KR100404881B1 - Method for preparing nitrile-based thermoplastic resin - Google Patents
Method for preparing nitrile-based thermoplastic resin Download PDFInfo
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- KR100404881B1 KR100404881B1 KR1019980003333A KR19980003333A KR100404881B1 KR 100404881 B1 KR100404881 B1 KR 100404881B1 KR 1019980003333 A KR1019980003333 A KR 1019980003333A KR 19980003333 A KR19980003333 A KR 19980003333A KR 100404881 B1 KR100404881 B1 KR 100404881B1
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
- C08L9/04—Latex
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
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- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/12—Monomers containing a branched unsaturated aliphatic radical or a ring substituted by an alkyl radical
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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Abstract
본 발명은 열가소성 니트릴 수지의 제조에 있어서 니트릴 단량체의 양과 단량체 간의 비율을 조절하여 중합체 내의 니트릴 단위체 배열 순서를 조절하여 투명도, 탁도, 황변도를 낮추는 니트릴 수지의 제조 방법에 관한 것으로 니트릴 단량체에 대한 다른 공중합 단량체의 비율 및 투입 순서를 반응도에 따라 조절하는 것을 특징으로 한다.The present invention relates to a method for preparing a nitrile resin which reduces transparency, turbidity and yellowing by adjusting the order of nitrile monomers in the polymer by adjusting the amount of nitrile monomer and the ratio between monomers in the preparation of the thermoplastic nitrile resin. It is characterized by adjusting the proportion and the addition order of the copolymerization monomers according to the reactivity.
Description
본 발명은 열 안정성이 우수한 니트릴계 열가소성 수지의 제조 방법 및 그를 위한 조성물에 관한 것이다.The present invention relates to a method for producing a nitrile thermoplastic resin having excellent thermal stability and a composition therefor.
일반적으로 니트릴계 열가소성 수지는 우수한 기체 차단성과 내화학성으로 이용 가능성이 높지만, 가공시 열 안정성이 좋지 않아 그 이용에 제한을 받고 있다. 니트릴계 열가소성 수지의 열 안정성을 나쁘게 하는 주원인은 연속적인 니트릴 단위체가 고온에서 고리형 화합물을 만들어 발색단을 이루기 때문인 것으로 알려져 있다. 니트릴계 단량체는 스티렌과 같은 소수성 단량체 보다 반응 속도 상수가 매우 크기 때문애 중합 반응시 급격히 반응이 진행되어 통제하기 어려운 속도로 진행되어 급격한 발열 현상이 일어나기도 한다. 이러한 니트릴계 단량체의 중합 특성은 니트릴 고무 라텍스를 제조할 때에도 그대로 나타나 부타디엔 고무 또는 스티렌 고무를 제조할 때보다 더 급격한 발열 반응이 진행된다. 특히 부타디엔과 같이 상온에서 기체인 단량체와 니트릴계 단량체를 공중합시키는 경우에, 급격한 발열 반응으로 반응기 내의 압력이 급격히 상승되는 문제점을 일으키기도 한다. 이와 같이 급격한 발열 반응 특성 때문에 니트릴 고무 라텍스 조성물 중 니트릴 고무 라텍스제조 방법에서 일반적으로 고온 제조 과정(Hot Process)이라 함은 50 ℃에서의 제조를 의미하며, 고형분 함량은 30∼40 %이다(USP 3,950,454). 즉, 반응 온도가 50 ℃를 넘거나 40 % 이상의 고형분 함량을 지닌 니트릴 고무 라텍스를 제조하게 되면 반응이 폭발적으로 일어나기 쉬우며, 최종 중합 라텍스의 안정성도 떨어지게 되어 반응기의 벽면에 피막이 형성되고, 응고물도 다량 석출된다. 따라서 40 % 이상의 고형분 함량을 지닌 니트릴 고무 라텍스는 낮은 고형분 함량의 라텍스를 제조한 후 진공 상태에서 수분을 제거함으로써 제조하기도 한다.In general, nitrile-based thermoplastic resins are highly usable due to their excellent gas barrier properties and chemical resistance, but are limited in their use due to poor thermal stability during processing. It is known that the main cause of poor thermal stability of nitrile-based thermoplastic resins is that continuous nitrile units form cyclic compounds at high temperatures to form chromophores. Since nitrile monomers have a much higher reaction rate constant than hydrophobic monomers such as styrene, the reaction proceeds rapidly during the polymerization reaction and proceeds at a rate that is difficult to control, causing