KR0177253B1 - Process for preparing heat resistant copolymer compositions - Google Patents
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- KR0177253B1 KR0177253B1 KR1019950003859A KR19950003859A KR0177253B1 KR 0177253 B1 KR0177253 B1 KR 0177253B1 KR 1019950003859 A KR1019950003859 A KR 1019950003859A KR 19950003859 A KR19950003859 A KR 19950003859A KR 0177253 B1 KR0177253 B1 KR 0177253B1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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
- 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
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Abstract
본 발명은 라텍스 고형분 함량이 높고 라텍스 안정성이 극히 우수한 내열성 공중합체 조성물의 제조방법에 관한 것으로, 방향족 비닐계 화합물 50∼80 중량부와 비닐 시안화 화합물 15∼35 중량부로 이루어진 단량체 조성물을 유화중합시켜 내열성 공중합체 조성물을 제조함에 있어서, 전해물을 0.01 내지 1 중량부 첨가하는 것을 특징으로 한다.The present invention relates to a method for preparing a heat-resistant copolymer composition having a high latex solid content and excellent latex stability. The present invention relates to emulsion-polymerizing a monomer composition composed of 50 to 80 parts by weight of an aromatic vinyl compound and 15 to 35 parts by weight of a vinyl cyanide compound to provide heat resistance. In preparing the copolymer composition, the electrolyte is characterized by adding 0.01 to 1 parts by weight.
Description
본 발명은 내열성 공중합체 조성물의 제조방법에 관한 것으로, 더욱 상세하게는 α-메틸스티렌계 내열성 공중합체 조성물을 제조하는데 있어서, 탄산수소나트륨(NaHCO3) 등의 전해물을 사용함으로써 라텍스 고형분 함량이 높고 라텍스 안정성이 극히 우수한 내열성 공중합체 조성물의 제조방법에 관한 것이다.The present invention relates to a method for producing a heat resistant copolymer composition, and more particularly, in preparing an α-methylstyrene-based heat resistant copolymer composition, by using an electrolyte such as sodium hydrogen carbonate (NaHCO 3 ), the latex solid content is high and The present invention relates to a method for producing a heat resistant copolymer composition having excellent latex stability.
일반적으로, 내열성 아트릴로니트릴-부타디엔-스티렌 수지(ABS 수지)와 같은 열가소성 수지 조성물을 제조하는 방법으로는 그라프트 ABS 수지에 α-메틸스티렌계 화합물을 포함하는 내열성 공중합체와 혼련하는 방법(미국특허 3,010,936호, 미국특허 4,659,790호). N-페닐말레이미드를 포함하는 내열성 공중합체와 혼련하는 방법(일본특허 소58-206657. 소63-162708. 미국특허 4,757,109). 폴리카보네이트 수지와 혼련하는 방법, 무기물을 충지시키는 방법 등이 알려져 있다.In general, a method for preparing a thermoplastic resin composition such as a heat resistant atrylonitrile-butadiene-styrene resin (ABS resin) is a method of kneading with a heat resistant copolymer comprising an α-methylstyrene compound in a graft ABS resin (US Patent 3,010,936, US patent 4,659,790). A method of kneading with a heat resistant copolymer comprising N-phenylmaleimide (Japanese Patent No. 58-206657. So 63-162708. US Patent 4,757,109). The method of kneading with a polycarbonate resin, the method of filling an inorganic substance, etc. are known.
이들 제조방법중 α-메틸스티렌계 화합물이 포함되는 내열성 공중합체와 혼련하는 방법이 경제적이어서 가장 널리 사용되는 제조방법이나 α-메틸스티렌계 화합물의 낮은 반응성과 고온에서의 열안정 저하, 라텍스 안정성 부족 등의 문제점을 가진다.Among these production methods, kneading with heat-resistant copolymers containing α-methylstyrene compounds is economical, and thus the most widely used manufacturing methods are low reactivity of α-methylstyrene compounds, low thermal stability at high temperatures, and lack of latex stability. And the like.
