KR20120058773A - Method for preparing polymethylmethacrylate resin composition with good thermal property and polymethylmethacrylate resin composition prepared by the method - Google Patents

Method for preparing polymethylmethacrylate resin composition with good thermal property and polymethylmethacrylate resin composition prepared by the method Download PDF

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KR20120058773A
KR20120058773A KR1020100120223A KR20100120223A KR20120058773A KR 20120058773 A KR20120058773 A KR 20120058773A KR 1020100120223 A KR1020100120223 A KR 1020100120223A KR 20100120223 A KR20100120223 A KR 20100120223A KR 20120058773 A KR20120058773 A KR 20120058773A
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mercaptan
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polymethyl methacrylate
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이영수
전은진
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엘지엠엠에이 주식회사
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    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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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    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • 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
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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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    • 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
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    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

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Abstract

PURPOSE: A manufacturing method of a polymethylmethacrylate resin composition is provided to use a cross-linkable monomer with fluorene structure at suspension polymerization, thereby providing a suspension-polymerized polymethylmethacrylate polymer with excellent thermals resistance. CONSTITUTION: A manufacturing method of a polymethylmethacrylate resin comprises a step of polymerizing 100.0 parts by weight of a monomer mixture, 0.01-1 parts by weight of an initiator, 0.1-5.0 parts by weight of a chain transfer agent, 0.1-5 parts by weight of a crosslinkable monomer having a functional group of fluorene structure. The monomer mixture comprises 60-99.9 weight% of methylmethacrylate monomer or methylmethacrylate, and 0.1-40 weight% of a comonomer. Alkyl acrylate containing a C1-8 alkyl group for improving processability, alpha-methylstyrene for obtaining high thermal resistance, or maleimide-based monomer containing cyclohexyl maleimide is used for the comonomer.

Description

내열성이 우수한 폴리메틸메타크릴레이트 수지 조성물을 제조하는 방법 및 그 방법에 의해 제조된 폴리메틸메타크릴레이트 수지 조성물 {METHOD FOR PREPARING POLYMETHYLMETHACRYLATE RESIN COMPOSITION WITH GOOD THERMAL PROPERTY AND POLYMETHYLMETHACRYLATE RESIN COMPOSITION PREPARED BY THE METHOD}METHOD FOR PREPARING POLYMETHYLMETHACRYLATE RESIN COMPOSITION WITH GOOD THERMAL PROPERTY AND POLYMETHYLMETHACRYLATE RESIN COMPOSITION PREPARED BY THE METHOD}

본 발명은 우수한 내열성을 요구하는 분야에 적용가능한 폴리메틸메타크릴레이트 수지 조성물에 관한 것이다.The present invention relates to a polymethyl methacrylate resin composition applicable to fields requiring excellent heat resistance.

폴리메틸메타크릴레이트 수지(polymethylmethacrylate resin)는 메틸메타크릴레이트의 중합체로서, 투명성 및 내후성이 우수하고, 기계적 물성이 우수해 투명성을 요구하는 다양한 분야에서 사용되고 있는 대표적인 수지이다.Polymethylmethacrylate resin (polymethylmethacrylate resin) is a polymer of methyl methacrylate, is a typical resin that is used in various fields that require transparency because of excellent transparency and weather resistance, excellent mechanical properties.

이러한 폴리메틸메타크릴레이트 수지는 메틸메타크릴레이트만을 단독으로 중합하거나 소량의 다른 아크릴레이트 단량체를 괴상중합, 현탁중합, 용액중합 등으로 공중합하여 제조되고 있다. 이렇게 제조된 폴리메틸메타크릴레이트 수지는 그 우수한 광학적 특성으로 인하여 광학재료로 많이 사용되고 있으나, 내열성이 부족하여 LCD용 광학 필름이나, 기타 내열 특성을 요구하는 분야에서는 그 사용이 제한되고 있으며, 그에 따라 지금도 폴리메틸메타크릴레이트 수지의 내열성을 향상시키기 위한 다양한 방법이 시도되고 있다.Such polymethyl methacrylate resins are prepared by polymerizing only methyl methacrylate alone or copolymerizing small amounts of other acrylate monomers by bulk polymerization, suspension polymerization, solution polymerization, and the like. Polymethyl methacrylate resin prepared as described above is widely used as an optical material due to its excellent optical properties, but its use is limited in areas requiring an optical film for LCD or other heat resistance properties due to its lack of heat resistance. Even now, various methods for improving the heat resistance of polymethyl methacrylate resin have been tried.