rapid exothermic phenomenon. The polymerization characteristics of the nitrile monomers are intact even when the nitrile rubber latex is produced, and the exothermic reaction proceeds more rapidly than when the butadiene rubber or the styrene rubber is prepared. In particular, in the case of copolymerizing a nitrile monomer and a gaseous monomer at room temperature, such as butadiene, a sudden exothermic reaction may cause a problem that the pressure in the reactor is rapidly increased. Due to such rapid exothermic properties, in the nitrile rubber latex composition, the nitrile rubber latex manufacturing method generally means a hot process at 50 ° C., and the solid content is 30 to 40% (USP 3,950,454). ). That is, when the nitrile rubber latex having a reaction temperature exceeding 50 ° C. or having a solid content of 40% or more is prone to explosive reactions, the stability of the final polymerized latex is lowered and a film is formed on the wall of the reactor. Much precipitates. Therefore, nitrile rubber latex having a solid content of 40% or more may be prepared by preparing a low solid content latex and then removing moisture in a vacuum state.
본 발명은 니트릴 고무 라텍스에 니트릴 단랑체와 공중합을 잘 이룰 수 있는 다른 단량체를 그라프트 중합할 때 각 단량체의 투입량과 투입 비율을 조절하이 중합체 내의 단위체 배열 순서를 조절함으로써 니트릴 단량체가 연속적으로 중합되는 것을 억제하여 니트릴 단위체가 고온에서 고리형 화합물을 만드는 것을 억제하여 열 안정성을 항상시키는 것을 목적으로 하고 있다.According to the present invention, when nitrile rubber latex is graft-polymerized with other monomers capable of copolymerizing with nitrile monomers, the nitrile monomers are continuously polymerized by controlling the order of monomers in the polymer by controlling the dosage and the ratio of the monomers. It is aimed at suppressing the nitrile unit from forming a cyclic compound at a high temperature to always maintain thermal stability.
상기 목적을 달성하기 위하여 본 발명에서는 중랑 평균 입자경이 1000∼2500 Å인 니트릴 고무 라텍스 8∼20 중량부에 비닐시안화 화합물 65∼80 중량부, 불포화 카르복실산 에스테르 20∼30 중량부, 방향족 비닐 화합물 0∼5 중량부를 혼합하여 비연속적 투입 방법으로 중합시켜 열가소성 수지를 제조하는 방법 및 그 조성물을 제공한다.In order to achieve the above object, in the present invention, 65 to 80 parts by weight of vinyl cyanide compound, 20 to 30 parts by weight of unsaturated carboxylic acid ester, and aromatic vinyl compound in 8 to 20 parts by weight of nitrile rubber latex having a median average particle diameter of 1000 to 2500 mm 3 Provided are a method for producing a thermoplastic resin by mixing 0 to 5 parts by weight and polymerizing by a discontinuous charging method, and a composition thereof.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명에서는 니트릴 단량체를 그라프트 공중합시킬 때 니트릴 단랑체가 연속적으로 중합되어 고분자가 생성된 후에 니트릴 단위체가 고리형 화합물을 형성하여 발색단을 이루는 것을 방지하는 방법에 관한 것이다. 이를 위하여 니트릴 고무 라텍스에 비닐 시안화 화합물, 불포화 카르복실산 에스테르, 방향족비닐 화합물을 적정 비율로 혼합하여 이를 단계적으로 투입하여 니트릴 고무의 연속적 중합 반응을 억제한다.The present invention relates to a method of preventing nitrile monomers from forming cyclic compounds by forming a cyclic compound after the nitrile monomer is polymerized continuously to produce a polymer when graft copolymerization of the nitrile monomer. To this end, a vinyl cyanide compound, an unsaturated carboxylic acid ester, and an aromatic vinyl compound are mixed in an appropriate ratio in nitrile rubber latex to suppress the continuous polymerization reaction of the nitrile rubber.
