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WO2015030415A1 - Résine abs transparente et composition de résine abs transparente - Google Patents

Résine abs transparente et composition de résine abs transparente Download PDF

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Publication number
WO2015030415A1
WO2015030415A1 PCT/KR2014/007745 KR2014007745W WO2015030415A1 WO 2015030415 A1 WO2015030415 A1 WO 2015030415A1 KR 2014007745 W KR2014007745 W KR 2014007745W WO 2015030415 A1 WO2015030415 A1 WO 2015030415A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
abs resin
transparent abs
parts
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2014/007745
Other languages
English (en)
Korean (ko)
Inventor
장석구
박상후
이루다
이원석
최정수
유근훈
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR20140106707A external-priority patent/KR20150026838A/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to US14/771,187 priority Critical patent/US9637583B2/en
Priority to CN201480013412.7A priority patent/CN105008406B/zh
Publication of WO2015030415A1 publication Critical patent/WO2015030415A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers

Definitions

  • the present invention relates to a transparent ABS resin and a transparent ABS resin composition, specifically, to minimize the penetration of the styrene monomer to the polybutadiene-based rubber latex, instead of inducing styrene monomer into the shell transparency through the formation of an effective graft shell And further it relates to a transparent ABS resin and a transparent ABS resin composition excellent in impact resistance.
  • ABS acrylonitrile-butadiene-styrene
  • the transparent resin which makes a methacrylate-styrene-acrylonitrile graft copolymerized with conjugated diene rubber and makes it transparent is produced.
  • the transparent resin using conjugated diene rubber has a limit of its transparency, and the rubber content is excellent at very low rubber content of 5% or less, but when it exceeds 5%, the transparency is worsened than PC or impact-resistant PMMA. It has a high Haze value.
  • the redox system is mainly used to obtain high conversion at low reaction temperature during polymerization.
  • the redox system is a method of adding Fe2 + as a colloidal dispersion, a method of adding reducing sugars (fructose, etc.), sodium formaldehyde. Three methods of using sulfoxylate (SFS) are representative.
  • Dual sodium formaldehyde sulfoxylate is mainly used because it can reduce the amount of iron ions relatively compared to other systems.
  • the present invention overcomes the problems of the prior art as described above to minimize the penetration of styrene-based monomers into the polybutadiene-based rubber latex and instead guide the styrene-based monomers into the shell to form an effective graft shell, thereby providing transparency and impact resistance. It is an object to provide this excellent transparent ABS resin and transparent ABS resin composition.
  • Methyl methacrylate monomer 50 to 40% by weight of the total amount of the styrene monomer and acrylonitrile monomer; and the permeation amount of the styrene monomer to the polybutadiene rubber latex is characterized in that less than 0.005. .
  • a second step of polymerizing to prepare a transparent ABS resin Characterized in that it comprises a.
  • the transparent ABS resin composition of this invention is transparent ABS resin; And SAN or MSAN resin; comprising, the transparent ABS resin,
  • thermoplastic transparent resin of the present invention is a thermoplastic resin obtained by extruding and injecting the transparent ABS resin composition described above, and has a total transmittance of 90.5 or more measured using ASTM D1003 at room temperature based on a 3 mm sheet. And Haze value of 2.0 or less, and Izod impact strength measured using ASTM D256 (1/4 ") is characterized in that 15 or more.
  • the transparent ABS resin according to the present invention will be described in detail with respect to the transparent ABS resin composition and the thermoplastic transparent resin including the same.
  • the present invention 50 to 60% by weight of polybutadiene-based rubber latex; And a total amount of methyl methacrylate monomer, a styrene monomer and a total amount of the acrylonitrile monomer in a total amount of 50 to 40 wt%, wherein the amount of penetration of the styrene monomer into the polybutadiene rubber latex is 0.005 or less.
  • the term "penetration amount of styrene monomer to polybutadiene-based rubber latex” refers to a methyl methacrylate monomer, a styrene monomer and an acrylonitrile-based monomer in a polybutadiene rubber latex.
  • the graft refers to the difference in refractive index between the polybutadiene-based rubber latex and the graft copolymer.
  • the refractive index of the graft copolymer can be calculated by the following equation:
  • WtA is the weight percent of the vinyl cyan compound
  • RIA is the refractive index of the vinyl cyan polymer
  • WtS is the weight percent of the aromatic vinyl compound
  • RIS is the refractive index of the aromatic vinyl compound
  • WtM is an alkyl methacrylate or alkyl acrylate.
  • RIM represents the refractive index of the methacrylic acid alkyl ester compound or the acrylic acid alkyl ester compound.
  • the transparent ABS resin of the present invention may have a penetration amount of the styrene monomer into the polybutadiene rubber latex 0.005 or less, or 0 to 0.005.
