WO2015046729A1 - Procédé de préparation de copolymère greffé renforcé par du caoutchouc et copolymère greffé renforcé par du caoutchouc ainsi préparé - Google Patents

Procédé de préparation de copolymère greffé renforcé par du caoutchouc et copolymère greffé renforcé par du caoutchouc ainsi préparé Download PDF

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Publication number
WO2015046729A1
WO2015046729A1 PCT/KR2014/006615 KR2014006615W WO2015046729A1 WO 2015046729 A1 WO2015046729 A1 WO 2015046729A1 KR 2014006615 W KR2014006615 W KR 2014006615W WO 2015046729 A1 WO2015046729 A1 WO 2015046729A1
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Prior art keywords
rubber
polymerization
weight
reinforced graft
graft copolymer
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PCT/KR2014/006615
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English (en)
Korean (ko)
Inventor
정유성
채주병
박은선
전태영
이진호
김영민
Original Assignee
(주) 엘지화학
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Priority claimed from KR1020140039949A external-priority patent/KR101633173B1/ko
Application filed by (주) 엘지화학 filed Critical (주) 엘지화학
Priority to US14/774,693 priority Critical patent/US9663606B2/en
Priority to CN201480013776.5A priority patent/CN105189587B/zh
Publication of WO2015046729A1 publication Critical patent/WO2015046729A1/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
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • 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
    • C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
    • C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

  • the present disclosure relates to a method for preparing a rubber-reinforced graft copolymer and a rubber-reinforced graft copolymer prepared therefrom, and more particularly, to a method for preparing a rubber-reinforced graft copolymer including alpha-methylstyrene, It relates to a rubber reinforced graft copolymer prepared by introducing a rubber latex and improved polymerization productivity and heat resistance characteristics, and rubber reinforced graft copolymer prepared therefrom.
  • the present invention also relates to a thermoplastic resin composition having excellent heat resistance including the rubber-reinforced graft copolymer and the heat-resistant styrene-acrylonitrile copolymer.
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resin acrylonitrile-butadiene-styrene copolymer
  • ABS resins that can satisfy these high thermal properties are usually produced by emulsion polymerization or solution polymerization, and has a high glass transition temperature (Tg) -Methylstyrene-acrylonitrile copolymer (AMSAN) is prepared by melt mixing a rubber-reinforced graft copolymer (acrylonitrile-butadiene-styrene copolymer) prepared by emulsion polymerization within a range having a predetermined rubber content. do.
  • Tg glass transition temperature
  • AMSAN Metal-reinforced graft copolymer
  • alpha-methylstyrene having a higher glass transition temperature may be used in place of styrene when preparing the rubber-reinforced graft copolymer to improve heat resistance.
  • alpha-methylstyrene when alpha-methylstyrene is used, alpha-methyl styrene is used in the emulsion polymerization step. Due to the low reactivity and the lowering of the polymerization stability, the polymerization rate is greatly lowered and the amount of coagulated product is increased, resulting in a problem of lowering productivity and heat resistance.
  • the present invention provides a rubber latex having an average particle diameter of 0.09 to 0.13 ⁇ m and a gel content of 85 to 99 wt% when preparing a rubber-reinforced graft copolymer including alpha-methylstyrene. It is an object of the present invention to provide a method for producing a rubber-reinforced graft copolymer and a rubber-reinforced graft copolymer prepared therefrom, in which not only polymerization productivity but also heat resistance are improved.
  • the present substrate is i) 40-50% by weight rubber latex having an average particle diameter of 0.25 to 0.45 ⁇ m and gel content of 80 to 95% by weight; ii) 10 to 20% by weight rubber latex having an average particle diameter of 0.09 to 0.13 mu m and a gel content of 85 to 99% by weight; iii) 20 to 35 weight percent of alpha-methylstyrene; And iv) 5 to 20% by weight of vinyl cyan monomer; emulsion polymerization using a polymerization water, an emulsifier, a molecular weight regulator, an initiator and an activator, wherein the rubber latex of i) and ii) is added to the entire polymerization initiation;
  • the vinyl cyan monomer of iv) provides a method for preparing a rubber-reinforced graft copolymer, characterized in that it is not added before the start of polymerization or a part is added and then the remainder is added after the start of poly
  • the present disclosure provides a rubber-reinforced graft copolymer, characterized in that it is prepared according to the method for producing the rubber-reinforced graft copolymer.