본 출원인에 의해 출원되어 등록된 발명의 명칭이 "내열성 및 투명성이 우수한 메타크릴계 공중합체"인 한국등록특허 제10-0653951호에는 내열성 및 투명성이 우수할 뿐만 아니라 내약품성, 내충격성, 성형 가공성에 있어 뛰어난 메타크릴계 공중합체를 제조하는 방법이 개시되어 있다. 이 특허문헌에 따르면, 말레이미드계 단량체를 포함하는 특정한 비의 단량체와 스티렌계 단량체를 사용하여 내열성을 향상하였으나, 이 경우, 중합시간이 길어지며, 말레이미드계 단량체의 경우, 환경 규제를 받는 물질이라는 문제가 있다. 또한, 메틸메타크릴레이트 단량체와 메타크릴산을 공중합하여 내열성이 우수한 폴리메틸메타크릴레이트를 제조하는 경우도 있으나, 이 경우, 메타크릴산에 의한 수분 흡수량이 증가하는 문제를 가지고 있다.Korean Patent No. 10-0653951, entitled "Methacrylic Copolymer Having Excellent Heat Resistance and Transparency," filed and registered by the present applicant, has excellent heat resistance and transparency as well as chemical resistance, impact resistance, and molding processability. A method for producing a methacrylic copolymer excellent in the present invention is disclosed. According to this patent document, the heat resistance is improved by using a specific ratio of monomers and styrene monomers containing maleimide monomers, but in this case, the polymerization time is long, and in the case of maleimide monomers, substances subject to environmental regulation There is a problem. In addition, although the methyl methacrylate monomer and methacrylic acid are copolymerized to produce polymethyl methacrylate having excellent heat resistance, in this case, there is a problem in that the amount of water absorption by methacrylic acid is increased.

