KR100360947B1 - Heat Resistant Thermoplastic Resin Composition and Process for Preparing thereof - Google Patents
Heat Resistant Thermoplastic Resin Composition and Process for Preparing thereof Download PDFInfo
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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
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Abstract
본 발명은 내열성, 내충격성, 가공성 등이 우수하고 라텍스 안정성이 극히 우수한 내열성 열가소성 수지 조성물의 제조방법에 관한 것으로, 방향족 비닐화합물, 시안화비닐 화합물, 말레이미드 화합물에 에틸렌계 불포화 아마이드로 이루어지는 단량체 조성물을 유화중합시킴을 특징으로 한다.The present invention relates to a method for producing a heat-resistant thermoplastic resin composition having excellent heat resistance, impact resistance, workability, etc., and extremely excellent latex stability. The present invention relates to a monomer composition comprising an ethylenically unsaturated amide in an aromatic vinyl compound, a vinyl cyanide compound, and a maleimide compound. It is characterized by emulsion polymerization.
Description
본 발명은 내열성 열가소성 수지조성물에 관한 것으로, 더욱 상세하게로는 말레이미드계 내열성 열가소성 수지를 제조하는 데에 있어 에틸렌계 불포화 아마이드 단량체를 사용함으로서 내열성, 내충격성, 가공성 등이 우수하고 라텍스 안정성이 극히 우수한 내열성 열가소성 수지의 제조방법에 관한 것이다.The present invention relates to a heat-resistant thermoplastic resin composition, and more particularly, by using an ethylenically unsaturated amide monomer in the production of maleimide-based thermoplastic resins, excellent heat resistance, impact resistance, processability, etc., and extremely latex stability It relates to a method for producing an excellent heat resistant thermoplastic resin.
최근 자동차 경량화의 필요성으로 인하여 ABS수지의 내열성을 향상시키기 위한 각종 제조방법이 연구되고 있으며, ABS수지의 열변형 온도를 향상시키기 위한 제조방법으로서 스티렌의 일부 또는 전량을 α-메틸스티렌으로 대체하여 내열성 ABS 수지를 제조하는 방법(미국특허 제 3,010,936호 및 4,659,790호), 말레이미드 화합물을 포함시켜 내열성 ABS 수지를 제조하는 방법(일본 특허공개 소 58-206657호, 59-135210호, 59-184243로, 63-162708호, 63-235350호, 미국특허 4,757,109호 등), 폴리카보네이트 수지와 혼련하는 방법, 무기물을 충전시키는 방법 등이 알려져 있다.Recently, various manufacturing methods for improving the heat resistance of ABS resins have been studied due to the necessity of lightening automobiles.As a manufacturing method for improving the heat deformation temperature of ABS resins, some or all of the styrene is replaced with α-methylstyrene to provide heat resistance. Method for producing ABS resin (US Pat. Nos. 3,010,936 and 4,659,790), Method for producing a heat-resistant ABS resin containing a maleimide compound (Japanese Patent Publication No. 58-206657, 59-135210, 59-184243, 63-162708, 63-235350, U.S. Patent 4,757,109 and the like), a method of kneading with a polycarbonate resin, a method of filling an inorganic material and the like are known.
그러나 α-메틸 스티렌을 이용하여 내열성 수지를 제조하는 경우 α-메틸 스티렌의 낮은 반응성과 가공시 열안정성이 떨어지는 단점이 있으며, 내열성 향상에 한계가 있다. 또한 폴리카보네이트 수지와 ABS 수지를 혼련하는 경우 가공성, 내약품성 등이 다소 문제가 있고 가격이 높아 사용에 한계가 있으며, 무기물을 증진하는 경우 내충격성이 저하되는 단점이 있다.However, when the heat-resistant resin is manufactured using α-methyl styrene, there is a disadvantage in that low reactivity of α-methyl styrene and thermal stability during processing are inferior, and there is a limit in improving heat resistance. In addition, when kneading a polycarbonate resin and an ABS resin, the processability, chemical resistance, etc. are somewhat problematic, and the price is high, so there is a limit to use, and when the inorganic material is promoted, the impact resistance is lowered.