  • the present invention is a) i) 40-50% by weight rubber latex having an average particle diameter of 0.25 to 0.45 ⁇ m, gel content of 80 to 95% by weight, ii) 0.09 to 0.13 ⁇ m average particle diameter and 85 to 99 gel content 10% to 20% by weight of rubber latex, iii) 20 to 35% by weight of alpha-methylstyrene, and iv) 5 to 20% by weight of vinyl cyan monomer, and a polymerization water, an emulsifier, a molecular weight regulator, a fat-soluble initiator and an activator.
  • the whole amount is added, and the vinyl cyan monomer of iv) provides a method for producing a thermoplastic resin composition, wherein the remaining amount is added after the start of the polymerization after the start of the polymerization or a part of the vinyl cyan monomer is added.
  • thermoplastic resin composition comprising the rubber-reinforced graft copolymer and a heat resistant styrene-acrylonitrile copolymer.
  • a method for preparing a rubber-reinforced graft copolymer including alpha-methylstyrene that can improve not only polymerization productivity but also heat resistance, and a rubber-reinforced graft copolymer prepared therefrom. It works.
  • thermoplastic resin composition having excellent heat resistance comprising the rubber-reinforced graft copolymer and the heat-resistant styrene-acrylonitrile-based copolymer.
  • the method for producing a rubber-reinforced graft copolymer of the present disclosure includes: i) 40-50 wt% of rubber latex having an average particle diameter of 0.25-0.45 ⁇ m and a gel content of 80-95 wt%; ii) 10 to 20% by weight rubber latex having an average particle diameter of 0.09 to 0.13 mu m and a gel content of 85 to 99% by weight; iii) 20 to 35 weight percent of alpha-methylstyrene; And iv) 5 to 20% by weight of vinyl cyan monomer; emulsion polymerization using a polymerization water, an emulsifier, a molecular weight regulator, an initiator and an activator, wherein the rubber latex of i) and ii) is added to the entire polymerization initiation; The vinyl cyan monomer of iv) is not added before the start of polymerization or after a part is added, and then the remainder is added after the start of polymerization.
  • the rubber latex of i) is less than 40% by weight, there is a decrease in impact resistance, and when the rubber latex is more than 50% by weight, there is a problem in that polymerization rate and stability are lowered.
  • the gel content of the rubber latex of i) is less than 80% by weight, the appearance characteristics are poor, and when it exceeds 95% by weight, the impact resistance is poor.
  • the gel content of the rubber latex of ii) is less than 85% by weight has a poor effect on the appearance properties, when it exceeds 99% by weight has a poor impact resistance.
  • the initiator of iv) is, for example, a fat-soluble redox initiator, in which case there is an advantageous effect in terms of polymerization rate.
  • the rubber latex of i) may have an average particle diameter of 0.25 to 0.35 ⁇ m, or 0.3 to 0.4 ⁇ m, and has excellent impact resistance within this range.
  • the rubber latex of i) and ii) may be, for example, a conjugated diene-based rubber latex, in which case the impact strength is excellent.
  • the conjugated diene rubber latex is, for example, a rubber latex prepared from one or more conjugated diene monomers selected from the group consisting of 1,3-butadiene, isoprene, chloroprene and pyerylene, and preferably 1,3-butadiene Rubber latex, in this case the impact strength is excellent.
  • the alpha-methylstyrene of iii) may not be added before the start of polymerization or after a part is added, and then the remaining amount may be added after the start of polymerization. In this case, polymerization stability is excellent.
  • the alpha-methylstyrene of iii) may be added in an amount of 10 to 50% by weight, or 30 to 40% by weight before the start of polymerization, and the remaining amount after the start of polymerization, based on the total amount of alpha-methylstyrene used for polymerization. In this range, the polymerization stability is excellent.
  • the vinyl cyan monomer of iv) is, for example, 10 to 15% by weight, and has an excellent effect on heat resistance within this range.
  • the vinyl cyan monomer of iv) may be added in an amount of 0 to 50% by weight, or 30 to 50% by weight before the start of polymerization, and the remaining amount after the start of polymerization, based on the total amount of vinyl cyan monomer used for polymerization. Within the range, there is an excellent effect of excellent heat resistance characteristics.
  • the vinyl cyan monomer of iv) may be, for example, acrylonitrile, methacrylonitrile, or a mixture thereof, preferably acrylonitrile, in which case there is an advantageous effect on the reaction rate and heat resistance characteristics.
  • the polymerization water, the emulsifier, the initiator and the activator may be dividedly injected before and after the start of polymerization, for example, in this case, the polymerization speed is high and the polymerization stability is excellent.
  • the molecular weight regulator may be added after the start of polymerization as an example, in this case there is an excellent molecular weight control effect.
  • molecular weight regulator it is a mercaptan type molecular weight regulator, for example, In this case, it is effective in molecular weight adjustment.
