KR0131574B1 - Composition of copolymer having heat resistance and preparation method using them - Google Patents

Composition of copolymer having heat resistance and preparation method using them

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KR0131574B1
KR0131574B1 KR1019930018487A KR930018487A KR0131574B1 KR 0131574 B1 KR0131574 B1 KR 0131574B1 KR 1019930018487 A KR1019930018487 A KR 1019930018487A KR 930018487 A KR930018487 A KR 930018487A KR 0131574 B1 KR0131574 B1 KR 0131574B1
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weight
parts
sodium
resistant copolymer
heat
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KR950008548A (en
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유근훈
이찬홍
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성재갑
엘지화학 주식회사
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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
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles
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    • 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
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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
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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    • 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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    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • 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
    • C08F222/00—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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or 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; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
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    • 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
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    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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Abstract

Methacrylamide was emulsion-polymerized to give the heat resistant copolymer having polymerization transfer rate more than 95%, solid content more than 33%, glass transition temperature more than 140 deg.C. 60-85 Wt.% of total monomer was reacted at 45-70 deg.C for 0.1 minute-2 hours, 15-40 wt.% of total monomer was added into the reactor at 65-80 deg.C for 2-5 hours, and residue monomer was added and reacted for 10 minutes-2 hours. 50-75 Parts of M-methyl styrene, 5-25 parts of acrylonitrile, 1-20 parts of methacrylonitrile, 5-20 parts of N-phenylmaleimide, and 0.1-5 parts of ethylenic unsaturated amide are used as monomer, methacrylamide is used as ethylenic unsaturated amide, and sodium and potassium salts of rosin acid and high fatty acid sodium and potassium salts of alkylbenzene sulfonic acid are used as emulsifier.

Description

내열성 공중합체 조성물과 이를 이용한 공중합체의 제조방법Heat resistant copolymer composition and method for preparing copolymer using same

본 발명은 라텍스 안정성과 열안정성이 우수하고 내열성이 극히 우수한(내열성) 공중합체 조성물과 이를 이용한 공중합체의 제조 방법에 관한 것이다.The present invention relates to a copolymer composition having excellent latex stability and thermal stability and extremely excellent heat resistance (heat resistance) and a method for producing a copolymer using the same.

아크릴로니트릴-부타디엔-스티렌(이하 ABS라함)수지는 내 충격성, 내 약품성, 가공성 및 표면 광택등이 우수하나 내열성이 부족하여 OA용 기기, 가전기기등의 전기, 전자 기기와 자동차등의 부품용으로 사용하기에는 극히 제한되는 문제점을 가져 최근 내열성의 향상에 대한 연구가 많이 진행되어 왔다.Acrylonitrile-butadiene-styrene (hereinafter referred to as ABS) resin has excellent impact resistance, chemical resistance, processability, and surface gloss, but lacks heat resistance, so it is used for electric, electronic devices such as OA devices, home appliances, and automobiles. In recent years, many studies have been conducted on improving heat resistance due to extremely limited problems.

예를 들면 미 합중국 특허 3010936호 및 4659790호에는 α - 메틸스티렌을 포함하는 내열성 공중합체 제조방법이 기재되어 있는데 이 방법은 중합체의 내열성은 향상되지만 중합전환율, 라텍스 안정성, 고온에서의 열 안정성이 저하되는 문제점을 가진다.For example, U.S. Patent Nos. 3010936 and 4659790 describe methods for producing heat resistant copolymers comprising α-methylstyrene, which improve the polymer's heat resistance but reduce polymerization conversion, latex stability, and thermal stability at high temperatures. Has the problem.

일본 특허 공개소 58-206657호, 59-135210호 및 59-184243호에는 N-페닐말레이미드를 포함하는 내열성 공중합체 제조방법이 기제되어 있는데 이 방법역시 내열성은 향상되지만 수지의 가공성과 충격강도 등의 물성 저하가 일어난다.Japanese Patent Laid-Open Nos. 58-206657, 59-135210, and 59-184243 describe a method for producing a heat resistant copolymer including N-phenylmaleimide, which also improves heat resistance but does not include processability and impact strength of the resin. Decreases in physical properties.