최근에는 ABS수지의 내열성을 향상시키는 가장 바람직한 방법으로서 말레이미드 화합물의 이용이 점차 확대되고 있다. 즉, 일본 특허공개 소 58-206657호, 소 63-162708호 등에서는 말레이미드 화합물과 방향족 비닐화합물 및 시안화 비닐화합물을 공중합한 후 고무 함유 중합체와 혼합하여 사용하는 방법이 제안되었으나 일반적인 유화중합을 이용할 경우 말레이미드 화합물의 빠른 중합속도 때문에 말레이미드 화합물 함량이 높은 사슬이 생성되어 높은 유리전이온도를 갖는 사슬의 과다로 내열성은 향상되나 내충격성 및 가공성이 저하되어 중합된 라텍스의 응고과정에서 응고온도를 상승시켜 제조공정이 복잡해 지고 생산효율이 떨어지는 단점이 있다.In recent years, the use of a maleimide compound is gradually expanding as the most preferable method of improving the heat resistance of ABS resin. That is, in Japanese Patent Application Laid-Open Nos. 58-206657 and 63-162708, a method of copolymerizing a maleimide compound, an aromatic vinyl compound, and a vinyl cyanide compound and then mixing it with a rubber-containing polymer has been proposed. In this case, due to the rapid polymerization rate of the maleimide compound, a chain having a high content of the maleimide compound is formed, and thus the heat resistance is improved due to excessive chains having a high glass transition temperature, but the impact resistance and processability are lowered. This increases the complexity of the manufacturing process and has the disadvantage of low production efficiency.
또한 미국특허 제 4,757,109호의 경우 방향족 비닐화합물 및 시안화 비닐화합물과 말레이미드 화합물을 투입하여 내열성 수지를 제조하는 방법이 제안되어 있으나 이 또한 제조공정이 복잡하고 말레이미드 화합물을 증량시키는 데에 한계가 있어 내열성이 높은 수지를 얻기가 어렵다.In addition, in the case of US Patent No. 4,757,109, a method of preparing a heat resistant resin by adding an aromatic vinyl compound, a vinyl cyanide compound, and a maleimide compound has been proposed, but this also has a complicated manufacturing process and a limitation in increasing the maleimide compound. It is difficult to obtain this high resin.
그리고 일본 특허공개 소 63-235350호의 경우 방향족 비닐화합물, 시안화 비닐화합물 및 말레이미드 화합물의 혼합물을 연속적으로 투여하는 방법이 제안되어 있으나 이 또한 내충격성은 우수하나 내열성이 높은 수지를 얻는 데 한계가 있다.그리고 상기에서 언급된 제조방법들은 라텍스 안정성 때문에 고형분 함량을 올리는 데 한계가 있어 생산성 향상의 한계가 있다.In Japanese Patent Application Laid-Open No. 63-235350, a method of continuously administering a mixture of an aromatic vinyl compound, a vinyl cyanide compound, and a maleimide compound has been proposed, but this also has a high impact resistance, but has a limitation in obtaining a resin having high heat resistance. And the above-mentioned manufacturing method has a limit to increase the solid content because of the latex stability there is a limit of productivity improvement.
본 발명자들은 이와 같은 문제점을 해결하기 위하여 방향족 비닐단량체, 시안화비닐 단량체, 말레이미드 단량체에 에틸렌계 불포화 아마이드 단량체를 사용하여 유화중합으로 투여방법과 시기를 조절하여 고형분 함량이 40% 이상되고 유리전이온도가 140℃ 이상되는 내열성 공중합체를 제조하고 또한 상기에서 제조된 내열성 공중합체와 ABS 그라프트 중합체와 혼련하여 열변형 온도가 120℃ 이상되고 아이조드 충격강도가 10 이상인 내열성 열가소성 수지를 제조하게 되어 본 발명을 완성하게 되었다.In order to solve the above problems, the present inventors use an ethylenically unsaturated amide monomer in an aromatic vinyl monomer, a vinyl cyanide monomer, and a maleimide monomer to control the administration method and timing by emulsion polymerization, and the content of solid content is 40% or more and the glass transition temperature. To prepare a heat-resistant copolymer having a temperature of 140 ℃ or more and further kneaded with the heat-resistant copolymer and ABS graft polymer prepared above to produce a heat-resistant thermoplastic resin having a heat deformation temperature of 120 ℃ or more and Izod impact strength of 10 or more. To complete.
