KR0141352B1 - Thermoplastic resin composition for use of processable improvement maetrial - Google Patents
Thermoplastic resin composition for use of processable improvement maetrialInfo
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- KR0141352B1 KR0141352B1 KR1019930032315A KR930032315A KR0141352B1 KR 0141352 B1 KR0141352 B1 KR 0141352B1 KR 1019930032315 A KR1019930032315 A KR 1019930032315A KR 930032315 A KR930032315 A KR 930032315A KR 0141352 B1 KR0141352 B1 KR 0141352B1
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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
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- C08F212/10—Styrene with nitriles
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- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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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
- C08F220/10—Esters
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- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- C08F220/10—Esters
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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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Abstract
방향족 비닐단량체 60-95중량부와 비닐시안계 단량체 5-40중량부, 알킬기의 탄소수가 1에서 8이하의 알킬아크릴레이트 단량체 0-10중량부, 알킬기의 탄소수가 1에서 8이하의 알킬메타크릴레이트 단량체 0-10중량부로 이루어진 혼합 단량체를 개시제, 유화제와 함께 2단계 또는 다단계 유화 중합하여 입자 직경 0.05-0.3μ인 라텍스를 얻고, 이를 산 또는 염으로 응집하여 건조한 중량평균 분자량 80만 이상임을 특징으로 하는 열가소성 수지 조성물.60-95 parts by weight of aromatic vinyl monomer, 5-40 parts by weight of vinyl cyanic monomer, 0-10 parts by weight of alkyl acrylate monomer having 1 to 8 carbon atoms in the alkyl group and alkyl methacrylate having 1 to 8 carbon atoms in the alkyl group A mixed monomer consisting of 0-10 parts by weight of a monomer is obtained by two-step or multi-step emulsion polymerization with an initiator and an emulsifier to obtain a latex having a particle diameter of 0.05-0.3 μ, and agglomerated with an acid or a salt to have a dry weight average molecular weight of 800,000 or more. Thermoplastic resin composition.
Description
본 발명은 열가소성 수지 특히 염화비닐 수지 또는 아크릴로 니트릴-부타디엔-스티렌수지(이하 ABS수지)의 가공성을 개량하기 위해 사용되는 고분자 수지의 조성물(이하 가공조제)에 관한 것이다.The present invention relates to a composition (hereinafter processing aid) of a polymer resin used for improving the processability of a thermoplastic resin, in particular a vinyl chloride resin or an acrylonitrile-butadiene-styrene resin (hereinafter ABS resin).
염화비닐 수지는 열가소성 성형수지로서 널리 알려져 있으며, 물리적 특성이나 전기적 특성 및 화학적 특성이 우수하기 때문에 통상적으로 매우 댜양한 용도로 광범위하게 적용되고 있다.Vinyl chloride resins are widely known as thermoplastic molding resins, and are widely applied in a wide variety of applications because of their excellent physical, electrical, and chemical properties.
그러나 염화비닐수지는 가공작업성이 불량한 단점을 가지고 있다.However, vinyl chloride resin has the disadvantage of poor workability.
즉 염화비닐수지는 지극히 제한된 온도범위에서 가공되어야 하며 그나마 이 가공온도의 범위도 염화비닐수지의 열적분해온도와 근접해 있는데, 이것은 염화비닐수지의 용융물의 점도가 높고 유동성이 나쁘며, 열적으로 분해하려는 성질을 갖고 있기 때문이다.In other words, the vinyl chloride resin should be processed in a very limited temperature range, but the processing temperature is also close to the thermal decomposition temperature of the vinyl chloride resin, which has high viscosity, poor fluidity, and thermal decomposition properties of the melt of the vinyl chloride resin. Because it has.
또한 염화비닐수지는 가공시 겔 상태에 도달하는 시간이 길고, 가공시 염화비닐수지의 입자로부터 단시간내에 일정한 용융물을 얻기가 어렵다.In addition, the vinyl chloride resin takes a long time to reach the gel state during processing, and it is difficult to obtain a constant melt from the particles of the vinyl chloride resin during processing in a short time.