또한 일본 특허 공보소 60-4544호에는 α-메틸스티렌에 N-페닐말레이미드 단량체를 도입하고 중합방법을 개량시켜 내열성을 향상시키는 방법이 기재되어 있는데 N-페닐말레이미드의 분산성저하로 응고물이 다량 발생하는 문제점을 가진다.In addition, Japanese Patent Publication No. 60-4544 discloses a method of introducing N-phenylmaleimide monomers into α-methylstyrene and improving the polymerization resistance to improve heat resistance. This has a problem that occurs a lot.

본 발명은 이와같은 문제점을 해결하기 위하여 α-메틸스티렌, 아크릴로 니트릴 N-페닐말레이미드 등의 단량체들에 열안정성과 내열성을 향상시키기 위해 메타크릴 아마이드를 사용해 유화중합을 행하여 중합전환율이 약 95%이상, 고형분 함량이 약 33% 이상이고 중합전환율, 라텍스 안정성, 고온에서의 열안정성이 우수하고 유리전이 온도가 약 140℃ 이상되는 내열성 공중합체를 얻었다.In order to solve this problem, the present invention provides emulsion polymerization using methacrylamide to improve thermal stability and heat resistance to monomers such as α-methylstyrene and acrylonitrile N-phenylmaleimide. A heat resistant copolymer having a solid content of about 33% or more, excellent polymerization conversion rate, latex stability, thermal stability at high temperature, and a glass transition temperature of about 140 ° C or more was obtained.

이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

본 발명은 유화중합 방법으로서 각 성분의 첨가방법은 각 성분을 일괄투여하는 방법, 전량 또는 일부를 연속적(순차적)으로 투여하는 방법을 사용할 수 있는데 본 발명에서는 일괄투여와 연속투여 방법을 조합하여 사용하는 복합형태로 취한다. 즉, 단량체 총 중량중 60내지 85 중량 %를 반응개시후 일괄투여하고 약 0.1분 내지 2시간 동안 45℃ 내지 70℃의 반응온도에서 반응시킨 다음 단량체 총 중량중 15 내지 40 중량%를 65 내지 80℃에서 2 내지 5시간에 걸쳐 연속투여한 후 잔여단량체를 투여하여 10분 내지 2시간동안 반응시켜 내열성 공중합체를 제조한다.In the present invention, the method of adding each component as an emulsion polymerization method may be a method of collectively administering each component, or a method of continuously or sequentially administering a total amount or a part thereof. In the present invention, a combination of a batch administration and a continuous administration method may be used. Taken in complex form. That is, 60 to 85% by weight of the total weight of the monomers are administered in a batch and then reacted at a reaction temperature of 45 ° C to 70 ° C for about 0.1 minutes to 2 hours, and then 15 to 40% by weight of the total weight of the monomers is 65 to 80 After continuous administration at 2 ° C. over 5 to 5 hours, the remaining monomer was administered to react for 10 minutes to 2 hours to prepare a heat resistant copolymer.

내열성 공중합체를 제조하는 방법에서 단량체는 α-메틸스티렌 50 내지 75 중량부, 아크릴로 니트릴 5 내지 25중량부, 메타크릴로니트릴 1 내지 20 중량부, N-페닐말레이미드 5 내지 20중량부, 에틸렌계 불포화 아마이드 0.1 내지 5중량부를 사용하여 유화중합으로 제조한 것이다.In the method for preparing a heat resistant copolymer, the monomer may include 50 to 75 parts by weight of α-methylstyrene, 5 to 25 parts by weight of acrylonitrile, 1 to 20 parts by weight of methacrylonitrile, 5 to 20 parts by weight of N-phenylmaleimide, It is prepared by emulsion polymerization using 0.1 to 5 parts by weight of ethylenically unsaturated amide.