구체적으로는 중량 평균 입자경이 1000∼2500 Å인 니트릴 고무 라텍스 8∼20 중랑부에 비닐시안화 화합물 65∼80 중량부, 불포화 카르복실산 에스테르 20∼30 중량부, 방향족 비닐 화합물 0∼5 중량부를 적정 비율로 혼합하여 비연속적인 투입 방법으로 중합을 시켜 열가소성 수지를 제조하는 방법에 관한 것이다.Specifically, 65 to 80 parts by weight of a vinyl cyanide compound, 20 to 30 parts by weight of unsaturated carboxylic acid ester, and 0 to 5 parts by weight of an aromatic vinyl compound are titrated into 8 to 20 cores of nitrile rubber latex having a weight average particle diameter of 1000 to 2500 mm 3. The present invention relates to a method for producing a thermoplastic resin by mixing in a ratio to polymerize by a discontinuous dosing method.
바람직하게는 3단계에 걸쳐서 단량체들을 투입하여 그라프트 공중합체를 제조하는데, 1단계에서는 니트릴 단량체 15∼20 중량부와 불포화 카르복실산에스터 7∼10 중량부를, 2단계에서는 니트릴 단량체 30∼40 중랑부와 불포화 카르복실산에스터 10∼20 중량부를, 3단계에서는 아크릴로니트릴 10∼5 중량부, 불포화 카르복실산에스터 5∼8 중량부, 그리고 방향족 비닐 단량체를 0∼5 중량부를 투입시키는 방법을 채택할 수 있다.Preferably, the graft copolymer is prepared by adding monomers in three stages, in which step 15 to 20 parts by weight of the nitrile monomer and 7 to 10 parts by weight of unsaturated carboxylic acid ester are prepared, and in step 2, 30 to 40 nitrile monomers are filled. Part and 10 to 20 parts by weight of unsaturated carboxylic acid ester, 10 to 5 parts by weight of acrylonitrile, 5 to 8 parts by weight of unsaturated carboxylic acid ester, and 0 to 5 parts by weight of an aromatic vinyl monomer in the third step. Can be adopted.
본 발명에서 사용되는 니트릴 단랑체는 아크릴로니트릴, 메타아크릴로니트릴, 아크릴로니트릴과 메타아크릴로니트릴의 혼합물이다. 또한 본 발명에서 사용되는 불포화 카르복실산에스터는 메틸아크릴레이트, 부틸아크릴레이트, 매틸아크릴레이트와 부틸아크릴레이트의 혼합물이다. 방향족 비닐 화합물을 스티렌, α-메틸스티렌, 스티렌, α-메틸스티렌 또는 이들의 혼합물이다.Nitrile monomers used in the present invention are acrylonitrile, methacrylonitrile, a mixture of acrylonitrile and methacrylonitrile. In addition, the unsaturated carboxylic acid ester used in the present invention is a mixture of methyl acrylate, butyl acrylate, methyl acrylate and butyl acrylate. The aromatic vinyl compound is styrene, α-methylstyrene, styrene, α-methylstyrene or mixtures thereof.
중합 개시제로는 아조 화합물, 퍼옥시드, 히드로퍼옥시드, 알킬퍼옥시드, 퍼옥시디카르보네이트, 퍼옥시에스테르, 디알킬퍼옥시드, 퍼설페이트, 퍼포스페이트와 환원제를 포함한 산화 환원 촉매 및 당해 분야에 공지된 개시제로부터 선택할 수 있으며, 0.01∼5 중랑 %의 양으로 사용하는 것이 바람직하다.Polymerization initiators include redox catalysts including azo compounds, peroxides, hydroperoxides, alkylperoxides, peroxydicarbonates, peroxyesters, dialkylperoxides, persulfates, perphosphates and reducing agents and are known in the art. It can select from the said initiator, and it is preferable to use in the quantity of 0.01-5 weight%.