아울러 염화비닐수지 혹은 ABS수지는 1차 혹은 2차 이상의 가공시 단순한 작업조건이나 첨가제의 보완으로 전반적인 가공성을 개선시킬 수는 있으나 고온에서 성형시킬 경우 고온신율의 저하로 정교한 성형품의 제조에 어려움을 가져올뿐만 아니라 작업온도 범위가 지극히 제한되어 작업조건 조절이 좋지 않은 단점이 있었다.In addition, polyvinyl chloride resin or ABS resin can improve overall processability by supplementing simple working conditions or additives when processing primary or secondary, but when forming at high temperature, it may cause difficulty in manufacturing sophisticated molded products due to low temperature elongation. In addition, the working temperature range is extremely limited, which makes it difficult to control the working conditions.
이와같은 염화비닐수지 혹은 ABS수지의 문제점을 해결하기 위해 사용되어지는 가공조제는 미국특허 제 3,673,283호, 제 3,833,686호, 제 3,903,198호, 제 3,919,137호, 제 3,991,135호, 제 4,051,200호, 제 4,668,740호 등에 이미 제시되어 있다.Processing aids used to solve such problems of vinyl chloride resin or ABS resin are U.S. Pat. Already presented.
제시된 방법으로는 염화비닐 수지 또는 ABS수지의 중합시 아크릴레이트계통의 단량체를 반응기 속에서 같이 중합하여 그 자체의 가공성을 향상시키는 방법과 아크릴레이트 수지를 다단계 공정에 의하여 중합한 후 염화비닐수지 또는 ABS수지와의 혼합에 의해 가공성을 향상시키는 방법이다.In the proposed method, the polymerization of vinyl chloride resin or ABS resin is carried out by polymerization of acrylate monomers in a reactor to improve its processability, and the polymerization of acrylate resin by a multi-step process, followed by polymerization of vinyl chloride resin or ABS. It is a method of improving workability by mixing with resin.
그러나 모든 조성물 및 제조방법이 아크릴계 단량체를 주성분으로 하는 것으로 가공조제의 주요특성에는 부합되지만 근본적으로 가공기기의 금속표면에의 점착문제와 기계적 부하상승 및 가격이 상대적으로 비싸다는 문제를 안고 있었다.However, although all compositions and manufacturing methods are based on acrylic monomers, they meet the main characteristics of processing aids, but they have problems of adhesion to the metal surface of the processing equipment, increase in mechanical load, and relatively high price.
이러한 문제점을 개선하기 위하여 여러가지 단량체를 갖는 조성물이 개발되고 있으나 아직 모든 성질을 만족할만한 성과를 보여주지 못하고 있어 열가소성 수지의 가공특성을 크게 개선시킬 수 있는 새로운 가공조제의 개발요구가 커지고 있다.In order to improve such a problem, a composition having various monomers has been developed, but it has not yet been shown to satisfy all the properties, the demand for the development of a new processing aid that can greatly improve the processing characteristics of the thermoplastic resin.
이에 본 발명자들은 상기와 같은 문제점을 예의 주시하며 아크릴계 가공조제가 갖고 있는 장점(투명성, 색상, 내후성, 무독성 등)은 최대한 살리면서 가격이 싼 방향족 비닐단량체와 비닐시안계 단량체를 주조성물로 하는 가공조제를 제조하여 사용해본 결과 열가소성 수지의 가공특성을 크게 개선시키는 결과를 얻을 수 있어 본 발명을 완성하게 되었다.The present inventors pay close attention to the above problems and process the acrylic vinyl processing aid and the cost-effective aromatic vinyl monomer and vinyl cyan monomer as a cast material while maintaining the advantages (transparency, color, weather resistance, non-toxicity, etc.) of the acrylic processing aid. As a result of preparing and using the preparation, a result of greatly improving the processing characteristics of the thermoplastic resin can be obtained, thus completing the present invention.
본 발명을 설명하면 방향족 비닐단량체 60-95 중량부와 비닐시안계 단량체 5-40 중량부, 알킬기의 탄소수가 1에서 8사이의 알킬아크릴레이트 단량체 0-10 중량부, 알킬기의 탄소수가 1에서 8사이의 알킬메타크릴레이트 0-10중량부를 유화제와 개시제, 증류수와 함께 30-110℃사이의 반응온도에서 2단계 이상의 할부 반응에 의해 중량 평균 분자량이 80만 이상인 고분자량 수지 조성물을 얻고 이를 염화비닐수지 또는 ABS수지와 일정량 혼합하여 고온신을 상승과 가공시의 기계적 부하감소를 확인하는 것이다.Referring to the present invention, 60-95 parts by weight of aromatic vinyl monomer, 5-40 parts by weight of vinyl cyanide monomer, 0-10 parts by weight of alkyl acrylate monomer having 1 to 8 carbon atoms of alkyl group, and 1 to 8 carbon atoms of alkyl group A high molecular weight resin composition having a weight average molecular weight of 800,000 or more was obtained by two or more installment reactions at an reaction temperature of 30 to 110 ° C with an emulsifier, an initiator, and distilled water. Mixing with resin or ABS resin in a certain amount to check the rise of high temperature and reduction of mechanical load during processing.