에틸렌계 불포화 아마이드로는 메타크릴아마이드가 사용되고 유화제로는 로진산과 고급 지방산류의 나트륨염 및 칼륨염, 알킬 벤젠 술폰산의 나트륨염 및 칼륨염 등을 단독 또는 복합체를 사용할 수 있다.Methacrylic amide may be used as the ethylenically unsaturated amide, and sodium salts or potassium salts of rosin acid and higher fatty acids, sodium salts and potassium salts of alkyl benzene sulfonic acid, or the like may be used alone or as a complex.

개시제로는 과황산염, 디이소프로필 벤젠 하이드로퍼옥사이드, 큐멘 하이드로퍼옥사이드 등과 같은 과산화물과 소디움 포름 알데히드 술폭실레이트, 소디움 에틸렌 디아만 테트라 아세티이트, 황산 제 1철, 덱스트로즈, 피롤린산나트륨, 아황산나트륨 등과 같은 환원제와의 혼합물로 된 산화-환원계 촉매를 사용한다.Initiators include peroxides such as persulfate, diisopropyl benzene hydroperoxide, cumene hydroperoxide, sodium formaldehyde sulfoxylate, sodium ethylene dimante tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate Oxidation-reduction catalysts in a mixture with a reducing agent such as sodium sulfite and the like are used.

분자량 조절제로는 3급 도데실메르캅탄이 사용되며, 총 단량체 100 중량부 당 0.6중량부 이하의 양으로 사용된다.As the molecular weight modifier, tertiary dodecyl mercaptan is used, and is used in an amount of 0.6 parts by weight or less per 100 parts by weight of the total monomers.

중합 종료후 중합전환율은 약 95% 이상이며, 수득된 라텍스를 약 130℃ 주위온도에서 염화칼슘 수용액으로 응고시켜 건조 시킨다.After completion of the polymerization, the polymerization conversion rate is about 95% or more, and the latex obtained is dried by coagulation with an aqueous calcium chloride solution at about 130 ° C.

상기에서 제조된 내열성 공중합체와, ABS 그라프트 중합체 라텍스 30내지 50 중량불르 혼련하고 혼련된 라텍스로 약 120도씨주위 온도에서 염화칼슘 수용액으로 응고시키고 탈수 및 건조시켜 분말형태의 내열성 ABS 수지를 제조하거나 또는 내열성 공중하베 라텍스를 단독으로 응고, 탈수 및 건조시켜 분말형태로 만들어 이 분말과 일반 ABS수지 30내지 60 중량부와 혼련하여총 고무함량이 약 15내지 22중량%가 되도록 하고 산화 방지제 및 기타 광안정제를 필요에 따라 투여하여 내열성 ABS수지를 제조한다.The heat-resistant copolymer prepared above was kneaded and kneaded with ABS graft polymer latex 30 to 50 weight, and coagulated with a calcium chloride aqueous solution at a temperature around 120 ° C., dehydrated and dried to prepare a powdery heat-resistant ABS resin. Alternatively, solidify, dehydrate, and dry heat-resistant airborne latex alone to form a powder, kneading the powder with 30 to 60 parts by weight of general ABS resin to give a total rubber content of about 15 to 22% by weight, and to prevent antioxidants and other optical Tablets are administered as needed to produce a heat resistant ABS resin.

본 발명은 예시하기 위해 실시예를 기술하지만 이에 본 발명이 제한되는 것은 아니다.The present invention has been described by way of example and not by way of limitation.

실시예에서 고형분 함량 및 생성 응고물 중량은 하기식으로부터 구할수 있다.In the examples, the solids content and the weight of the resulting coagulant can be obtained from the following formula.

생성 응고물 중량이 약 0.5%이상일때는 제조된 라텍스의 안정성이 극히 떨어져 본 발명의 목적에 적합치 않다.When the product coagulant weight is about 0.5% or more, the stability of the prepared latex is extremely poor, which is not suitable for the purpose of the present invention.