  • the initiator and the activator may be added after the addition of all monomers is completed, in which case there is an advantageous effect in terms of polymerization rate.
  • the emulsifier may be at least one selected from the group consisting of, for example, an anionic adsorptive emulsifier, a nonionic emulsifier, a reactive emulsifier and a polymer reactive emulsifier, in which case the polymerization stability and latex storage stability are excellent.
  • the anionic adsorption-type emulsifier is, for example, potassium rosin acid, fatty acid potassium, sodium lauryl sulfonate, sodium alkyl benzene sulfonate, and the like. In this case, polymerization stability and latex storage stability are excellent.
  • the fat-soluble redox initiator is, for example, a redox-based polymerization initiator comprising a peroxide as a component, in which case there is an advantageous effect in terms of the polymerization rate.
  • the peroxide may be at least one selected from the group consisting of hydrogen peroxide, cumene hydroperoxide, diisopropyl benzene hydroperoxide, tertiary butyl hydroperoxide, and paramethane hydroperoxide, in this case, It has a beneficial effect.
  • the polymerization water or the like is not particularly limited when the amount (parts by weight) that can be conventionally used in the production of rubber-reinforced graft copolymers.
  • the emulsion polymerization has an polymerization conversion of 97% or more, and has excellent heat resistance within this range.
  • the amount of coagulum produced is less than 0.1 wt% with respect to the total solid content, the balance of physical properties is excellent within this range, and the heat resistance is excellent.
  • the method of preparing the rubber-reinforced graft copolymer is, for example, at least one selected from the group consisting of sulfuric acid, MgSO 4 , CaCl 2 and Al 2 (SO 4 ) 3 in the rubber-reinforced graft copolymer latex prepared by the emulsion polymerization. After the coagulant is added and coagulated, the aggregate may be washed, dehydrated if necessary, and dried to prepare a powder.
  • a method of preparing the rubber-reinforced graft copolymer may include a) a rubber latex having an average particle diameter of 0.25 to 0.35 ⁇ m, a gel content of 80 to 95 wt%, an average particle diameter of 0.09 to 0.13 ⁇ m, and a gel content of 85 to Administering 99% by weight of rubber latex, alpha-methylstyrene, vinyl cyan monomer, emulsifier, deionized water, and molecular weight adjusting agent to the reactor, and then initiating polymerization by administering a fat-soluble redox initiator and an activator in a batch; b) reacting the monomer emulsion comprising a residual amount of alpha-methylstyrene, a residual amount of vinyl cyan monomer, an emulsifier, a molecular weight regulator, and deionized water, a fat-soluble redox initiator and an activator after the polymerization in step a) step; And c
  • the method of manufacturing the rubber-reinforced graft copolymer is a) 40-50 parts by weight of rubber latex having an average particle diameter of 0.25 to 0.45 ⁇ m, gel content of 80 to 95 wt%, and average particle diameter of 0.09 to 0.13 ⁇ m.
  • the rubber-reinforced graft copolymer of the present disclosure is characterized in that it is prepared according to the preparation method of the rubber-reinforced graft copolymer.
  • the method for preparing the thermoplastic resin composition of the present invention includes a) i) 40-50 wt% of rubber latex having an average particle diameter of 0.25-0.45 ⁇ m and a gel content of 80-95 wt%, ii) a gel having an average particle size of 0.09-0.13 ⁇ m 10 to 20% by weight of rubber latex containing 85 to 99% by weight, iii) 20 to 35% by weight of alpha-methylstyrene, and iv) 5 to 20% by weight of vinyl cyan monomer, polymerized water, emulsifier, molecular weight regulator, initiator And emulsion polymerization using an activator; And b) blending the rubber-reinforced graft copolymer prepared by the emulsion polymerization with a heat-resistant styrene-acrylonitrile-based copolymer; wherein the rubber latex of steps i) and ii) is polymerized. The whole amount is added, and the vinyl
  • the initiator of iv) is, for example, a fat-soluble redox initiator, and in this case, there is an advantageous effect in terms of polymerization rate.
  • thermoplastic resin composition of the present disclosure is characterized in that it is prepared according to the method for producing the thermoplastic resin composition.
  • thermoplastic resin composition may have a total rubber content of 10 to 20% by weight, or 15 to 20% by weight, and have an excellent balance of physical properties and excellent heat resistance within these ranges.
  • thermoplastic resin composition of the present invention is characterized in that it comprises 20 to 50 parts by weight of the rubber-reinforced graft copolymer and 80 to 50 parts by weight of the heat-resistant styrene-acrylonitrile copolymer.