본 발명을 상세히 설명하면 다음과 같다.The present invention is described in detail as follows.
본 발명은 유화중합 방법으로서 각 성분의 첨가방법은 각 성분을 일괄 투여하는 방법, 전량 또는 일부를 연속(순차적으로) 투여하는 방법을 사용할 수 있는 데, 일괄 투여과 연속 투여방법을 조합하여 사용하는 복합형태가 바람직하다.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 (sequentially) administering a total amount or a part thereof. The form is preferred.
즉, 단량체 총 중량 중 1 내지 30중량%를 반응 개시 후 일괄 투여하고 1분 내지 2시간 동안 약 45 내지 80℃에서 반응시킨 다음, 단량체 총 중량 중 70 내지 99 중량%를 약 65 내지 80℃에서 2시간 내지 5시간에 걸쳐 연속 투여한 후 잔여 개시제를 투여하여 30분 내지 2시간 동안 반응시켜 내열성 공중합체를 제조하는 것이 바람직하다.That is, 1-30% by weight of the total weight of the monomers are collectively administered after the start of the reaction and reacted at about 45-80 ° C for 1 minute to 2 hours, and then 70-99% by weight of the total weight of the monomers is about 65-80 ° C After continuous administration over 2 to 5 hours, it is preferable to prepare a heat resistant copolymer by reacting for 30 minutes to 2 hours by administering a residual initiator.
사용되는 단량체의 조성비는 방향족 비닐화합물 30 내지 65중량부, 시안화 비닐화합물 10 내지 25중량부, 말레이미드 화합물 15 내지, 45중량부, 에틸렌 불포화아마이드 화합물 1 내지 20중량부가 적절하다.As for the composition ratio of the monomer used, 30-65 weight part of aromatic vinyl compounds, 10-25 weight part of vinyl cyanide compounds, 15-45 weight part of maleimide compounds, and 1-20 weight part of ethylenically unsaturated amide compounds are suitable.
본 발명에 사용 가능한 방향족 비닐화합물은 스티렌, α-메틸스티렌, α-에틸스티렌, o-에틸스티렌, p-에틸스티렌, 2,4-디메틸스티렌 등이며, 시안화비닐화합물로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 등이고, 말레이미드 화합물은 N-페닐말레이미드, N-메틸말레이미드, 사이클로헥실 말레이미드 등이다. 에틸렌계 불포화 아마이드로는 메타크릴아마이드, 아크릴 아마이드가 사용될 수 있고, 유화제로는 알킬 벤젠 술폰산의 나트륨염 및 칼륨염 또는 라우릴 황산의 나트륨염 및 칼륨염이 사용되며, 개시제로는 과황산염, 디이소프로필벤젠 하이드로퍼옥사이드, 큐멘 하이드로퍼옥사이드 등과 같은 과산화물과 소디움포름알데히드 술폭실레이트, 소디움에틸렌디아민 테트라아세테이트, 황산 제1철, 덱스트로즈, 피롤린산 나트륨, 아황산나트륨과 같은 환원제와의 혼합물로 된 산화-환원 촉매를 사용할 수 있다. 분자량 조절제로는 3급 도데실 메르캅탄이 사용되며 총단량체 100중량부당 0.2중량부 이하의 양으로 사용된다.Aromatic vinyl compounds usable in the present invention are styrene, α-methylstyrene, α-ethylstyrene, o-ethylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and the like, and acrylonitrile, meta And a maleimide compound are N-phenyl maleimide, N-methyl maleimide, cyclohexyl maleimide, and the like. Methacrylamide and acrylamide may be used as the ethylenically unsaturated amide, and sodium salts and potassium salts of alkyl benzene sulfonic acid or sodium salts and potassium salts of lauryl sulfate are used as emulsifiers, and persulfate, di Mixture of peroxides such as isopropylbenzene hydroperoxide, cumene hydroperoxide, and reducing agents such as sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, sodium sulfite Redox catalyst can be used. As the molecular weight regulator, tertiary dodecyl mercaptan is used and is used in an amount of 0.2 parts by weight or less per 100 parts by weight of total monomers.