본발명을 구체적으로 설명하면 다음과 같다.The present invention will be described in detail as follows.
염화비닐수지의 단점인 겔화 속도지연, 열안정성 불량, 가공온도의 제한, 고온가공시의 신율부족으로 인한 정교한 제품 생산의 한계등을 개선하기 위해 첨가되는 물질인 가공 조제로는 초기에 가소제를 사용하였으나 이는 열변형온도의 저하, 충격강도의 저하, 인장강도의 저하 및 휘발물질의 문제 등으로 현재는 거의 사용되지 않고 있다.Plasticizers are initially used as processing aids, which are added to improve the disadvantages of vinyl chloride resins such as gelation delay, poor thermal stability, limitation of processing temperature, and limitation of production of sophisticated products due to lack of elongation at high temperature. However, this is rarely used at present because of a decrease in thermal deformation temperature, a decrease in impact strength, a decrease in tensile strength and a problem of volatile materials.
위의 가소제의 문제점을 개선하기 위해 최근 개발된 아크릴레이트를 주성분으로 하는 가공조제는 염화비닐수지 가공의 단점을 상당부분 해소 하였으나 수지자체가 고분자량일뿐 아니라 조성물의 특성상 기계와의 점착력 증대로 인한 가공시의 기계적인 부하상승 문제뿐 아니라 장기간의 생산시 탄화물 발생빈도가 높게 되었다.In order to improve the above problems of plasticizers, the recently developed acrylate-based processing aids have largely eliminated the disadvantages of vinyl chloride resin processing, but the resin itself is not only high molecular weight but also due to the increased adhesive strength with the machine due to the characteristics of the composition. Not only the mechanical load rise problem in the city, but also the occurrence of carbides in the long-term production became high.
따라서, 염화비닐 수지의 가공조제가 갖추어야 할 기본적인 특징인 겔화시간 단축, 열안정성 개선, 고온신율증대 등을 부여하면서 아크릴레이크계 가공조제가 갖고 있는 독특한 장점인 투명성을 유지하면서 색상조절이 용이하고, 내후성 및 특성 문제가 없는 점등을 갖추면서 여러 단점을 보완하여 기계적 부하감소와 탄화물 발생억제를 위해 별도의 조성물을 갖는 수지가 요구되었고 본 발명자들은 그의 한 방법으로 방향족 비닐 단량체와 비닐시안계 단량체를 주조성물로 하는 고분자량 가공조제를 개발하였다.Therefore, it is easy to adjust color while maintaining transparency, which is a unique advantage of acrylic flake processing aids, while giving gelation time, thermal stability improvement, and high temperature elongation, which are basic characteristics of processing aid of vinyl chloride resin, The resin having a separate composition is required for reducing mechanical load and suppressing carbide generation by supplementing various disadvantages while having lighting without weather resistance and characteristic problems, and the present inventors have used aromatic vinyl monomers and vinyl cyanide monomers as their methods. A high molecular weight processing aid has been developed as a composition.
여기에서 다시 살펴보아야 할 첫번째 사항으로는 조성물의 비율에 따라 염화비닐수지와의 상용성이 결정되고 이것은 염화비닐수지내에 가공조제의 균일한 분산능력과 관계가 있기 때문에 비율결정이 매우 중요하다는 것이다.The first point to be reexamined here is that the compatibility with the vinyl chloride resin is determined by the proportion of the composition, which is related to the uniform dispersion ability of the processing aid in the vinyl chloride resin.
상용성은 일반적으로 얻어진 용해도 계수의 차이로 비교할 수 있는데 용해도 계수의 차이가 클수록 상용성이 떨어진다고 말할 수 있다.The compatibility can generally be compared with the difference in solubility coefficients obtained. It can be said that the greater the difference in solubility coefficients, the lower the compatibility.
각 수지조성물의 용해도 계수를 표 1에 나타내었다.Table 1 shows the solubility coefficients of each resin composition.