히라타(Toshimi Hirata)와 공동연구자들은 상업적으로 판매되는 폴리메틸메타크릴레이트를 질소 분위기와 대기 분위기에서 열 중량 분석한 그들의 연구결과(Macromolecules, 1985, V18, p1410-1418)에서 폴리메틸메타크릴레이트의 열에 의한 중량감소는 160~240℃의 영역에서 초기에 불순물과 잔류단량체의 휘발에 의해 발생하고 이후 주쇄 말단의 이중결합의 분해에 의해 발생하며, 240℃ 이상에서는 주쇄의 불규칙 절단이 발생하는 것으로 보고하였다. 그리고 그들의 연구결과에 의하면 열 중량분석 시 질소분위기에 비해 대기 분위기에서는 160~240℃의 영역에서 중량감소가 덜하나, 240℃ 이상의 영역에서는 오히려 중량감소가 급격히 발생하였다. 이는 산소가 주쇄말단의 구조를 보다 열에 안정하게 개질하거나, 분해에 의해 발생하는 알킬 라디칼을 소모해주는 역할을 하기 때문인 것으로 추측하였다. 또한 276℃ ~ 336℃ 사이에서 몇 가지 온도에 대하여 등온에서 중량감소를 측정하여 질소분위기 하에서 주쇄의 불규칙 절단이 발생할 수 있는 활성화 에너지가 224kJ/mol, 빈도인자가 2.9ㅧ 1016/초(sec) 인 것으로 보고하였다.Toshimi Hirata and co-workers found that polymethylmethacrylates in their study (Macromolecules, 1985, V18, p1410-1418) were thermogravimetrically analyzed for commercially available polymethylmethacrylate in nitrogen and atmospheric atmospheres. The weight loss due to heat is caused by the volatilization of impurities and residual monomers in the region of 160 ~ 240 ℃ initially, and then by the decomposition of double bonds at the end of the main chain. Reported. According to the results of their studies, the weight loss was less in the range of 160 ~ 240 ℃ in the air atmosphere than in the nitrogen atmosphere in the thermal gravimetric analysis. It is assumed that this is because oxygen plays a role of more stably modifying the structure of the main chain terminal or consuming alkyl radicals generated by decomposition. In addition, by measuring the weight loss at isothermal temperature at several temperatures between 276 ℃ and 336 ℃, the activation energy for irregular cleavage of the main chain under nitrogen atmosphere is 224kJ / mol and the frequency factor is 2.9 ㅧ 1016 / sec. Reported. 카시와기(Takashi Kashiwagi)와 공동연구자들은 그들의 연구결과('Effects of Weak Linkages on the Thermal and Oxidative Degradation of Poly(methyl methacrylate)', Macromolecules, 1986, V19, p2160-2168)에서 라디칼 중합에 의해 제조된 폴리메틸메타크릴레이트의 열분해는 크게 세 가지의 반응에 의해 시작되며, 낮은 온도에서는 중합 정지반응 시 생성되는 결합구조 1) 불균등화 반응에 의한 주쇄 말단의 이중결합과 2)머리-머리 정지반응에 의한 탄소원자간 3차 결합에 의해 열분해가 시작되고, 온도가 높아지면 3) 주쇄의 불규칙 절단이 병행하며 열분해가 이루어지며, 특히 머리-머리 정지반응에 의한 탄소원자간 3차 결합이 열에 가장 불안정하다고 보고하고 있다. 그리고 사슬 전이 이동제를 사용하면 주쇄 말단의 이중결합과 머리-머리 정지반응에 의한 탄소원자간 3차 결합의 생성을 감소시켜 폴리메틸메타크릴레이트의 열안정성을 향상시킬 수 있다고 보고하고 있다.Takashi Kashiwagi and co-workers described their results ('Effects of Weak Linkages on the Thermal and Oxidative Degradation of Poly (methyl methacrylate)', Macromolecules, 1986, V19, p2160-2168). Pyrolysis of methyl methacrylate is largely initiated by three kinds of reactions. At low temperatures, the bond structure formed during the polymerization termination reaction is 1) double bonds at the end of the main chain by disproportionation and 2) head-to-head stop reaction. Pyrolysis starts by tertiary bonds between carbon atoms, and when temperature rises, 3) irregular cleavage of the main chain is performed in parallel, and pyrolysis occurs. In particular, it is reported that tertiary bonds between carbon atoms by the head-head stop reaction are the most unstable to heat. have. It is reported that the use of a chain transfer transfer agent can improve the thermal stability of polymethyl methacrylate by reducing the formation of tertiary bonds between carbon atoms by double bonds at the main chain ends and head-head stop reactions.

본 발명은 종래기술의 문제점을 해결하기 위해 안출된 것으로, 본 발명의 목적은 내열성이 우수한 폴리메틸메타크릴레이트 수지 조성물을 제공하는 데에 있다.The present invention has been made to solve the problems of the prior art, an object of the present invention is to provide a polymethyl methacrylate resin composition excellent in heat resistance.

본 발명은 내열성이 향상된 폴리메틸메타크릴레이트 수지 조성물을 제조하는 방법을 제공한다. The present invention provides a method for producing a polymethyl methacrylate resin composition having improved heat resistance.

본 발명의 방법은 메틸메타크릴레이트 단독 또는 적어도 1종 이상의 공단량체와 현탁중합을 함에 있어서 중합안정성을 위한 현탁제와 더불어 플루오렌(fluorene) 구조의 가교성 모노머를 소량 투입하여 중합하는 것을 포함한다.The method of the present invention includes polymerizing by adding a small amount of a crosslinkable monomer having a fluorene structure together with a suspending agent for polymerization stability in the suspension polymerization of methyl methacrylate alone or at least one or more comonomers. .

본 발명의 하나의 바람직한 구체예에 따른 폴리메틸메타크릴레이트 수지 조성물 제조 방법은 메틸메타크릴레이트 단독 또는 메틸메타크릴레이트 60~99.9%와 공단량체 0.1~40 중량%를 혼합한 단량체 혼합물 100 중량부에 대해서, 개시제 0.01 ~ 1 중량부, 사슬전이 이동제 0.1 ~ 5.0 중량부, 플루오렌 구조의 작용기를 가진 가교성 단량체 0.1 ~ 5 중량부를 이용하는 것을 포함한다.Polymethyl methacrylate resin composition production method according to one preferred embodiment of the present invention 100 parts by weight of a mixture of methyl methacrylate alone or 60 to 99.9% methyl methacrylate and 0.1 to 40% by weight comonomer It includes about 0.01 to 1 part by weight of an initiator, 0.1 to 5.0 parts by weight of a chain transfer agent, and 0.1 to 5 parts by weight of a crosslinkable monomer having a fluorene structure.