[실시 예 A1]Example A1

반응조에 아래 표 1의 조성비 A1의 1단계 성분 즉, 이온교환수 190중량부, 유화제로 소디움 도데실 벤젠 술포네이트 2.8 중량부, α-메틸스티렌 60중량부, N-페닐말레이미드 5중량부, 메타아크릴로 니트릴 10 중량부 메타 아크릴 아마이드 2 중량부, 3급 도데실 메르캅탄(이하TDDM) 0.5중량부, 소디움 에틸렌 디아민 테트라 아세테이트 0.1 중량부, 황산 제 1철 0.003 중량부, 포름 알데히드 0.2 중량부 개시제로 디이소프로필 벤젠 하이드로 퍼옥사이드 0.2 중량부를 약 45도씨주위온도에서 일괄투여 하고 반응온도를 약 65도씨 주위온도까지 상승시키면서 약 1시간 동안 반응시킨다.In the reactor, the first stage component of composition ratio A1 of Table 1 below, namely 190 parts by weight of ion-exchanged water, 2.8 parts of sodium dodecyl benzene sulfonate as an emulsifier, 60 parts by weight of α-methylstyrene, 5 parts by weight of N-phenylmaleimide, 10 parts by weight of methacrylonitrile 2 parts by weight of methacrylamide, 0.5 part by weight of tertiary dodecyl mercaptan (hereinafter referred to as TDDM), 0.1 part by weight of sodium ethylene diamine tetra acetate, 0.003 part by weight of ferrous sulfate, 0.2 part by weight of formaldehyde 0.2 parts by weight of diisopropyl benzene hydroperoxide as an initiator was collectively administered at an ambient temperature of about 45 degrees Celsius and reacted for about 1 hour while the reaction temperature was raised to about 65 degrees Celsius.

그후 조성비 A1의 2단계 성분 즉, 아크릴로니트릴 12중량부, N-페닐말레이미드 10중량부, TDDM 0.1 중량부의 혼합물과 개시제로 디이소프로필 벤젠 하이드로 퍼옥사이드 0.1 중량부를 혼합하여 반응온도를 약 65도씨에서 약 75도씨로 올리면서 4시간에 걸여 연속투여 하였다.Thereafter, the reaction temperature was adjusted by mixing a two-step component of composition ratio A1, that is, 12 parts by weight of acrylonitrile, 10 parts by weight of N-phenylmaleimide, 0.1 part by weight of TDDM, and 0.1 part by weight of diisopropyl benzene hydroperoxide with an initiator. Dosing was continued in 4 hours while raising to about 75 degrees from Do.

그리고 반응온도를 약 80도씨로 올린후 조성비 A1의 3단계 성분, 즉, 이온교환수 8중량부, 유화제 0.1중량부, 스티렌 1중량부의 유화 혼합물과 개시제로 디이소프로필 벤젠 하이드로 퍼옥사이드 0.05 중량부를 혼합하여 일괄투여한 다음 약 30분 동안 반응시킨후 1시간동안 숙성시켰다.After raising the reaction temperature to about 80 degrees Celsius, the three-stage components of the composition ratio A1, that is, 8 parts by weight of ion-exchanged water, 0.1 parts by weight of an emulsifier, 1 part by weight of styrene, and 0.05 parts of diisopropyl benzene hydroperoxide as an initiator. The mixture was mixed and administered in batches and then reacted for about 30 minutes and then aged for 1 hour.

반응을 종료시킨후 적외선 램프를 이용하여 제조된 라텍스의 고형분 함량(%)를 측정하고 중합 전환율을 측정하였다. 그리고 라텍스의 안정성 여부를 판단하기 위해 생성 응고물 중량(%)을 측정하였다.After the reaction was completed, the solids content (%) of the latex prepared using an infrared lamp was measured, and the polymerization conversion rate was measured. And the weight of the resulting coagulum (%) was measured to determine the stability of the latex.

또한 제조된 라텍스를 약 130도씨 부근 온도에서 염화칼슘 수용액으로 응고시키고 세척하여 건조시킨 다음 DSC(시차 주사열 분석기)로 유리 전이 온도를 측정하였다.In addition, the prepared latex was coagulated with an aqueous calcium chloride solution at about 130 ° C., washed, dried, and the glass transition temperature was measured by DSC (differential scanning heat analyzer).