최근 α-메틸스티렌계 내열성 공중합체에 라텍스 안정성을 부여하여 생산성을 향상시키려는 연구가 활발히 진행되고 있는데, 라텍스 안정성을 향상시키는 방법으로는 유화제를 증량시키는 방법, 메타크릴아마이드 단량체를 포함시키는 방법 등이 제안되고 있다. 그러나 유화제를 증량시키는 방법은 점도문제와 응집문제, 물성저하 등의 문제점을 가지고 있으며, 메타크릴아마이드 단량체를 포함시키는 방법은 라텍스 안정성과 내열성은 증대시키지만 메타크릴아마이드 단량체의 가격이 높아 사용상의 한계를 가지는 문제점을 가지고 있다.Recently, studies have been actively conducted to improve latex stability by providing latex stability to α-methylstyrene-based heat-resistant copolymers. Examples of improving latex stability include increasing an emulsifier and a method including a methacrylamide monomer. It is proposed. However, the method of increasing the emulsifier has problems such as viscosity problem, coagulation problem, and deterioration of physical properties, and the method of including methacrylamide monomer increases latex stability and heat resistance, but the price of methacrylamide monomer is high, thereby limiting the limitation of use. Branch has a problem.
본 발명자는 상기의 이와같은 문제점을 해결하기 위하여 예의 연구한 결과, α-메틸스티렌계 화합물을 포함하는 내열성 공중합체 조성물을 유화중합 방법으로 제조할 때 전해물을 첨가함으로써, 내열성과 내충격성이 우수하고 고형분 함량이 36% 이상이 되며, 라텍스 안정성이 극히 우수한 내열성 공중합체 조성물을 제조하게 되었다.MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said problem, the present inventors added electrolyte when manufacturing the heat resistant copolymer composition containing the (alpha) -methylstyrene type compound by the emulsion polymerization method, and it is excellent in heat resistance and impact resistance, The solid content is 36% or more, and a heat resistant copolymer composition having excellent latex stability is prepared.
즉 본 발명은 방향족 비닐계 화합물과 비닐시안화 화합물로 이루어지는 단량체 조성물을 유화중합시켜 내열성 공중합체를 제조함에 있어서, 탄산수소나트륨 등의 전해물을 첨가하여 라텍스 고형분 함량이 높고 라텍스 안정성이 극히 우수한 내열성 공중합체를 제조함을 특징으로 한다.That is, in the present invention, in preparing a heat-resistant copolymer by emulsion-polymerizing a monomer composition comprising an aromatic vinyl compound and a vinyl cyanide compound, an electrolyte such as sodium hydrogen carbonate is added to provide a latex solid content with extremely high latex stability. Characterized in that the manufacturing.
이하 본 발명을 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에서의 내열성 공중합게 조상물은 방향족 비닐계 화합물 50 내지 80 중량 부와 비닐 시안화 화합물 15 내지 35 중량부로 이루어진 단량체 조성물로서, 전해물이 첨가되고, 유화중합방법에 의해 제조된 것이다.The heat-resistant copolymer crab precursor in the present invention is a monomer composition consisting of 50 to 80 parts by weight of an aromatic vinyl compound and 15 to 35 parts by weight of a vinyl cyanide compound, to which an electrolyte is added and prepared by an emulsion polymerization method.
각 성분의 참가방법으로는 각 성분을 일괄투여하는 방법과 전량 또는 일부를 연속(순차적으로) 투여하는 방법을 사용할 수 있는데, 본 발명에서는 일괄투여와 연속 투여방법을 조절하여 사용하는 복합형태를 취한다.As a method of participating in each component, a method of collectively administering each component and a method of continuously (sequentially) administering all or part of the components may be used. do.