상기에서 살펴본 바와 같이, 본 발명은 종래의 기술에 비해, 폴리메틸메타크릴레이트 수지 현탁중합시에 플루오렌 구조의 가교성 단량체를 사용함으로써, 기존의 폴리메틸메타크릴레이트 수지에 비하여 우수한 내열성을 가진 폴리메틸메타크릴레이트 현탁중합체를 제공할 수 있다.As described above, the present invention has a superior heat resistance compared to the conventional polymethyl methacrylate resin by using a crosslinkable monomer of fluorene structure at the time of polymethyl methacrylate resin suspension polymerization, compared to the prior art. Polymethylmethacrylate suspension polymers can be provided.

이하, 상기 각 구성성분에 대하여 상세하게 설명한다.Hereinafter, each said component is demonstrated in detail.

본 발명에서 상기 중합단량체로는 메틸메타크릴레이트 단독으로 사용하거나, 또는 메틸메타크릴레이트 60 ~ 99.9중량%와 공단량체 0.1~40 중량%를 혼합한 단량체 혼합물을 사용하는 것도 가능하다.In the present invention, as the polymerization monomer, methyl methacrylate may be used alone, or a monomer mixture of 60 to 99.9% by weight of methyl methacrylate and 0.1 to 40% by weight of comonomer may be used.

본 발명에서 상기 공단량체로는 가공성 향상을 위한 알킬기가 1 내지 8개의 탄소로 이루어진 알킬 아크릴레이트, 보다 높은 내열성을 얻기 위한 알파 메틸 스타이렌, 사이클로 헥실 말레이미드와 같은 말레이미드계 단량체를 사용하는 것이 바람직하며, 그 함량은 0.1 ~ 40 중량%, 보다 바람직하게는 2 ~ 15 중량 % 사용한다.In the present invention, as the comonomer, it is preferable to use a maleimide monomer such as an alkyl acrylate having an alkyl group for improving processability, an alpha methyl styrene for obtaining higher heat resistance, and a cyclohexyl maleimide. Preferably, the content is used in an amount of 0.1 to 40% by weight, more preferably 2 to 15% by weight.

본 발명에서 사슬전이 이동제는 폴리메틸메타크릴레이트 수지의 분자량 조절을 통하여 폴리메틸메타크릴레이트 수지의 유동성을 조절하고, 플루오렌계 단량체의 가교 반응을 억제하기 위하여 사용하였다. 사용가능한 사슬전이 이동제로는 알킬기의 탄소수가 1 내지 12개이고 하나의 티올관능기를 가지는 알킬 메르캡탄(alkyl mercaptan), 또는 2개 이상의 티올관능기를 가진 폴리티올 메르캡탄이 적합하다. 알킬 메르캡탄으로서는 이소프로필 메르캡탄(Isopropyl mercaptan), 노르말 부틸 메르캡탄(normal butyl mercaptan), 터셔리-부틸 메르캡탄(tertiary butyl mercaptan), 노르말-아밀 메르캡탄(normal amyl mercaptan), 노르말-옥틸 메르캡탄(normal-octyl mercaptan), 노르말-도데실 메르캡탄(normal-dodecyl mercaptan) 등이 사용가능하다. 그 함량은 단량체 또는 단량체 혼합물 100 중량부에 대하여 0.1 내지 5.0 중량부, 바람직하게는 0.2 내지 1.0 중량부를 사용한다. 0.1 중량부보다 낮을 경에는 분자량이 커져 충분한 유동성을 확보하지 못하고, 5.0 중량부를 초과하는 경우에는 분자량이 지나치게 작아져 물성이 효과적으로 발현되지 아니한다.In the present invention, the chain transfer agent was used to control the fluidity of the polymethyl methacrylate resin through the molecular weight control of the polymethyl methacrylate resin and to suppress the crosslinking reaction of the fluorene monomer. Suitable chain transfer transfer agents are alkyl mercaptans having 1 to 12 carbon atoms in the alkyl group and one thiol functional group, or polythiol mercaptans having two or more thiol functional groups. Alkyl mercaptans include isopropyl mercaptan, normal butyl mercaptan, tertiary butyl mercaptan, normal-amyl mercaptan, and normal-octyl mer Normal-octyl mercaptan, normal-dodecyl mercaptan and the like can be used. The content is used 0.1 to 5.0 parts by weight, preferably 0.2 to 1.0 parts by weight based on 100 parts by weight of the monomer or monomer mixture. When the amount is lower than 0.1 part by weight, the molecular weight is increased to ensure sufficient fluidity, and when the amount is higher than 5.0 parts by weight, the molecular weight is too small to effectively express physical properties.