중합 억제제는 니트릴 단랑체의 연속 단위체 생성을 억제하여 백색도 감소를 방지하고 열 안정성 및 광안정성의 저하를 방지하는 역할을 하며, para-tert-부틸카테콜, α-니트로소-β-나프톨, 디-tert-아밀하이드로퀴논, 디니트로벤젠티올, 디니트로페닐벤조차아디설파이드, 소듐하이드로설파이드, 테트라메틸티우람디설파이드, 태트라메틸티우라이드설파이드, 소디움디메틸디와바메이트칼륨, 디메틸디티오카바메이트 등의 디알킬티오카바메이트 금속염, 페닐히드라진, 하이드록시나프틸아민, para-니트로소메틸아닐린, 비스(para-히드록시페닐)아민 등을 들 수 있다. 사용량은 0.2 중량 % 이하가 바람직하다.The polymerization inhibitor inhibits the formation of continuous monomers of nitrile monomers, thereby preventing whiteness reduction and preventing degradation of thermal stability and light stability, and para-tert-butylcatechol, α-nitroso-β-naphthol, di -tert-amylhydroquinone, dinitrobenzenethiol, dinitrophenylbenzocaradisulfide, sodium hydrosulfide, tetramethylthiuram disulfide, tatramethylthiuride sulfide, sodium dimethyldiwabamate potassium, dimethyldithiocarbamate, etc. And dialkylthiocarbamate metal salts, phenylhydrazine, hydroxynaphthylamine, para-nitrosomethyl aniline, bis (para-hydroxyphenyl) amine, and the like. The amount of use is preferably 0.2% by weight or less.
이외에도 적당한 유화제 또는 수성매질 분산제 및 pH 조절재를 포함할 수 있다.In addition, a suitable emulsifier or an aqueous medium dispersant and a pH adjusting agent may be included.
유화제로는 로진산칼륨, 라우린산칼륨, 올레인산칼륨 또는 알킬벤젠술폰산나트륨, 알킬나프탈렌술폰산나트륨이 있으며, 바람직한 사용량은 0.1∼10 중랑 % 이다.Examples of the emulsifier include potassium rosin, potassium laurate, potassium oleate or sodium alkylbenzenesulfonate and sodium alkylnaphthalenesulfonate.
pH 조절제로는 염화나트륨, 탄산수소나트륨, 탄산나트륨, 인산나트륨, 염화칼륨, 탄산수소칼륨, 탄산칼륨 또는 인산칼륨 등의 전해질을 사용할 수 있다.As the pH adjusting agent, an electrolyte such as sodium chloride, sodium hydrogen carbonate, sodium carbonate, sodium phosphate, potassium chloride, potassium hydrogen carbonate, potassium carbonate or potassium phosphate can be used.
본 발명의 조성물은 일반적인 방법으로 니트릴 고무 라텍스로 제조할 수 있다. 예를 들면, 교반기 또는 교반 기구가 설치된 깨끗한 반응기에 반응물을 주입하는데, 바람직하게는 반응 용기 및 반응물을 비활성 기체, 더욱 바람직하게는 질소 또는 아르곤 기체로 깨끗하게 한다. 상기 반응물을 50∼80 ℃, 바람직하게는 60∼70 ℃로 가열한 다음 연속적으로 또는 간힐적으로 예를 들면 150 rpm으로 교반한다. 중합화 반응이 소망 수준, 통상 40∼100 %, 바람직하게는 60∼90 % 전환으로 진행될 때까지 교반을 계속하여 니트릴 고무 라텍스를 제조한다. 본 발명의 조성물을 사용한 제조 방법에서는 온도를 상승시키는 것이 용이하므로 니트릴 고무 라텍스의 겔 함량을 높일 수 있다.The composition of the present invention can be made of nitrile rubber latex in a general manner. For example, the reactants are injected into a clean reactor equipped with a stirrer or agitation mechanism, preferably the reaction vessel and reactants are cleaned with an inert gas, more preferably nitrogen or argon gas. The reaction is heated to 50-80 ° C., preferably 60-70 ° C. and then stirred continuously or intermittently at eg 150 rpm. Stirring is continued until the polymerization reaction proceeds to the desired level, usually 40-100%, preferably 60-90% conversion, to produce nitrile rubber latex. In the production method using the composition of the present invention, it is easy to raise the temperature, so that the gel content of the nitrile rubber latex can be increased.