즉 단량체 총 중량중 70 내지 90 중량부와 이온교환수, 유화제, 분자량조절제, 전해물, 중합개시제의 총 중량중 일부를 반응개시 후 일괄투여하고,1 내지 2시간 동안 55℃ 내지 80℃의 온도에서 반응시킨 다음 단량체 총 중량중 5내지 30 중량부와 이온교환수, 유화제 일부와, 잔여 분자량조절제, 전해물, 중합개시제를 65℃내지 80℃의 온도에서 2 내지 6시간에 걸쳐 연속 투여한 후 잔여 단량체와 유화제, 이온교환수를 투여하여 1 내지 2시간 동안 유화중합 반응을 시켜 내열성 공중합체 조성물을 제조한다.That is, 70 to 90 parts by weight of the total weight of the monomers and a portion of the total weight of ion exchanged water, emulsifiers, molecular weight regulators, electrolytes, and polymerization initiators are administered in batches after the reaction is initiated, and at a temperature of 55 ° C. to 80 ° C. for 1 to 2 hours. After the reaction, 5 to 30 parts by weight of the total monomer, ion-exchanged water, a part of the emulsifier, and a residual molecular weight regulator, an electrolyte, and a polymerization initiator were continuously administered at a temperature of 65 ° C. to 80 ° C. over 2 to 6 hours, and then the remaining monomers. And an emulsifier and ion-exchanged water are then subjected to emulsion polymerization for 1 to 2 hours to prepare a heat resistant copolymer composition.
본 발명에 사용되는 방향족 비닐계 화합물로는 스티렌, α-에틸스티렌, α-에틸스티렌, o-에틸스티렌, p-에틸스티렌, 2,4-디메틸스티렌 등이 사용되며, 비닐 시안화 화합물로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 등이 사용되고, 유화제로는 알킬벤젠술폰산의 나트륨 염 및 칼륨염 또는 로진산과 고급 지방산류의 나트륨 염 및 칼륨염 등이 사용되어진다.As the aromatic vinyl compound used in the present invention, styrene, α-ethyl styrene, α-ethyl styrene, o-ethyl styrene, p-ethyl styrene, 2,4-dimethyl styrene and the like are used. Ronitrile, methacrylonitrile, ethacrylonitrile and the like are used, and as the emulsifier, sodium salts and potassium salts of alkylbenzenesulfonic acid or sodium salts and potassium salts of rosin acid and higher fatty acids are used.
종합개시제로는 과황산염, 디이소프로필벤젠하이드로퍼옥사이드, 큐멘하이드로퍼 옥사이드 등과 같은 과산화물과 소디움포름알데히드설폭시레이트, 소디움 에틸렌 디아민 테트라아세테이트, 황산제일철, 덱스트로즈, 피롤린산나트륨, 아황산나트륨등과 같은 환원제와의 혼합물로 된 산화-환원 촉매를 사용한다.Synthetic initiators include peroxides such as persulfate, diisopropylbenzene hydroperoxide, cumene hydroperoxide, sodium formaldehyde sulfoxylate, sodium ethylene diamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite, etc. An oxidation-reduction catalyst in a mixture with a reducing agent such as is used.
분자량 조절제로는 3급 도데실메르캅탄이 사용되며, 총 단량체 100 중량부당 0.7 중량부 이하의 양으로 사용된다.As the molecular weight regulator, tertiary dodecyl mercaptan is used, and is used in an amount of 0.7 parts by weight or less per 100 parts by weight of the total monomers.