그 결과는 표 1에 제시되어 있다.The results are shown in Table 1.

[실시예 A2 내지 A7]Examples A2 to A7

실시예 A1과 동일한 방법으로 실시하되 조성비를 표 1의 A1의 대신에 A2내지 A7의 조성비를 사용하였다.The composition was carried out in the same manner as in Example A1, but the composition ratio of A2 to A7 was used instead of A1 in Table 1.

그 결과는 표 1에 나타내었다.The results are shown in Table 1.

[비교 예1 비교 예2]Comparative Example 1 Comparative Example 2

실시예 A1과 동일한 방법으로 실시하되 조성비를 표 1의 A 1대신에 비교 예1, 비교 예2의 조성비를 사용하였다.The composition was carried out in the same manner as in Example A1, but the composition ratio of Comparative Example 1 and Comparative Example 2 was used instead of A of Table 1.

그 결과는 표 1에 나타내었다.The results are shown in Table 1.

[사용예 B1][Example B1]

상기 실시에 A1에서 제조된 내열성 공중합체 라텍스 60 중량부와 ABS 그라프트 중합체[(주)럭키제품 DP210] 라텍스 40 중량부를 혼련하고 약 120도씨 주위온도에서 염화칼슘 수용액으로 응고시켜 세척 건조하여 분말형태로 제조하고 이 분말 100 중량부당 활제 0.4 중량부, 산화방지제 0.4 중량부 및 자외선 안정제 0.2중량부를 투여하여 250도씨 내지 260도씨의 실린더 온도에서 2축 혼련기를 사용하여 압출시켜 펠렛형태로 제조하였다.In the above embodiment, 60 parts by weight of the heat-resistant copolymer latex prepared in A1 and 40 parts by weight of ABS graft polymer [Lucky DP210] latex were kneaded, solidified with an aqueous calcium chloride solution at about 120 ° C., dried, washed and dried to form a powder. 0.4 parts by weight of lubricant, 0.4 parts by weight of antioxidant and 0.2 parts by weight of UV stabilizer per 100 parts by weight of the powder were extruded using a twin screw kneader at a cylinder temperature of 250 ° C to 260 ° C to prepare pellets. .

이 펠렛을 이용하여 시편을 제조해 물성을 측정하여 표 2에 도시하였다.Specimens were prepared using this pellet and measured for physical properties.

그리고 열안정성 정도는 약 240도씨 주위온도에서 사출기 체류 시간에 따라 ASTM D 1295의 방법에 의해 YI(Yellow ness Index)값으로 시험하여 표 3에 도시하였다.The degree of thermal stability is shown in Table 3 by a YI (Yellow ness Index) value by the method of ASTM D 1295 according to the injection machine residence time at about 240 ° C ambient temperature.

[사용예 B2 내지 B9][Example B2 to B9]

사용예 B1 과 동일한 방법으로 실시하되 조성비를 표 2의 B1 대신에 B2 내지 B9의 조성비를 사용하였다.The same method as in Example B1 was used, but the composition ratio of B2 to B9 was used instead of B1 in Table 2.

그 결과는 표 -2 에 나타내었다.The results are shown in Table-2.

Claims (6)