본 발명의 조성물로 제조된 니트릴 고무 라텍스는 고형분 함량이 40 % 이상이면서 니트릴 함량이 30 중랑 % 초과되어도 안정하므로, 고함랑의 니트릴계 차단성 수지 제조 시 충격 보강을 위해 사용되는 것 외에도 종이 가공 분야의 접착제 분야 및 섬유 처리 분야에 이용될 수 있다.Nitrile rubber latex prepared with the composition of the present invention is stable even when the solid content is more than 40% and the nitrile content is more than 30 weight%, so that in addition to being used for impact reinforcement in the production of high-quality nitrile-based barrier resin, paper processing field It can be used in the adhesive field and fiber processing field of the.
이하 니트릴 고무 라텍스 제조 단계와 그라프트 공중합체 제조 단계를 나누어서 본 발명 니트릴 고무 라텍스 제조 방법을 설명한다.Hereinafter, the nitrile rubber latex manufacturing method of the present invention will be described by dividing the nitrile rubber latex manufacturing step and the graft copolymer manufacturing step.
탈이온수 120 중량부에 0.5∼2.0 중량부의 음이온계 유화제, 0.7 중량부의 염화칼륨, 0.3 중량부의 α-메틸스티렌 이합체, 0.05 중량부의 소디움하이드로설파이드, 40 중량부의 아크릴로니트릴, 0.2 중량부의 과황산 칼륨을 깨끗한 반응기에 주합한다. 반응기 및 반응물을 질소 또는 아르곤 기체를 이용하여 세척한다. 60 중량부의 부타디엔을 반응기에 가하고 상기 혼합물을 교반하면서 65 ℃로 가열한다.전환율이 40 %에 도달하면 음이온계 유화제 1.0 중량부를 30분에 걸쳐 서서히 투입한다. 절환율이 90 %에 도달하면 중합 정지제로서 디에틸하이드록실아민을 투입하고 냉각시킨다. 상기 반응이 진행되는 동안 반응기 내 온도는 계속 65 ℃를 유지하고 압력도 6.0 kgf/cm2를 넘지 않고 전환율이 50 %가 될 때까지 일정하게 유지한다.To 120 parts by weight of deionized water 0.5 to 2.0 parts by weight of anionic emulsifier, 0.7 parts by weight of potassium chloride, 0.3 parts by weight of α-methylstyrene dimer, 0.05 parts by weight of sodium hydrosulfide, 40 parts by weight of acrylonitrile, 0.2 parts by weight of potassium persulfate Cast into a clean reactor. The reactor and reactants are washed with nitrogen or argon gas. 60 parts by weight of butadiene are added to the reactor and the mixture is heated to 65 ° C. while stirring. When the conversion reaches 40%, 1.0 part by weight of anionic emulsifier is slowly added over 30 minutes. When the switching rate reaches 90%, diethylhydroxylamine is added as a polymerization terminator and cooled. During the reaction, the temperature in the reactor was continuously maintained at 65 ° C. and the pressure was kept constant until the conversion rate reached 50% without exceeding 6.0 kgf / cm 2 .