본 발명에서 사용한 방향족 비닐 단량체로서는 스티렌이 가장 바람직하나 α-메틸스티렌, 비닐나프탈렌 또는 3,4-디메틸스티렌, 비닐톨루엔, 등의 스티렌의 알킬치환체등도 사용될 수 있는데 투입되는 양은 전체 수지조성물의 60이상 95이하 중량부가 사용 가능한데 가장 바람직하게는 70이상 80이하 중량부이다.As the aromatic vinyl monomer used in the present invention, styrene is most preferred, but alkyl substituents of styrene such as α-methylstyrene, vinylnaphthalene or 3,4-dimethylstyrene, vinyltoluene, and the like may also be used. 95 parts by weight or more may be used, most preferably 70 parts by weight or less and 80 parts by weight.
본 발명에서 사용한 비닐시안계 단량체로서는 아크릴로니트릴이 가장 바람직하나 메타크릴로니트릴 등도 사용될 수 있는데 투입되는 양은 전체수지 조성물의 5 이상 40이하 중량부가 사용 가능한데 가장 바람직하게는 20이상 30이하 중량부이다.Acrylonitrile is most preferred as the vinyl cyanide monomer used in the present invention, but methacrylonitrile and the like may also be used. The amount added is 5 to 40 parts by weight of the total resin composition, and most preferably 20 to 30 parts by weight. .
본발명에서 10중량부 이하로 소량 사용되기는 하지만 염화비닐수지와의 상용성 증대를 위하여 쓰여지는 단량체로서는 알킬기의 탄소수가 1-8개의 알킬메타크릴레이트와 알킬아크릴레이트를 들 수 있는데 가장 바람직하게는 메틸메타크릴레이트와 에틸아크릴레이트이다.Although used in a small amount of less than 10 parts by weight in the present invention, monomers used for increasing compatibility with vinyl chloride resin include alkyl methacrylates and alkyl acrylates having 1 to 8 carbon atoms. Methyl methacrylate and ethyl acrylate.
두번째로 살펴보아야 할 사항으로는 분자량의 조절이다.The second thing to look at is the control of molecular weight.
염화비닐 수지의 일반적인 가공시의 겔화 촉진과 고온가공시의 신율향상은 일반적인 기술로는 동시에 완벽한 만족이 어렵다는 것이다.The acceleration of gelation in general processing of vinyl chloride resins and the improvement of elongation at high temperatures are difficult to achieve at the same time with general techniques.
가공조제의 분자량이 낮을 경우 겔화는 촉진되지만 고온신율은 향상되지 못하고 분자량이 높을 경우 그와 반대의 특성을 나타내기 때문이다.If the molecular weight of the processing aid is low, the gelation is promoted, but the high temperature elongation does not improve, but if the molecular weight is high, the opposite characteristics are shown.
본 발명에서는 일반적인 겔화촉진 기능뿐만 아니라 고도의 고온신율 향상을 꾀하기 위해 독특한 중합방법을 택하였다.In the present invention, a unique polymerization method was selected in order to achieve high temperature elongation as well as general gelation promoting function.
중합반응 온도는 중합속도와 밀접한 연관이 있기 때문에 이의 조절이 매우 중요하다.Since the polymerization temperature is closely related to the polymerization rate, its control is very important.
중합이 진행되고 있는 부분에 새로운 단량체가 계속 투입되어야 고분자량의 수지조성물을 얻을 수 있기 때문에 중합초기에 많은 단량체를 한꺼번에 투입하여 반응을 진행시킨다.Since a new monomer is continuously added to the portion where the polymerization is being progressed to obtain a high molecular weight resin composition, a large number of monomers are added at the beginning of the polymerization to proceed with the reaction.
그러나 일단 반응이 진행되면 급격한 반응속도에 의해 반응온도가 상승하고 분자량이 낮은 수지조성물이 얻어지고 분자량 조절이 용이하지 못하다.However, once the reaction proceeds, the reaction temperature rises due to the rapid reaction rate, and a resin composition having a low molecular weight is obtained, and molecular weight control is not easy.
이런 문제를 해결하기 위해 투입해야할 단량체들을 일정시간 동안 균등 적가시켜 반응온도 상승을 억제하여 원하는 분자량을 얻는 방법이 제시되었다.In order to solve this problem, a method of obtaining a desired molecular weight by suppressing an increase in the reaction temperature by adding the monomers to be added uniformly for a certain time has been proposed.