α-메틸스티렌50∼75중량부, 아크릴로니트릴 5∼25중량부, 메타크릴로니트릴 1∼20중량부, N-페닐말레이미드 5∼20 중량부, 에틸렌계 불포화아마이드 0.1∼5 중량부로 구성됨을 특징으로 하는 내열성 공중합체 조성물.50 to 75 parts by weight of α-methylstyrene, 5 to 25 parts by weight of acrylonitrile, 1 to 20 parts by weight of methacrylonitrile, 5 to 20 parts by weight of N-phenylmaleimide, and 0.1 to 5 parts by weight of ethylenically unsaturated amide Heat-resistant copolymer composition, characterized in that. 제1항에 있어서, 상기 에틸렌계 불포화아마이드가 메타크릴 아마이드임을 특징으로 하는 내열성 공중합체 조성물.The heat resistant copolymer composition according to claim 1, wherein the ethylenically unsaturated amide is methacrylamide. 제1항에 있어서, α-메틸스티렌, 아크릴로 니트릴, 메타크릴로니트릴, N-페닐말레이미드, 에틸렌계 불포화아마이드로 분자량 조절제, 개시제 및 유화제의존재하에 유화중합을 행하여 내열성 공중합체를 제조함에 있어서 1) 단량체 총 중량 중 60∼85 중량 %를 유화중합 반응 개시시에 일괄 투여하고, 생성된 중합 반응 혼합물을 45내지 70도씨의 온도에서 0.1분 내지 2시간 동안 유화중합하고,2) 상기 1)에서 수득된 중합생성물에 단량체 총 중량 중 15∼45 중량%를 65∼80도씨의 온도에서 2∼5시간동안에 걸쳐 연속(순차적으로)투여한 다음3) 상기 2)에서 수득된 중합생성물에 잔여 단량체를(순차적으로) 연속 투여하여 30분 내지 2시간 동안 유화중합시킴을 특징으로 하는 내열성 공중합체의 제조 방법.The method of claim 1 wherein the emulsion-polymerization of α-methylstyrene, acrylonitrile, methacrylonitrile, N-phenylmaleimide, ethylenically unsaturated amide in the presence of a molecular weight regulator, initiator and emulsifier to prepare a heat-resistant copolymer 1) 60-85% by weight of the total weight of the monomers are collectively administered at the start of the emulsion polymerization reaction, and the resulting polymerization reaction mixture is emulsion-polymerized at a temperature of 45 to 70 degrees for 0.1 minutes to 2 hours, 2) 15 to 45% by weight of the total weight of the monomers were continuously (sequentially) administered at a temperature of 65 to 80 ° C. for 2 to 5 hours to the polymerization product obtained in 1), and 3) the polymerization product obtained in 2) above. Method for producing a heat-resistant copolymer, characterized in that the emulsion is polymerized for 30 minutes to 2 hours by continuously (sequential) to the residual monomer. 제3항에 있어서, 에틸렌계 불포화 아마이드가 메타크릴아마이드임을 특징으로 하는 내열성 공중합체의 제조 방법.4. The process for producing a heat resistant copolymer according to claim 3, wherein the ethylenically unsaturated amide is methacrylamide. 제3항에 있어서, 유화제로는 로진산과 고급 지방산류의 나트륨 및 칼뮬 염, 알킬벤젠술폰산의 나트륨 염 및 칼륨 염의 단독 또는 복합체를 사용함을 특징으로하는 내열성 공중합체의 제조 방법.The method for producing a heat resistant copolymer according to claim 3, wherein an emulsifier is used alone or as a complex of rosin acid and sodium and calm salts of higher fatty acids, sodium salts and potassium salts of alkylbenzenesulfonic acid. 제3항에 있어서, 개시제로는 과황산염, 디이소프로필벤젠 하이드로퍼옥사이드 및 큐맨 하이드로퍼옥사이드 중에서 선택된 산화제와 소디움 포름알데히드 술푹실레이드, 소디움 에틸렌 디아민 테트라 아세테이트, 황산 제 1철 엑스트로즈, 피롤린산 나트륨 및 아황산나트륨 중에서 선택된 환원제와의 혼합물로 된 산화 환원 촉매를 사용함을 특징으로 하는 내열성 공중합체의 제조방법.The method of claim 3, wherein the initiator is an oxidizing agent selected from persulfate, diisopropylbenzene hydroperoxide, and cuman hydroperoxide, sodium formaldehyde sulfoxylide, sodium ethylene diamine tetra acetate, ferrous sulfate exrose, pyrrole A method for producing a heat resistant copolymer characterized by using a redox catalyst made of a mixture with a reducing agent selected from sodium phosphate and sodium sulfite.
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