그라프트 공중합체의 제조Preparation of Graft Copolymer
위의 방법에 의해 제조된 겔 함량이 80∼95 %, 중량 평균 입자경이 1000∼2500 Å인 고무 입자 40 % 이하로 구성된 고무 라텍스를 8∼20 중량부, 음이온계 유화제를 1∼2 중량부, 메르캅탄 1∼3 중량부와 적량의 탈이온수를 45 ℃의 반응기에 넣은 후, 비닐시안화 화합물 30∼20 중량부, 불포화 카르복실산 에스테르 5∼10 중량부를 투여하고, 반응기의 온도를 상승시켜 60 ℃에 이르면 개시제로서 퍼설페이트 0.05∼0.2 중량부를 투입한 후 2∼4 시간 반응을 시킨다.8 to 20 parts by weight of a rubber latex composed of 80 to 95% of the gel content prepared by the above method, 40% or less of rubber particles having a weight average particle diameter of 1000 to 2500 mm 3, 1 to 2 parts by weight of an anionic emulsifier, 1 to 3 parts by weight of mercaptan and an appropriate amount of deionized water were added to a reactor at 45 ° C, and then 30 to 20 parts by weight of the vinyl cyanide compound and 5 to 10 parts by weight of unsaturated carboxylic acid ester were added, and the temperature of the reactor was raised to 60 When the temperature is reached, 0.05 to 0.2 parts by weight of persulfate is added as an initiator, followed by reaction for 2 to 4 hours.
전환율이 단랑체 기준으로 60 %를 넘어섰을 때 비닐시안화 화합물 40∼30 중량부, 불포화 카르복실산 에스테르 15∼10 중량부, 방향족 비닐 화합물 2 중량부 이하를 혼합하여 투입하고 전환율이 단량체 기준으로 70 % 이상이 될 때까지 2∼3 시간 반응을 시킨다. 그 후 비닐시안화 화합물 15 중량부 이하, 불포화 카르복실산 에스테르 10∼5 중랑부, 방향족 비닐 화합물 5 중량부 이하의 혼합액과 0.01∼0.02 중량부의 퍼설페이트 개시제를 투입하고 8 시간 반응을 시킨다. 얻어진 라텍스는 고형분이 33∼37 %이고 중량 평균 입자경은 1600∼3800 Å 이다.When the conversion rate exceeds 60% based on the monomer, 40 to 30 parts by weight of the vinyl cyanide compound, 15 to 10 parts by weight of the unsaturated carboxylic acid ester, and 2 parts by weight or less of the aromatic vinyl compound are mixed, and the conversion rate is 70 based on the monomer. The reaction is carried out for 2 to 3 hours until it is at least%. Thereafter, 15 parts by weight or less of the vinyl cyanide compound, 10-5 unsaturated unsaturated carboxylic acid esters, 5 parts by weight or less of the aromatic vinyl compound, and 0.01 to 0.02 parts by weight of the persulfate initiator are added to react for 8 hours. The latex obtained was 33 to 37% solids and had a weight average particle diameter of 1600 to 3800 mm 3.
얻어진 라텍스를 염화 칼슘 2∼4 중량부로 응집하여 수세, 건조하여 분말을얻어낸다.The obtained latex is agglomerated with 2 to 4 parts by weight of calcium chloride, washed with water and dried to obtain a powder.
실시예 1Example 1
1단계Stage 1
니트릴 고무 라텍스(중랑 평균 입자경 1500Å) 10 중량부, 탈이온수 180부, Rodafac RE610 2부, 메르캅단 1.0부, 아클리로니트릴 30부, 메틸아크릴레이트 8.5부를 반응기에 투입한 후 반응기의 온도가 45 ℃에 이르면 퍼설페이트 0.1부를 투입하고 반응기의 온도를 60 ℃까지 상승시킨다.10 parts by weight of nitrile rubber latex (medium average particle size 1500Å), 180 parts of deionized water, 2 parts of Rodafac RE610, 1.0 part of mercapdan, 30 parts of acrylonitrile and 8.5 parts of methyl acrylate were added to the reactor, and the temperature of the reactor was 45 0.1 parts of persulfate was added when the temperature was reached, and the temperature of the reactor was raised to 60 ° C.
2단계Tier 2
1단계 반응의 전환율이 단량체 기준으로 60 %를 넘어섰을 때(2∼4 시간 소요) 메르캅탄 1.0부, 아크릴로니트릴 25부, 메타아크릴로니트릴 10부, 메틸아크릴레이트 10부를 일괄 투입한다.When the conversion rate of the first stage reaction exceeds 60% based on the monomer (takes 2 to 4 hours), 1.0 part of mercaptan, 25 parts of acrylonitrile, 10 parts of methacrylonitrile, and 10 parts of methyl acrylate are added at once.