  • the polybutadiene-based rubber latex may have a gel content of 85 to 94%, or 86 to 87%.
  • the polybutadiene-based rubber latex may have an average particle diameter of 2500 to 4000 mm 3, or 2900 to 3300 mm 3.
  • methyl methacrylate monomer examples include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid propyl ester, (meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid decyl ester, and ( It may be in the range of 27 to 36% by weight, as one or more monomers selected from meth) acrylic acid lauryl ester.
  • the styrene-based monomer may be, for example, in the range of 10 to 13% by weight as one or more monomers selected from styrene, ⁇ -methylstyrene, p-methylstyrene, and vinyl toluene.
  • the acrylonitrile-based monomer may be, for example, in the range of 2 to 6% by weight as one or more monomers selected from acrylonitrile, methacrylonitrile, and ethacrylonitrile.
  • Method for producing a transparent ABS resin of the present invention for example, the first step of preparing a polybutadiene-based rubber latex having a gel content of 85 to 94% by dividing the butadiene-based monomer;
  • a second step of polymerizing to prepare a transparent ABS resin may be configured to include.
  • the butadiene-based monomer may be to be continuously divided into 60 to 80% of the polymerization conversion rate of the first step.
  • the butadiene-based monomer 10 to 20, or 10 to 15 parts by weight of butadiene 10 to 60 minutes, or 15 to 25 minutes at the polymerization conversion rate of 50 to 60%, or 55 to 60% of the first step Continuous injection, and then heated to 40 °C to 55 °C 40 to 60 parts by weight of butadiene, or 50 to 55 parts by weight may be continuously added for 7 to 9 hours to reach a polymerization conversion of 80%.
  • the polybutadiene-based rubber latex may be, for example, polybutadiene rubber latex, styrene-butadiene copolymer rubber latex, butadiene-acrylonitrile copolymer rubber latex, ethylene-propylene copolymer rubber latex or rubber latex derived therefrom.
  • the polymerization conversion rate is raised to 70 to 80 °C, or 70 to 75 °C at 80% point, the final polymerization conversion may be 95 to 99%, or 97 to 98%.
  • divinylbenzene ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, aryl methacrylate and 1,3-butylene glycol diacrylate
  • One or more crosslinking agents selected from polyethylene glycol (meth) acrylate, polyethylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate are used in the first step.
  • Butadiene monomer may be included in the range of 0.1 to 5 parts by weight, 0.1 to 5 parts by weight, or 0.1 to 1 parts by weight based on a total of 100 parts by weight.
  • the reactive emulsifiers include, for example, sodium dodecyl allylsulfosuccinate (TREM LF-40), C16-C18 alkenyl succinate dipotassium salt (Latemul ASK series), sodium acrylamide stearate (NaAAS) and sodium 3-sulfo
  • TEM LF-40 sodium dodecyl allylsulfosuccinate
  • Latemul ASK series C16-C18 alkenyl succinate dipotassium salt
  • NaAAS sodium acrylamide stearate
  • M14 propyl tetradodecyl maleate
  • M14 propyl tetradodecyl maleate
  • the emulsifier maintains latex stability, which is an inherent characteristic of latex, while also reinforcing thermal stability and reinforcing color of the resin.
  • the oil-soluble polymerization initiator may be, for example, diisopropylbenzene hydroperoxide, t-hexyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, dicumyl peroxide, t-butyl cumyl peroxide, Methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, 1,1-di (t-butyl Peroxy) cyclohexane, 1,1-di (t-butyl peroxy) 3,3,5-trimethylcyclohexane, t-butyl peroxybenzoate, t-butyl peroxy 2-ethyl hexanoate, and bis One or more selected from (4-t-butylcyclohex
  • the oil-soluble polymerization initiator may be used in combination with one or more activators selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, and sodium sulfite.
  • the anionic adsorptive emulsifier is an anionic adsorptive emulsifier selected from at least one selected from potassium rosin, potassium fatty acid, sodium lauryl sulfonate and sodium alkylbenzene sulfonate, molecular weight modifiers such as tertiary dodecyl mercaptan, Reducing agents such as sodium formaldehyde sulfoxylate can be added in the content ranges commonly used in the art.
  • the first step may have a total reaction time of 18 to 20 hours, or 18 to 19 hours.
  • the swelling index of the polybutadiene-based rubber latex may be 10 to 20, 10 to 18, 14 to 20, or 16 to 18, the monomer absorption within the above range is reduced and occlusion during grafting ), And as a result, the penetration of styrene monomer into polybutadiene-based rubber latex can be reduced.
  • the prepared transparent ABS resin may be recovered in powder form by a process of coagulation, dehydration and drying as a latex form.
  • the flocculant salts such as calcium chloride, magnesium sulfate, aluminum sulfate, and acidic substances such as sulfuric acid, nitric acid, hydrochloric acid, and mixtures may be used.
  • the transparent ABS resin composition of the present invention is a transparent ABS resin; And SAN or MSAN resin, wherein the transparent ABS resin comprises: 50 to 60 wt% of a polybutadiene-based rubber latex; And a total amount of the methyl methacrylate monomer, the styrene monomer and the acrylonitrile monomer in a total amount of 50 to 40 wt%; and the penetration amount of the styrene monomer into the polybutadiene rubber latex may be 0.005 or less. .