본 발명에서 방향족 비닐단량체를 40중량부 미만 사용하게 되면 가공성 및 충격강도의 저하가 일어나고 70 중량부를 초과하여 사용하게 되면 내열성이 저하된다. 또한 시안화 비닐단량체를 10중량부 미만 사용하게 되면 가공성 및 충격강도의 저하가 일어나며 30중량부를 초과하여 사용하게 되면 가공시 변색이 일어난다.In the present invention, when the aromatic vinyl monomer is used in less than 40 parts by weight, workability and impact strength are lowered, and when used in excess of 70 parts by weight, heat resistance is lowered. In addition, when using less than 10 parts by weight of vinyl cyanide monomer, workability and impact strength are lowered, and when used in excess of 30 parts by weight, discoloration occurs during processing.
그리고 말레이미드 단량체를 10중량부 미만 사용하게 되면 내열성이 저하되고 45중량부를 초과하여 사용하게 되면 충격강도와 유동성이 저하된다. 또한 중합체의 pH는 2 내지 9를 유지하여야 하며 이 범위를 초과하게 되면 말레이미드의 가수분해 현상이 일어나 물성이 저하되고 이 범위 미만의 경우에는 사용되는 유화제의 유화능력이 저하된다.When the maleimide monomer is used in less than 10 parts by weight, the heat resistance is lowered. When the maleimide monomer is used in excess of 45 parts by weight, impact strength and fluidity are lowered. In addition, the pH of the polymer should be maintained at 2 to 9, and if it exceeds this range, hydrolysis of maleimide occurs, resulting in a decrease in physical properties, and in the case below this range, the emulsifying capacity of the emulsifier used is lowered.
또한 일괄투여 방법을 사용하게 되면 말레이미드 단량체와 방향족 비닐 단량체 간의 Charge-transfer Complex 형성으로 분자량 분포와 조성분포가 넓어지고 연속투여 방법만 사용하면 수율이 낮고 열분해 및 내열성이 저하된다.In addition, when the batch administration method is used, charge-transfer complex formation between the maleimide monomer and the aromatic vinyl monomer broadens the molecular weight distribution and composition distribution, and using only the continuous administration method yields low yield and thermal decomposition and heat resistance.
중합 종료 후 중합전환율은 98% 이상이며 수득된 라텍스를 단독으로 135℃ 이상의 온도에서 염화칼슘 수용액으로 응고시켜 건조시키거나 ABS 그라트트 중합체 라텍스 40중량부와 혼련하여 염화칼슘 수용액으로 응고시켜 탈수 및 건조시켜 분말 형태를 만든다. 이 때 필요에 따라 산화방지제 및 광안정제 등을 투여할 수 있다.After the completion of the polymerization, the polymerization conversion rate is 98% or more, and the latex obtained is solidified alone with an aqueous solution of calcium chloride at a temperature of 135 ° C. or higher, or kneaded with 40 parts by weight of ABS graft polymer latex, solidified with an aqueous solution of calcium chloride, dehydrated and dried. Make a powder form. At this time, antioxidant, light stabilizer, etc. can be administered as needed.
본 발명을 예시하기 위해 아래의 실시예를 기술하지만 이에 본 발명이 제한되는 것을 아니다.The following examples are described to illustrate the invention but are not intended to limit the invention thereto.
실시예에서 고형분 함량 및 생성 응고물 총량은 하기식으로부터 구할 수 있다.In the Examples, the solid content and the total amount of coagulum produced can be obtained from the following formula.
고형분 함량(%) = 고형분 무게/라텍스무게 × 100Solid content (%) = solid weight / latex weight × 100
생성응고물 총량(%) = 반응조 안의 생성응고물 무게/투여된 총 단량체의 무게 × 100% Of product coagulant = weight of product coagulant in the reactor / weight of total monomers administered × 100
생성응고물 총량이 약 0.5%를 초과할 경우에는 제조된 라텍스의 안정성이 떨어져 본 발명의 목적에 적합하지 않다. 또한 유리전이온도는 DSC(시차 주사열 분석기)로 측정하였다.If the total amount of product coagulant exceeds about 0.5%, the prepared latex is not stable and is not suitable for the purpose of the present invention. In addition, glass transition temperature was measured by DSC (differential scanning heat analyzer).