그러나 균등적가 방식은 반응의 진행과정에 따라 다소의 품질편차를 가져오는 단점이 발견 되었다.However, it has been found that the equalization method has some quality deviations depending on the progress of the reaction.
이에 본 발명자들은 일시에 반응 시킬 단량체를 투입하면서도 반응온도의 급격한 상승시 일정량의 냉각수를 반응기 내에 직접 투입하여 반응온도 상승을 억제하여 반응속도를 조절하는 독특한 반응온도 조절 방식(Post-Cooling방식)을 택하여 고분자량의 수지조성물을 얻을 수 있었다.Therefore, the present inventors introduced a unique reaction temperature control method (Post-Cooling method) to control the reaction rate by suppressing the rise of the reaction temperature by directly adding a certain amount of cooling water into the reactor when the reaction temperature is rapidly increased while the monomer to be reacted at one time. To obtain a high molecular weight resin composition.
이하 본 발명을 실시예와 비교예로서 설명하면 다음과 같다.Hereinafter, the present invention will be described as Examples and Comparative Examples.
그러나 실시예와 비교예로서 본발명이 한정되는 것은 아니다.However, the present invention is not limited to Examples and Comparative Examples.
[실시예 1]Example 1
(Ⅰ) 1단계 반응(Ⅰ) One step reaction
스티렌 30중량부30 parts by weight of styrene
아크릴로니트릴 10중량부10 parts by weight of acrylonitrile
올레인산나트륨 0.7중량부0.7 parts by weight of sodium oleate
칼륨퍼설페이트 0.15중량부0.15 parts by weight of potassium persulfate
증류수 100중량부100 parts by weight of distilled water
상기 조성물을10ℓ들이 중합반응기에 넣고 70℃까지 내부온도를 승온시킨 뒤 반응이 시작되어 내부 반응온도가 상승하여 95℃에 이르면The composition was placed in a 10-l polymerization reactor and the internal temperature was raised to 70 ° C., and then the reaction started. The internal reaction temperature was increased to 95 ° C.
(Ⅱ) 2단계 반응(II) two-step reaction
증류수 20중량부20 parts by weight of distilled water
를 반응기에 넣어 더 이상의 온도상승을 막는다.To prevent further rise in temperature.
중합반응은 약 3시간 이내에 완결되며 입자직경 0.12μ, pH 9.0, 중합전환율 96%인 라텍스를 얻는다.The polymerization reaction was completed within about 3 hours to obtain a latex having a particle diameter of 0.12 mu, pH 9.0, and a polymerization conversion rate of 96%.
(Ⅲ) 3단계 반응(III) three-step reaction
2단계에서 얻은 라텍스 140중량부140 parts by weight of latex obtained in step 2
스티렌 45중량부45 parts by weight of styrene
아크릴로니트릴 15중량부15 parts by weight of acrylonitrile
올레인산나트륨 1.2중량부1.2 parts by weight of sodium oleate
칼륨퍼설페이트 0.15중량부0.15 parts by weight of potassium persulfate
증류수 60중량부60 parts by weight of distilled water
상기 조성물을 10ℓ들이 중합반응기에 넣고 70℃까지 내부온도를 승온시킨 뒤 반응이 시작되어 내부반응온도가 상승하여 95℃에 이르면The composition was put into a 10-l polymerization reactor and the internal temperature was raised to 70 ° C., and then the reaction started. The internal reaction temperature increased to 95 ° C.
(Ⅳ) 4단계 반응(Iv) four-step reaction
증류수 20중량부20 parts by weight of distilled water
를 반응기에 투입하여 더 이상의 온도상승을 막고 반응온도가 80℃에 이르면 같은 온도에서 2시간 숙성 반응시켜 반응을 종결시킨다.To the reactor to prevent further rise in temperature and when the reaction temperature reaches 80 ℃ by aging at the same temperature for 2 hours to terminate the reaction.
중합반응은 약 5시간 이내에 완결되며 입자직경 0.15μ, pH 9.0, 중합전환율 98%인 라텍스를 얻는다.The polymerization reaction is completed within about 5 hours to obtain a latex having a particle diameter of 0.15 mu, pH 9.0, and a polymerization conversion rate of 98%.