  • the transparent ABS resin may be 5 to 25%, or 10 to 20% of the composition.
  • the SAN or MSAN resin is, for example, from 0 to 75 parts by weight of the (meth) acrylic acid alkyl ester monomer, 10 to 50 parts by weight of the styrene monomer, and 10 to 20 parts by weight of the acrylonitrile monomer, bulk polymerization, solution polymerization or suspension. It may be a polymerized resin.
  • the composition may be prepared by adding additives selected from a lubricant, an antioxidant, an antistatic agent, a mold release agent and an ultraviolet stabilizer according to the use.
  • the dual lubricant may be selected from, for example, ethylene bis stearamide, polyethylene oxide wax, metal stearate, and various silicone oils, and the amount thereof may be used in an amount of 0 to 5 parts by weight, more preferably 0.1 to about 100 parts by weight of the thermoplastic resin composition. It is in the range of 2 parts by weight.
  • the transparent ABS resin composition may be kneaded to finally prepare a thermoplastic transparent resin.
  • the composition is uniformly dispersed using a single screw extruder, twin screw extruder or Banbury mixer or the like.
  • the water bath is then passed through and cut to obtain a transparent resin in pellet form.
  • thermoplastic transparent resin of the present invention is a thermoplastic resin obtained by extruding and injecting the above-mentioned transparent ABS resin composition, which has a total transmittance of 90.5 or more measured using ASTM D1003 at room temperature based on a 3 mm sheet, Haze value 2.0 or less, and the Izod impact strength measured using ASTM D256 (1/4 ") may be 15 or more.
  • the transparent ABS resin and the transparent ABS resin excellent in transparency and further impact resistance through formation of an effective graft shell by minimizing the penetration of styrene monomer into the polybutadiene rubber latex and inducing the styrene monomer into the shell instead.
  • a composition can be provided.
  • an emulsion consisting of 4 parts by weight of ion-exchanged water, 0.5 parts by weight of potassium rosinate and 0.3 parts by weight of tertiary butyl hydroperoxide was added over 6 hours at the same time as the start of continuous butadiene injection. Subsequently, 0.0003 parts by weight of ferrous sulfide, 0.05 parts by weight of dextrose, 0.04 parts by weight of sodium pyrrole phosphate, and 0.3 parts by weight of tertiary butyl hydroperoxide were further administered to sustain the reaction for 4 hours and terminate the reaction.
  • ion-exchanged water 50 parts by weight of ion-exchanged water was added to a nitrogen-substituted polymerization reactor (autoclave), followed by stirring by adding 0.8 parts by weight of fatty acid potassium, 1.0 parts by weight of potassium rosinate, and 1.0 parts by weight of potassium carbonate at room temperature, followed by stirring.
  • reaction polymerization conversion reached 60%
  • 15 parts by weight of 1,3-butadiene was additionally added over 20 minutes, and the reaction temperature was raised to 55 ° C.
  • 45 parts by weight of 1,3-butadiene was continuously added over 8 hours, and the reaction temperature was raised to 75 ° C. at a reaction conversion rate of 80%.
  • an emulsion consisting of 4 parts by weight of ion-exchanged water, 0.5 part by weight of potassium rosinate and 0.3 part by weight of tertiary butyl hydroperoxide was added over 6 hours at the same time as the start of continuous butadiene injection.
  • the rubbery polymer latex of Preparation Examples 1 to 3 was coagulated using dilute acid or metal salt, washed, dried in a vacuum oven at 60 ° C. for 24 hours, and finely chopped the obtained rubber mass with scissors and then 1 g of rubber. Sections were put in 100 g of toluene, stored in a dark room at room temperature for 48 hours, separated into sol and gel, and the gel content and swelling index were measured according to the following equations.
  • Swelling index weight of swollen gel / weight of gel
  • Example 1 60 parts by weight of polybutadiene-based rubber latex of Preparation Example 1 was prepared in the same manner as in Example 1 except that 27 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.
  • Example 2 50 parts by weight of polybutadiene-based rubber latex of Preparation Example 2 was prepared in the same manner as in Example 1 except that 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.
  • Example 3 50 parts by weight of polybutadiene-based rubber latex of Preparation Example 3 was prepared in the same manner as in Example 1 except that 34 parts by weight of methyl methacrylate, 13 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.
  • Example 3 60 parts by weight of polybutadiene-based rubber latex of Preparation Example 3 was prepared in the same manner as in Example 1 except that 27 parts by weight of methyl methacrylate, 10 parts by weight of styrene, and 3 parts by weight of acrylonitrile were used.
  • the transparent ABS resin latex obtained in Examples 1-4 and Comparative Examples 1-3 was prepared as a powder through agglomeration and drying process, and mixed with MSAN (XT500, manufactured by LG Chem) so that the rubber content was 15%.
  • MSAN XT500, manufactured by LG Chem
  • Notched Izod Impact Strength Impact strength was measured using 1/4 "specimens using ASTM D256.