(실시예 A1)(Example A1)
질소치환된 중합반응기에 표1의 조성비 A1의 1단계 성분, 즉 이온교환수 40중량부 및 알킬벤젠술폰산 나트륨염 0.6중량부와 스티렌 8중량부, 아크릴로 니트릴 2중량부, N-페닐말레이미드 5중량부, 분자량 조절제로 3급 도데실 메르캅탄(T-DDM) 0.1중량부 혼합액을 넣고 반응기를 70℃로 올리면서 과황산 칼륨 0.1중량부를 일괄투여하여 반응을 개시하고 1시간 동안 80℃로 승온시킨 다음 표1의 조성비 A1의 2단계 성분, 즉 이온교환수 90중량부, 알킬벤제술폰산 나트륨염 1.0중량부, 스티렌 40중량부, 아크릴로니트릴 15중량부, N-페닐말레이미드 25중량부, 메타크릴아마이드 5중량부, TDDM 0.1중량부, 과황산 칼륨 0.25중량부의 혼합액을 4시간에 걸쳐 연속적으로 투여하였다.In the nitrogen-substituted polymerization reactor, the first stage component of composition ratio A1 in Table 1, namely 40 parts by weight of ion-exchanged water, 0.6 parts by weight of sodium alkylbenzenesulfonate, 8 parts by weight of styrene, 2 parts by weight of acrylonitrile, and N-phenylmaleimide Add 5 parts by weight of a 0.1 parts by weight mixture of tertiary dodecyl mercaptan (T-DDM) as a molecular weight modifier, and raise the reactor to 70 ° C., in a batch dose of 0.1 parts by weight of potassium persulfate to start the reaction, and then to 80 ° C. for 1 hour. After heating up, the two-stage components of the composition ratio A1 of Table 1, namely 90 parts by weight of ion-exchanged water, 1.0 parts by weight of alkylbenzesulfonic acid sodium salt, 40 parts by weight of styrene, 15 parts by weight of acrylonitrile, and 25 parts by weight of N-phenylmaleimide , 5 parts by weight of methacrylamide, 0.1 parts by weight of TDDM, and 0.25 parts by weight of potassium persulfate were continuously administered over 4 hours.
투입완료 후 이온교환수 10중량부, 알킬벤젠술폰산 나트륨염 0.1 및 과황산 칼륨 0.05중량부 혼합액을 일괄 투여하고 1시간 동안 교반하여 중합을 완료하였다. 중합완료 후 중합전환율은 99% 이고 생성응고물은 0.15% 정도였다.After the addition, 10 parts by weight of ion-exchanged water, 0.1 parts of alkylbenzenesulfonic acid sodium salt and 0.05 parts by weight of potassium persulfate were collectively administered and stirred for 1 hour to complete the polymerization. After completion of the polymerization, the polymerization conversion was 99% and the resultant coagulum was about 0.15%.
실시예 A2 - A4)Examples A2-A4)
상기 실시예 A1과 동일한 방법으로 실시하되 조성비를 표1의 A1 대신에 A2 내지 A4의 조성비로 실시하였다.The composition was carried out in the same manner as in Example A1, but the composition ratio was performed in the composition ratio of A2 to A4 instead of A1 in Table 1.
그 결과는 표1에 나타 내었다.The results are shown in Table 1.
비교예 B1 내지 B3)Comparative Examples B1 to B3)
실시예 A1과 동일한 방법으로 실시하되 조성비를 표1의 비교예 B1 내지 B3의 조성비를 사용하였다. 그 결과는 표1에 나타내었다.The composition was carried out in the same manner as in Example A1, but the composition ratio of Comparative Examples B1 to B3 in Table 1 was used. The results are shown in Table 1.