  • the heat-resistant styrene-acrylonitrile-based copolymer may be a polymerized copolymer including, for example, 70 to 85% by weight of alpha-methylstyrene, 13 to 29% by weight of acrylonitrile, and 1 to 2% by weight of styrene. In this case, the physical property balance is excellent and heat resistance is excellent.
  • the heat-resistant styrene-acrylonitrile-based copolymer may be a polymerized copolymer including 60 to 80% by weight of alpha-methylstyrene, 15 to 35% by weight of acrylonitrile and 0.1 to 5% by weight of styrene. In this case, there is an excellent balance of physical properties and excellent heat resistance.
  • Rubber latex A having an average particle diameter of 0.32 ⁇ m and a gel content of 85 wt% (based on solids), a rubber latex having an average particle diameter of 0.12 ⁇ m and a gel content of 95 wt% (based on a solids)
  • Rubber latex B 15 parts by weight, 120 parts by weight of deionized water, 0.6 parts by weight of alkenyl potassium succinate emulsifier, and maintained the temperature in the reactor at 50 °C, 10 parts by weight of alpha-methylstyrene, 5 parts by weight of acrylonitrile , 0.087 parts by weight of sodium pyrophosphate, 0.11 parts by weight of dextrose, 0.002 parts by weight of ferrous sulfide, and 0.2 parts by weight of cumyl peroxide, and then the reaction temperature was raised to 70 ° C. for 60 minutes.
  • Monomer emulsion and sodium pyrophosphate 0.019 consisting of 10 parts by weight of ion-exchanged water, 20 parts by weight of alpha-methylstyrene, 5 parts by weight of acrylonitrile, 0.6 parts by weight of alkenyl potassium succinate emulsifier, and 0.1 parts by weight of tertiary dodecylmercaptan.
  • 0.025 part by weight of dextrose, 0.001 part by weight of ferrous sulfide and 0.1 part by weight of cumyl peroxide were continuously administered for 120 minutes.
  • thermoplastic resin composition ⁇ Production of the thermoplastic resin composition>
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 40 parts by weight of latex A and 20 parts by weight of latex B were used in Example 1.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 7 parts by weight of acrylonitrile was used.
  • Example 1 except that 6.5 parts by weight of alpha-methylstyrene and 3.5 parts by weight of acrylonitrile were used in the polymerization initiation step, and 19.5 parts by weight of alpha-methylstyrene and 10.5 parts by weight of acrylonitrile were used in the polymerization step.
  • the rubber-reinforced graft copolymer latex and thermoplastic resin composition was prepared.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 60 parts by weight of latex A was used without using latex B in the polymerization initiation step of Example 1.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 8 parts by weight of acrylonitrile was used.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that 35 parts by weight of latex A and 25 parts by weight of latex B were used in the polymerization initiation step of Example 1.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 95 wt% and an average particle diameter of 0.05 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 95 wt% and an average particle diameter of 0.20 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex A having a gel content of 85 wt% and an average particle diameter of 0.2 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex A having a gel content of 83 wt% and an average particle diameter of 0.5 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex B having a gel content of 70 wt% and an average particle size of 0.12 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were manufactured in the same manner as in Example 1, except that latex A having a gel content of 70 wt% and an average particle diameter of 0.32 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • a rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1, except that latex B having a gel content of 97 wt% and an average particle size of 0.32 ⁇ m was used in the polymerization initiation step of Example 1. It was.
  • Example 1 In the polymerization initiation step of Example 1, 5 parts by weight of alpha-methylstyrene, 5 parts by weight of styrene, 5 parts by weight of acrylonitrile and 10 parts by weight of alpha-methylstyrene, 10 parts by weight of styrene and acrylonitrile in the polymerization step A rubber-reinforced graft copolymer latex and a thermoplastic resin composition were prepared in the same manner as in Example 1 except that 5 parts by weight was used.
  • Average particle diameter measured using an intensity Gaussian distribution (Nicomp 380) by dynamic laser light scattering method.
  • Gel content The gel content was measured by centrifugation after stirring for 24 hours in acetone.