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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 concerne une résine ABS transparente et une composition de résine ABS transparente. Selon la présente invention, il est possible de réaliser une résine ABS transparente et une composition de résine ABS transparente ayant une excellente transparence et de plus une excellente résistance au choc, grâce à la formation d'une coque greffée efficace par minimisation de la quantité de monomères à base de styrène s'infiltrant dans un latex de caoutchouc à base de polybutadiène, et à la place par introduction du monomère à base de styrène dans la coque. En particulier, selon la présente invention, il est possible de fournir une composition de résine ABS transparente ayant une grande transparence et une grande résistance au choc, tout en appliquant à une résine ABS un agent réducteur et des ions fer, qui ont un effet d'abaissement de la transparence de la résine ABS dans la technique classique.
PCT/KR2014/007745 2013-08-29 2014-08-21 Résine abs transparente et composition de résine abs transparente Ceased WO2015030415A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/771,187 US9637583B2 (en) 2013-08-29 2014-08-21 Transparent ABS resin and transparent ABS resin composition
CN201480013412.7A CN105008406B (zh) 2013-08-29 2014-08-21 透明abs树脂和透明abs树脂组合物

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2013-0102811 2013-08-29
KR20130102811 2013-08-29
KR20140106707A KR20150026838A (ko) 2013-08-29 2014-08-18 투명 ａｂｓ 수지 및 투명 ａｂｓ 수지 조성물
KR10-2014-0106707 2014-08-18