사용예 C1)Example C1)
상기 실시예 A1에서 제조된 내열성 열가소성 수지 라텍스 A1 60중량부와 ABS 그라프트 중합체 [(주) 럭키제품 DP210] 라텍스 40중량부, 산화방지제 0.2중량부를 혼련하여 응고하고 세척하여 건조시켜 분말형태로 제조하고 이 분말 100중량부 당 활제 0.5중량부, 산화방지제 0.4중량부 및 자외선 안정제 0.2중량부를 투여하여 240℃ 내지 250℃의 실린더 온도에서 2축 혼련기를 사용하여 압출시켜 펠렛 행태로 제조하였다. 이 펠렛을 이용하여 시편을 제조하고 물성을 측정하여 표2에 나타 내었다.60 parts by weight of the heat-resistant thermoplastic resin latex A1 prepared in Example A1 and ABS graft polymer [Lucky Products DP210] 40 parts by weight of latex, 0.2 parts by weight of antioxidant, kneaded, washed and dried to prepare a powder form 0.5 part by weight of lubricant, 0.4 part by weight of antioxidant and 0.2 part by weight of UV stabilizer were administered per 100 parts by weight of the powder, and extruded using a twin screw kneader at a cylinder temperature of 240 ° C to 250 ° C to prepare pellets. Specimens were prepared using this pellet and the physical properties thereof were shown in Table 2.
사용예 C2)Example C2)
상기 실시예 A1에서 제조된 내열성 열가소성 수지 라텍스를 응고시켜 제조한 분말과 ABS 그라프트 중합체를 응고시켜 제조한 분말을 혼련하여 사용예 C1의 방법으로 부원료를 투입하고 가공하여 물성을 측정하여 표2에 나타 내었다.The powder prepared by coagulating the heat-resistant thermoplastic latex prepared in Example A1 and the powder prepared by coagulating the ABS graft polymer were kneaded, and the raw materials were added and processed by the method of Example C1 to measure physical properties. Appeared.
사용예 C3 내지 C6)Use Examples C3 to C6)
사용예 C1과 C2의 방법과 동일한 방법으로 실시하되 조성비를 사용예 C3내지 C6의 조성비를 사용하였다. 그 결과는 표2에 나타내었다.The composition was carried out in the same manner as in Examples C1 and C2, but the composition ratio of Composition C3 to C6 was used. The results are shown in Table 2.
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| US12091549B2 (en) | 2020-05-26 | 2024-09-17 | Lg Chem, Ltd. | Method for preparing carboxylic acid modified-nitrile based copolymer latex |
| US12286490B2 (en) | 2020-11-05 | 2025-04-29 | Lg Chem, Ltd. | Polymer production method |
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| JPS63273612A (en) * | 1987-04-30 | 1988-11-10 | Kanegafuchi Chem Ind Co Ltd | Methacrylamide based copolymer |
| JPH01249817A (en) * | 1988-02-26 | 1989-10-05 | Bayer Ag | Terpolymer latex |
| KR890014598A (en) * | 1988-03-31 | 1989-10-24 | 리히터스, 바르츠 | Heat-resistant strained thermoplastic molding materials comprising copolymers, their preparation and uses |
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| KR910004685A (en) * | 1989-08-31 | 1991-03-29 | 아더 엠. 킹 | Quaternary copolymers and blends of ABS and quaternary copolymers |
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| JPS63256633A (en) * | 1987-04-14 | 1988-10-24 | Kanegafuchi Chem Ind Co Ltd | Extruded foam made of heat-resistant methacrylamide copolymer |
| JPS63273612A (en) * | 1987-04-30 | 1988-11-10 | Kanegafuchi Chem Ind Co Ltd | Methacrylamide based copolymer |
| JPH01249817A (en) * | 1988-02-26 | 1989-10-05 | Bayer Ag | Terpolymer latex |
| KR890014598A (en) * | 1988-03-31 | 1989-10-24 | 리히터스, 바르츠 | Heat-resistant strained thermoplastic molding materials comprising copolymers, their preparation and uses |
| JPH024810A (en) * | 1988-06-23 | 1990-01-09 | Showa Denko Kk | Production of thermoplastic resin containing maleimide |
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| US12091549B2 (en) | 2020-05-26 | 2024-09-17 | Lg Chem, Ltd. | Method for preparing carboxylic acid modified-nitrile based copolymer latex |
| US12286490B2 (en) | 2020-11-05 | 2025-04-29 | Lg Chem, Ltd. | Polymer production method |
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