전해물로는 탄산수소나트륨(NaHCO3)과 인산나트륨(Na3PO4), 탄산칼륨(K2CO3), 아황산나트륨(NaHSO3), 염화칼륨(KCl) 등이 사용되며, 그 사용량은 0.01 내지 1 중량부이다. 본 발명에서 투여되는 전해물량이 증대될수록 중합전환율은 감소하므로, 중합전환율이 96% 이상되는 중합체를 얻기 위해서는 전해물의 투여량과 투여시기조절이 아주 중요하다.Examples of the electrolyte include sodium hydrogen carbonate (NaHCO 3 ), sodium phosphate (Na 3 PO 4 ), potassium carbonate (K 2 CO 3 ), sodium sulfite (NaHSO 3 ), potassium chloride (KCl), and the like. 1 part by weight. As the amount of the electrolyte administered in the present invention increases, the polymerization conversion rate decreases. Therefore, in order to obtain a polymer having a polymerization conversion rate of 96% or more, the dosage and the timing of administration of the electrolyte are very important.
중합 종료 후 중합전환율은 96% 이상이며, 수득된 라텍스를 120℃ 이상의 온도에서 염화칼슘 수용액으로 응고시켜 탈수 및 건조 후 분말형태를 만든다.After the completion of the polymerization, the polymerization conversion rate is 96% or more, and the latex obtained is solidified with an aqueous calcium chloride solution at a temperature of 120 ° C. or higher to form a powder after dehydration and drying.
이하 본 발명을 실시예를 통해 기술하지만, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described by way of Examples, but the present invention is not limited by the Examples.
실시예에서의 고형분 함량 및 생성응고물 총량은 하기식으로부터 구할 수 있다.The solids content and the total amount of coagulant produced in the examples can be obtained from the following formula.
생성응고물 총량이 0.5% 이상일 때는 제조된 라텍스의 안정성이 떨어져 본 발명의 목적에 적합하지 않다.When the total amount of product coagulant is 0.5% or more, the stability of the latex produced is not suitable for the purpose of the present invention.
또한 라택스 입경은 다이나믹 레이저 라이트 스케터링(Dynamic Laser Light Scattering)법으로 Nicomp 370HPL을 사용하여 측정하였다.In addition, the particle size of the latex was measured using a Nicomp 370HPL by the Dynamic Laser Light Scattering method.
[실시예 1]Example 1
질소치환된 중합반응기에 표 1의 조성비 A1의 1단계 성분 즉 이온교환수 110 중량부 및 유화제인 라우릴 황산 칼륨염 2.2 중량부와 α-메틸스티렌 64 중량부, 아크릴로니트릴 14 중량부, 분자량 조절제인 3급 도데실메르캅탄(TDDM) 0.4중량부, 탄산수소나트륨 0.3중량부와 중합개시제로 디이소프로필벤젠하이드로퍼옥사이드 0.3중량부, 소디움에틸렌디아민테트라아세테이트 0.1중량부, 황산 제일철 0.005중량부, 포름알데히드 소디움설폭시레이트 0.2중량부로 구성된 산화-환원 촉매를 45℃에서 일괄 투여하고 반응시키면서 70℃까지 연속적으로 1시간 30분동안 상승시켰다.In the nitrogen-substituted polymerization reactor, the first stage component of composition ratio A1 of Table 1, namely 110 parts by weight of ion-exchanged water, 2.2 parts by weight of potassium lauryl sulfate, emulsifier, 64 parts by weight of α-methylstyrene, 14 parts by weight of acrylonitrile, and molecular weight 0.4 parts by weight of tertiary dodecyl mercaptan (TDDM) as a regulator, 0.3 parts by weight of sodium bicarbonate and 0.3 parts by weight of diisopropylbenzenehydroperoxide as a polymerization initiator, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate , An oxidation-reduction catalyst composed of 0.2 parts by weight of formaldehyde sodium sulfoxylate was dosed at 45 ° C. in a batch, and raised to 70 ° C. continuously for 1 hour and 30 minutes while reacting.