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WO2015030415A1 true WO2015030415A1 (fr) 2015-03-05

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190059037A (ko) 2017-11-22 2019-05-30 주식회사 엘지화학 그라프트 공중합체 분말의 제조방법
CN112876623A (zh) * 2021-01-18 2021-06-01 万华化学(四川)有限公司 一种abs接枝胶乳的制备方法及制备的abs树脂
CN112940204A (zh) * 2021-02-04 2021-06-11 万华化学(四川)有限公司 一种用于附聚的聚丁二烯胶乳的制备方法及制备的abs树脂
CN113024728A (zh) * 2021-03-10 2021-06-25 万华化学(四川)有限公司 一种聚丁二烯胶乳及其制备方法，一种abs树脂
CN116063805A (zh) * 2023-02-15 2023-05-05 万华化学集团股份有限公司 一种具有石榴结构的高流动透明abs树脂及其制备方法

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KR20070064925A (ko) * 2005-12-19 2007-06-22 주식회사 엘지화학 고경도 열가소성 투명 ａｂｓ 수지 조성물
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KR20120040771A (ko) * 2010-10-20 2012-04-30 제일모직주식회사 저온 백화가 발생하지 않는 고투명, 고충격 열가소성 수지 조성물

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KR20030009856A (ko) * 2001-07-24 2003-02-05 주식회사 엘지화학 내충격성이 우수한 아크릴로니트릴-부타디엔-스티렌열가소성 수지의 제조방법
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KR20070064925A (ko) * 2005-12-19 2007-06-22 주식회사 엘지화학 고경도 열가소성 투명 ａｂｓ 수지 조성물
KR20120004261A (ko) * 2010-07-06 2012-01-12 주식회사 엘지화학 고무질 중합체의 제조방법 및 이를 이용한 고무 강화 열가소성 수지 조성물
KR20120040771A (ko) * 2010-10-20 2012-04-30 제일모직주식회사 저온 백화가 발생하지 않는 고투명, 고충격 열가소성 수지 조성물

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190059037A (ko) 2017-11-22 2019-05-30 주식회사 엘지화학 그라프트 공중합체 분말의 제조방법
WO2019103369A2 (fr) 2017-11-22 2019-05-31 주식회사 엘지화학 Procédé de fabrication de poudre de copolymère greffé
CN110382571A (zh) * 2017-11-22 2019-10-25 株式会社Lg化学 接枝共聚物粉末的制备方法
US11421103B2 (en) 2017-11-22 2022-08-23 Lg Chem, Ltd Method for preparing graft copolymer powder
CN112876623A (zh) * 2021-01-18 2021-06-01 万华化学(四川)有限公司 一种abs接枝胶乳的制备方法及制备的abs树脂
CN112876623B (zh) * 2021-01-18 2023-04-07 万华化学(四川)有限公司 一种abs接枝胶乳的制备方法及制备的abs树脂
CN112940204A (zh) * 2021-02-04 2021-06-11 万华化学(四川)有限公司 一种用于附聚的聚丁二烯胶乳的制备方法及制备的abs树脂
CN112940204B (zh) * 2021-02-04 2023-04-07 万华化学(四川)有限公司 一种用于附聚的聚丁二烯胶乳的制备方法及制备的abs树脂
CN113024728A (zh) * 2021-03-10 2021-06-25 万华化学(四川)有限公司 一种聚丁二烯胶乳及其制备方法，一种abs树脂
CN116063805A (zh) * 2023-02-15 2023-05-05 万华化学集团股份有限公司 一种具有石榴结构的高流动透明abs树脂及其制备方法

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