이와같이 4단계 반응으로 얻은 가공조제 라텍스 100중량부에 증류수 100중량부를 첨가하여 희석한 후 가열 교반하는데, 온도가 70℃에 이르면 10% 염화칼슘 용액 12중량부를 첨가하여 라텍스를 응집시킨 다음 온도를 110℃까지 상승시켜 서스펜션 상태의 단단한 입자들을 형성시킨다.Thus, 100 parts by weight of distilled water was added to 100 parts by weight of the processing aid latex obtained by the four-step reaction, and the mixture was diluted by heating. When the temperature reached 70 ° C, 12 parts by weight of 10% calcium chloride solution was added to agglomerate the latex and the temperature was 110 ° C. Ascending to form hard particles in suspension state.
이어서 원심분리기에서 탈수, 세척하여 건조함으로써 가공조제를 얻는다.Subsequently, the processing aid is obtained by dehydration, washing and drying in a centrifuge.
얻어진 가공조제를 아래와 같이 열안정제와 활제를 첨가하여 별도의 시험기기와 방법에 따라 물성을 측정하여 표 2에 나타내었다.Thermal stabilizers and lubricants were added to the obtained processing aids, and their physical properties were measured according to separate test equipment and methods.
염화비닐수지(중합도 1000) 100중량부100 parts by weight of vinyl chloride resin (polymerization degree 1000)
가공조제 4중량부4 parts by weight of processing aid
다이부틸틴 말레이트 1중량부Dibutyltin maleate 1 part by weight
활제(폴리에틸렌왁스) 0.2중량부0.2 parts by weight of lubricant (polyethylene wax)
[비교예 1-10, 실시예 2-3][Comparative Example 1-10, Example 2-3]
실시예 1의 1단계 및 3단계에서 사용한 단량체가 다른 것 이외에는 동일한 순서와 방법(공정)절차에 의하여 중합 전환율 96-99.5% 라텍스를 얻었고 이에 대한 응집, 건조, 물성 비교도 실시예 1과 같다.Polymerization conversion rate 96-99.5% latex was obtained by the same procedure and method (procedure) procedure except that the monomers used in steps 1 and 3 of Example 1 were the same as those of Example 1.
사용되어진 단량체의 종류와 양을 표 3에 나타내었다.Table 3 shows the types and amounts of monomers used.
(약어)(Abbreviation)
ST:스티렌ST: Styrene
AN:아크릴로니트릴AN: Acrylonitrile
MMA:메틸 메타크릴레이트MMA: methyl methacrylate
EA:에틸 아크릴레이트EA: Ethyl Acrylate
BA:부틸 아크릴로니트릴BA: Butyl acrylonitrile
BMA:부틸 메타크릴레이트BMA: Butyl methacrylate
EA:에틸 아크릴로니트릴EA: Ethyl Acrylonitrile
* Test 방법 및 조건* Test method and condition
1) 인장강도:ASTM D638(at 25℃)1) Tensile Strength: ASTM D638 (at 25 ℃)
2) 신율:ASTM D6382) Elongation: ASTM D638
① 25℃:10mm/min 속도로 당김① Pull at 25 ℃: 10mm / min speed
② 100℃, 140℃:3분 예열후 100mm/min 속도로 당김② 100 ℃, 140 ℃: Pulled at 100mm / min speed after 3 minutes preheating
3)용융특성:Brabender Fusion Test (175℃, 30rpm, 48g)3) Melting Characteristics: Brabender Fusion Test (175 ℃, 30rpm, 48g)
(Compound:106.2→D-Comp'd, 2.0→가공조제)(Compound: 106.2 → D- Comp'd, 2.0 → Processing Aids)
4)중량평균분자량:GPC4) Weight average molecular weight: GPC
[비교예 11-13]Comparative Example 11-13
실시예 1과 전체적으로 투입되는 조성물과 1단계의 반응 절차는 전적으로 동일하나 2, 4단계의 반응 진행방법이 다르며 이를 표 4에 나타내었다.The composition and the one-step reaction procedure of the first step and the composition as a whole are completely the same, but the reaction proceeding method of step 2, 4 is different and shown in Table 4.
93%이상의 중합 전환율을 갖는 라텍스를 실시예 1과 동일한 방법으로 응집, 건조하여 물성을 확인 하였고, 그 결과를 표 5에 나타내었다.Latex having a polymerization conversion of 93% or more was agglomerated and dried in the same manner as in Example 1 to check physical properties, and the results are shown in Table 5.
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