  • TSC total solid content
  • Proportion of product aggregate weight of aggregate produced in the reactor / weight of total monomers administered * 100
  • Example 1 Example 2
  • Example 3 Example 4 Composition of Rubber Reinforced Graft Copolymer Rubber Latex A 45 40 50 45 Rubber Latex B 15 20 20 15 AMS 30 30 21 26 AN 10 10 9 14 Sum 100 100 100 100 % Polymerization conversion 97.2 97.5 97.2 98.2 Polymerized coagulum (%) 0.05 0.02 0.01 0.04
  • Comparative Example 10 Comparative Example 11 Comparative Example 12 Composition of Rubber Reinforced Graft Copolymer Rubber Latex A Rubber Latex 45 45 45 45 45 45 Gel content 85 85 70 90 85 85 Particle diameter 0.5 0.32 0.32 0.32 0.32 0.32 Rubber Latex B Rubber Latex 15 15 15 15 15 Gel content 95 70 95 95 95 95 95 Particle size ( ⁇ m) 0.12 0.12 0.12 0.12 0.12 0.12 0.12 Monomer AMS 30 30 30 30 10 30 SM 20 AN 10 10 10 10 10 4 Sum 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 % Polymerization conversion 92.1 97.1 96.9 97.1 98.1 88.1 Polymerized coagulum (%) 0.01 0.01 0.03 0.09 0.01 1.29
  • the rubber-reinforced graft copolymers (Examples 1 to 4) of the present substrate were compared with the rubber-reinforced graft copolymers (Comparative Examples 1 to 12) not containing rubber latex B. It was confirmed that the polymerization conversion rate was high and the polymerization coagulation product was largely small.
  • Example 1 Example 2
  • Example 3 Example 4 Impact Strength 1/4 (Kg.cm/cm) 18.8 18.1 18.5 19.0 HDT (°C) 107.5 107.7 104.1 106.9 Polish 100.9 100.9 101.3 101.2
  • thermoplastic resin compositions (Examples 1 to 4) of the present substrate were compared with the thermoplastic resin compositions (Comparative Examples 1 to 12) not containing the rubber-reinforced graft copolymer of the present substrate. It was confirmed that the impact strength, heat resistance and appearance characteristics were all excellent, and in particular, the physical property balance was excellent.

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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)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention porte sur un procédé de préparation d'un copolymère greffé renforcé par du caoutchouc et sur un copolymère greffé renforcé par du caoutchouc préparé par ce dernier et, plus précisément, sur un procédé de préparation d'un copolymère greffé renforcé par du caoutchouc dans lequel i) 40 à 50 % en poids de latex de caoutchouc, ayant une taille moyenne des particules de 0,25 à 0,45 ㎛ et une teneur en gel de 80 à 95 % en poids ; ii) 10 à 20 % en poids de latex de caoutchouc, ayant une taille moyenne des particules de 0,49 à 0,13 ㎛ et une teneur en gel de 85 à 99 % en poids ; iii) 20 à 35 % en poids d'α-méthylstyrène et iv) 5 à 20 % en poids d'un monomère cyanure de vinyle sont polymérisés en émulsion à l'aide d'eau de polymérisation, d'un agent émulsifiant, d'un agent de réglage de la masse moléculaire, d'un initiateur et d'un agent activateur, la quantité totale de latex de caoutchouc de i) et ii) étant introduite avant l'amorce de la polymérisation et le monomère cyanure de vinyle de iv) n'étant pas introduit ou étant seulement partiellement introduit avant l'amorce de la polymérisation, le reste étant introduit après l'amorce de la polymérisation. La présente invention porte également sur un copolymère greffé renforcé par du caoutchouc préparé par le procédé selon l'invention. La présente invention concerne un copolymère greffé renforcé par du caoutchouc à base d'α-méthylstyrène qui permet d'améliorer la résistance à la chaleur, ainsi que la productivité de la polymérisation et un copolymère greffé renforcé par du caoutchouc préparé de cette manière.
PCT/KR2014/006615 2013-09-30 2014-07-21 Procédé de préparation de copolymère greffé renforcé par du caoutchouc et copolymère greffé renforcé par du caoutchouc ainsi préparé WO2015046729A1 (fr)

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US14/774,693 US9663606B2 (en) 2013-09-30 2014-07-21 Method for preparing rubber reinforced graft copolymer and rubber reinforced graft copolymer prepared thereby
CN201480013776.5A CN105189587B (zh) 2013-09-30 2014-07-21 制备橡胶增强的接枝共聚物的方法和由该方法制备的橡胶增强的接枝共聚物

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KR10-2013-0116819 2013-09-30
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KR10-2014-0039949 2014-04-03
KR1020140039949A KR101633173B1 (ko) 2013-09-30 2014-04-03 고무강화 그라프트 공중합체의 제조방법 및 이로부터 제조된 고무강화 그라프트 공중합체

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KR20110071663A (ko) * 2009-12-21 2011-06-29 금호석유화학 주식회사 증착이 용이한 열가소성 수지 및 그의 제조 방법
KR20120021786A (ko) * 2010-08-17 2012-03-09 주식회사 엘지화학 알루미늄 증착성 및 밀착성이 우수한 열가소성 수지 조성물

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