3단계Tier 3
2단계 반응의 전환율이 단량체 기준으로 70 %를 넘어섰을 때(2∼3 시간 소요) 메르캅탄 0.2부, 아크릴로니트릴 5부, 메타아크릴로니트릴 5부, 메틸아크릴레이트 6.5부와 퍼설페이트 0.01부를 탈이온수 10부에 녹여 반응기에 투입하고 8 시간 동안 반응시킨다.When the conversion rate of the two-step reaction exceeds 70% based on the monomer (takes 2-3 hours), 0.2 parts of mercaptan, 5 parts of acrylonitrile, 5 parts of methacrylonitrile, 6.5 parts of methyl acrylate and 0.01 part of persulfate Dissolved in 10 parts of deionized water, added to the reactor and reacted for 8 hours.
얻어진 라텍스를 금속염으로 응집시켜 수제, 건조한 후 분말을 얻어낸다. 제조된 그라르트 중합체를 프레스로 가압성형하여 시편을 제조한 후 탁도, 투과도, 황변도를 측정하였다. 투과도와 탁도는 Nippon Denshoku Kogyo Co., Ltd.의 Color & Color Difference Meter(Model 1001 DP)를 이용하여 측정하였고, 황변도는Spectrogard Color System)을 이용하여 측정하였다.The latex obtained is aggregated with a metal salt to obtain powder after being handmade and dried. The graft polymer was press-molded with a press to prepare a specimen, and then turbidity, permeability, and yellowing were measured. Permeability and turbidity were measured using a Color & Color Difference Meter (Model 1001 DP) by Nippon Denshoku Kogyo Co., Ltd., and yellowing was measured using a Spectrogard Color System.
실시예 2Example 2
1단계Stage 1
니트릴 고무 라텍스(중랑 평균 입자경 1500Å) 10 중량부, 탈이온수 180부, Rodafac RE610 2부, 메르캅단 1.0부, 아클리로니트릴 13부, 메틸아크릴레이트 10부, 메타아크릴로니트릴 7부를 반응기에 투입한 후 반응기의 온도가 45 ℃에 이르면 퍼설페이트 0.1부를 투입하고 반응기의 온도를 60 ℃까지 상승시킨다.10 parts by weight of nitrile rubber latex (medium diameter 1500Å), 180 parts of deionized water, 2 parts of Rodafac RE610, 1.0 part of mercapdan, 13 parts of acrylonitrile, 10 parts of methyl acrylate, and 7 parts of methacrylonitrile After that, when the temperature of the reactor reaches 45 ° C, 0.1 part of persulfate is added and the temperature of the reactor is increased to 60 ° C.
2단계Tier 2
1단계 반응의 전환율이 단량체 기준으로 60 %를 넘어섰을 때(2∼4 시간 소요) 메르캅탄 1.0부, 아크릴로니트릴 23부, 메타아크릴로니트릴 12부, 메틸아크릴레이트 10부를 일괄 투입한다.When the conversion rate of the first stage reaction exceeds 60% based on the monomer (takes 2 to 4 hours), 1.0 part of mercaptan, 23 parts of acrylonitrile, 12 parts of methacrylonitrile, and 10 parts of methyl acrylate are added at once.
3단계Tier 3
2단계 반응의 전환율이 단량체 기준으로 70 %를 넘어섰을 때(2∼3 시간 소요) 메르캅탄 0.2부, 아크릴로니트릴 10부, 메타아크릴로니트릴 5부, 메틸아크릴레이트 10부를 일괄 투입한 후, 실시예 1과 같은 방법으로 반응시킨다.When the conversion rate of the two-stage reaction exceeds 70% based on the monomer (takes 2-3 hours), 0.2 parts of mercaptan, 10 parts of acrylonitrile, 5 parts of methacrylonitrile, and 10 parts of methyl acrylate are collectively added. The reaction was carried out in the same manner as in Example 1.
