA80) and potassium oleate (LG Household & Health Care, Elofad TL070) as an emulsifier mixture in an amount of 7:1 was used, except that the mixture was used. In the same manner as in Example 1, a nitrile-based rubber was prepared.
  • Mooney viscosity was measured using a Mooney viscometer (MV2000, Alpha Technology Co., Ltd.) by measuring and reading the value 4 minutes after starting the rotor in 1 minute of preheating with a large rotor at 100°C.
  • the Mooney viscosity of the nitrile-based rubbers of Examples 1 to 5 and the nitrile-based rubbers of Comparative Examples 1 to 8 according to an embodiment of the present invention is at a similar level, through which It can be seen that through the manufacturing method using the emulsifier mixture of the present invention, a nitrile-based rubber as in the conventional manufacturing method can be easily manufactured.
  • each nitrile rubber 100 parts by weight of each nitrile rubber, 1.5 parts by weight of sulfur powder, 3 parts by weight of zinc oxide and 0.7 parts by weight of N-tert-butyl-2-benzothiazolesulfenamide as a vulcanization accelerator, 1 part by weight of stearic acid as a dispersant, reinforcing properties
  • 40 parts by weight of carbon black was added to the reactor, followed by mixing at 50° C. for 8 minutes (1 minute for premixing, 7 minutes for compounding) while stirring at 50 rpm to prepare a nitrile rubber composition.
  • Each rubber composition was vulcanized at 170° C. using an oscillating disc rheometer to measure the maximum torque (MH) value.
  • Ts'1 time required until 1% vulcanization
  • Tc'90 90% vulcanization time
  • each rubber composition was vulcanized at 145° C. for 45 minutes, and then elongation and 300% modulus were measured according to ASTM D412.
  • the content of the residual emulsifier contained in each nitrile-based rubber prepared in Examples and Comparative Examples was measured as the content with respect to the total weight of the nitrile-based rubber. Specifically, the raw rubber sample to be measured was dissolved in tetrahydrofuran (THF) and pretreated with methanol reprecipitation twice, and then the content of the emulsifier in the polymer was analyzed using an LC/MS chromatogram. The measurement result was compared with the standard sample, and the content of the emulsifier relative to the total weight of the sample was calculated as wt%.
  • THF tetrahydrofuran
  • Examples 1 to 5 showed similar levels of hardness and Mooney viscosity as Comparative Examples 1 to 8, while the vulcanization and mechanical properties were greatly improved, and the content of the residual emulsifier was also reduced. I can check..
  • Examples 1 to 5 significantly improved tensile strength, elongation, and 300% modulus as compared to Comparative Examples 2 and 4 in which a larger amount of the emulsifier was used.
  • emulsion polymerization can proceed smoothly even with a smaller amount of use, and the content of the remaining emulsifier is reduced. It can be seen that the mechanical properties can be improved.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

La présente invention concerne : un procédé de fabrication d'un caoutchouc à base de nitrile qui présente une faible teneur en émulsifiants résiduaires et fait preuve d'excellentes propriétés mécaniques ; un caoutchouc à base de nitrile fabriqué à partir dudit procédé ; et une composition de caoutchouc comprenant le caoutchouc à base de nitrile.
PCT/KR2020/013720 2019-10-11 2020-10-08 Procédé de fabrication d'un caoutchouc à base de nitrile, caoutchouc à base de nitrile fabriqué selon le procédé, et composition de caoutchouc le comprenant WO2021071273A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2021539444A JP7299987B2 (ja) 2019-10-11 2020-10-08 ニトリル系ゴムの製造方法、それから製造されたニトリル系ゴム、および前記ゴムを含むゴム組成物
US17/422,254 US20220089801A1 (en) 2019-10-11 2020-10-08 Method for Manufacturing Nitrile-Based Rubber, Nitrile-Based Rubber Manufactured Thereby, and Rubber Composition Comprising Same Rubber
EP20874984.6A EP3892656B1 (fr) 2019-10-11 2020-10-08 Procédé de fabrication d'un caoutchouc à base de nitrile, caoutchouc à base de nitrile fabriqué selon le procédé, et composition de caoutchouc le comprenant
CN202080008786.5A CN113272342B (zh) 2019-10-11 2020-10-08 腈类橡胶的制备方法、由其制备的腈类橡胶和包含腈类橡胶的橡胶组合物

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KR20190126408 2019-10-11
KR10-2019-0126408 2019-10-11
KR10-2020-0126181 2020-09-28
KR1020200126181A KR102536743B1 (ko) 2019-10-11 2020-09-28 니트릴계 고무의 제조방법, 이로부터 제조된 니트릴계 고무 및 상기 고무를 포함하는 고무 조성물

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4920176A (en) * 1988-12-05 1990-04-24 The B. F. Goodrich Company Nitrile emulsion polymers having improved adhesion properties
US6492446B1 (en) * 1999-06-21 2002-12-10 Takeda Chemical Industries, Ltd. Alatex compound for dip molding and a dip-molded product
US20020198309A1 (en) * 2000-10-27 2002-12-26 Cheil Industries Inc. Method of preparing diene latex having a large particle size by addition of a pretreated seed latex to an agglomerating agent
WO2010019180A1 (fr) * 2008-05-06 2010-02-18 Mallard Creek Polymers, Inc. Latex anionique utilisé comme véhicule d'ingrédients actifs et procédés de fabrication et d'utilisation de ce dernier
KR20150016093A (ko) * 2013-08-02 2015-02-11 주식회사 엘지화학 고무강화 열가소성 수지의 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4920176A (en) * 1988-12-05 1990-04-24 The B. F. Goodrich Company Nitrile emulsion polymers having improved adhesion properties
US6492446B1 (en) * 1999-06-21 2002-12-10 Takeda Chemical Industries, Ltd. Alatex compound for dip molding and a dip-molded product
US20020198309A1 (en) * 2000-10-27 2002-12-26 Cheil Industries Inc. Method of preparing diene latex having a large particle size by addition of a pretreated seed latex to an agglomerating agent
WO2010019180A1 (fr) * 2008-05-06 2010-02-18 Mallard Creek Polymers, Inc. Latex anionique utilisé comme véhicule d'ingrédients actifs et procédés de fabrication et d'utilisation de ce dernier
KR20150016093A (ko) * 2013-08-02 2015-02-11 주식회사 엘지화학 고무강화 열가소성 수지의 제조방법

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