온도가 70℃에 도달하였을 때, 표1의 조성비 A1의 2단계 성분 즉, 이온교환수 60중량부, 라우릴 황산 칼륨 0.8중량부, α-메틸스티렌 10중량부, 아크릴로니트릴 10중량부, TDDM 0.2중량부, 탄산수소나트륨 0.05중량부의 유화혼합물과 개시제로 디이소프로필 벤젠하이드로퍼옥사이드 0.1중량부를 혼합하여 약 4시간에 걸쳐 연속투여하였다. 그리고 표1의 A1의 3단계 성분 즉 이온교환수 5중량부, 라우릴 황산 칼륨 0.1중량부, 아크릴로니트릴 2중량부를 일괄투여 한 다음 2시간 숙성시킨 후 반응을 종료시키고 제조된 라텍스의 안정성 여부를 판단키 위해 생성응고물(%)을 측정하였다.When the temperature reached 70 ° C., the two-stage components of the composition ratio A1 of Table 1, namely, 60 parts by weight of ion-exchanged water, 0.8 parts by weight of potassium lauryl sulfate, 10 parts by weight of α-methylstyrene, 10 parts by weight of acrylonitrile, 0.2 parts by weight of TDDM, 0.05 parts by weight of sodium bicarbonate, and 0.1 parts by weight of diisopropyl benzenehydroperoxide as an initiator were mixed and continuously administered over about 4 hours. In addition, the three steps of A1 in Table 1, that is, 5 parts by weight of ion-exchanged water, 0.1 parts by weight of potassium lauryl sulfate, and 2 parts by weight of acrylonitrile were collectively administered, and then aged for 2 hours to terminate the reaction. The product coagulum (%) was measured to determine.
그리고 중합전환율과 라텍스 입경을 측정하였다.And polymerization conversion and latex particle size were measured.
[실시예 2 내지 3][Examples 2 to 3]
상기 실시예 1과 동일반 방법으로 실시하되 조성비를 표 1의 A1 대신 A2 내지 A3의 조성비로 실시하였다.The composition was carried out in the same manner as in Example 1, but the composition ratio was performed in the composition ratio of A2 to A3 instead of A1 in Table 1.
그결과는 표 1에 나타내었다.The results are shown in Table 1.
[비교예 1 내지 2][Comparative Examples 1 and 2]
실시예 1과 동일한 방법으로 실시하되 조성비를 표 1의 B1 내지 B2의 조성비로 실시하였다. 그 결과는 표 1에 나타내었다.It carried out in the same manner as in Example 1, but the composition ratio was carried out in the composition ratio of B1 to B2 in Table 1. The results are shown in Table 1.
[사용예 1][Example 1]
상기 실시예 3에서 제조된 내열성 공중합체 라텍스를 응고시켜 제조한 분말 55 중량부와 ABS 그라프트 중합체 분말 45 중량부에 분말 100 중량부당 활제 0.5 중량부, 산화방지제 0.4 중량부 및 자외선 안정제 0.2 중량부를 투여하여 240℃ 내지 250℃의 실린더 온도에서 2축 혼련기를 사용하여 압출시켜 펠릿 형태로 제조하였다. 이 펠릿을 이용하여 시편을 제조하고 물성을 측정하여 그 결과를 표 2에 나타내었다.55 parts by weight of powder prepared by solidifying the heat-resistant copolymer latex prepared in Example 3 and 45 parts by weight of ABS graft polymer powder 0.5 part by weight of lubricant, 0.4 part by weight of antioxidant and 0.2 part by weight of UV stabilizer per 100 parts by weight of powder Dosing was extruded using a twin screw kneader at a cylinder temperature of 240 ℃ to 250 ℃ to prepare a pellet form. Using the pellets to prepare a specimen and to measure the physical properties are shown in Table 2 the results.
[사용예 2 내지 3][Use Examples 2 to 3]
상기 사용예 1과 동일한 방법으로 실시하되 C1 대신에 C2 내지 C3의 조성비로 실시하였고, 물성을 측정하여 그 결과를 표 2에 나타내었다.It was carried out in the same manner as in Use Example 1, but was carried out in the composition ratio of C2 to C3 instead of C1, and measured the physical properties are shown in Table 2.
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