이후 공정은 실시예 1과 같다.The process is then the same as in Example 1.
실시예 3Example 3
1, 2 단계1, 2 steps
실시예 1과 동일Same as Example 1
3단계Tier 3
2단계 반응의 전환율이 단랑체 기준으로 70 %를 넘어섰을 때(2∼3 시간 소요) 메르캅탄 0.2부, 아크릴로니트릴 10부, 메타아크릴로니트릴 5부, 메틸아크릴레이트 7부, 스티렌 3부를 넣고 실시예 1과 같은 방법으로 반응시킨다.When the conversion rate of the two-stage reaction exceeds 70% on the basis of monolayer (2-3 hours), 0.2 parts of mercaptan, 10 parts of acrylonitrile, 5 parts of methacrylonitrile, 7 parts of methyl acrylate, and 3 parts of styrene The reaction was carried out in the same manner as in Example 1.
이후 공정은 실시예 1과 같다.The process is then the same as in Example 1.
비교예 1Comparative Example 1
탈이온수 180부, Rodafac RE610 2.0부 메르캅탄 2.0부, 아크릴로니트릴 54부, 메틸아크릴레이트 22.5부, 메타아크릴로니트릴 13.5부, 니트릴고무라텍스 10부(고형분 기준), 퍼설패이트 0.1부를 60 ℃의 반응기에 일괄 투여한 후 14 시간 동안 반응시킨다.Deionized water 180 parts, Rodafac RE610 2.0 parts mercaptan 2.0 parts, acrylonitrile 54 parts, methyl acrylate 22.5 parts, methacrylonitrile 13.5 parts, nitrile rubber latex (based on solids), persulfate 0.1 part 60 ℃ After batch administration to the reactor, the reaction was carried out for 14 hours.
이후 공정은 실시예 1과 같다.The process is then the same as in Example 1.
실험 결과Experiment result
실시예 1∼3과 비교예 1에서 얻어진 그라프트 중합체를 이용하여 각각 시련을 제조한 후, 투명도, 탁도, 황변도를 측정한 결과를 아래 표 1에 제시하였다.After the trials were prepared using the graft polymers obtained in Examples 1 to 3 and Comparative Example 1, the results of measuring transparency, turbidity, and yellowing were shown in Table 1 below.
[표 1]TABLE 1
Claims (9)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138256A (en) * | 1983-01-28 | 1984-08-08 | Mitsubishi Rayon Co Ltd | resin composition |
| JPH03199214A (en) * | 1989-12-27 | 1991-08-30 | Sumitomo Chem Co Ltd | Modified polymer rubber and production thereof |
| JPH06179772A (en) * | 1992-12-11 | 1994-06-28 | Asahi Chem Ind Co Ltd | Production of carboxyl-modified butadiene-based copolymer latex |
| KR960022733A (en) * | 1994-12-30 | 1996-07-18 | 성재갑 | Method for producing a thermoplastic resin composition excellent in surface gloss and fluidity |
| KR0161057B1 (en) * | 1994-06-12 | 1999-01-15 | 성재갑 | Process for the preparation of the thermoplastic resin compositions |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59138256A (en) * | 1983-01-28 | 1984-08-08 | Mitsubishi Rayon Co Ltd | resin composition |
| JPH03199214A (en) * | 1989-12-27 | 1991-08-30 | Sumitomo Chem Co Ltd | Modified polymer rubber and production thereof |
| JPH06179772A (en) * | 1992-12-11 | 1994-06-28 | Asahi Chem Ind Co Ltd | Production of carboxyl-modified butadiene-based copolymer latex |
| KR0161057B1 (en) * | 1994-06-12 | 1999-01-15 | 성재갑 | Process for the preparation of the thermoplastic resin compositions |
| KR960022733A (en) * | 1994-12-30 | 1996-07-18 | 성재갑 | Method for producing a thermoplastic resin composition excellent in surface gloss and fluidity |
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