본 발명에서 플루오렌(fluorene) 구조의 가교성 단량체는 화학식 1의 구조를 갖는다:In the present invention, the crosslinkable monomer having a fluorene structure has the structure of Formula 1:

화학식 1Formula 1

Figure pat00001
Figure pat00001

상기 화학식 1에서,In Chemical Formula 1,

R1은 탄소수 1개 내지 8개의 알킬기를 나타내고, 탄소수의 개수에 따라 플루오렌 구조의 가교성 단량체 점도가 2,000에서 100,000까지 증가한다.R 1 represents an alkyl group having 1 to 8 carbon atoms, and the crosslinkable monomer viscosity of the fluorene structure increases from 2,000 to 100,000 according to the number of carbon atoms.

R2는 수소원자 또는 메틸기를 나타낸다.R 2 represents a hydrogen atom or a methyl group.

이 플루오렌 구조의 가교성 단량체는 그 구조로 인하여 아주 작은 양을 사용하여도 폴리메틸메타크릴레이트 수지의 유리전이온도(Tg)를 효과적으로 올려준다. 이때 사용되는 플루오렌 구조의 가교성 단량체의 함량은 단량체 또는 단량체 혼합물 100 중량부에 대하여, 0.1 내지 5.0 중량부, 바람직하게는 0.2 내지 1.0 중량부이다. 사용되는 플루오렌 구조의 가교성 단량체의 양이 0.1 중량부보다 작을 경우에는 플루오렌 구조의 단량체 량이 너무 작아 유리전이온도(Tg)를 효과적으로 올려주지 못하며, 5.0 중량부를 초과하는 경우에는 가교반응으로 인하여 제조된 폴리메틸메타크릴레이트 수지의 후가공이 불가능하게 된다.The crosslinkable monomer of the fluorene structure effectively raises the glass transition temperature (Tg) of the polymethyl methacrylate resin even in a very small amount due to its structure. In this case, the content of the crosslinkable monomer having a fluorene structure is 0.1 to 5.0 parts by weight, preferably 0.2 to 1.0 part by weight based on 100 parts by weight of the monomer or monomer mixture. When the amount of the crosslinkable monomer of the fluorene structure used is less than 0.1 part by weight, the amount of the monomer of the fluorene structure is too small to effectively raise the glass transition temperature (Tg), and when it exceeds 5.0 parts by weight due to the crosslinking reaction. Post-processing of the produced polymethyl methacrylate resin becomes impossible.

하기의 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 설명하기 위한 것이지 본 발명이 하기 실시예로 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following examples and comparative examples. However, the following examples are intended to illustrate the present invention, but the present invention is not limited to the following examples.

실시예Example 1 One

메틸메타크릴레이트 95 중량%와 메틸 아크릴레이트 5 중량%를 혼합한 단량체 혼합물 100 중량부에 대하여, 개시제로 AIBN 0.1 중량부, 물 200 중량부, 현탁제로 폴리비닐알콜 수용액을 고형분 기준으로 0.3 중량부를 투입하였다. 사슬 전이 이동제로 노르말 옥틸메르캡탄(normal octyl-mercaptan)을 단량체 혼합물 100 중량부에 대하여 0.5 중량부를 사용하고, 플루오렌 구조의 가교성 단량체는 단량체 혼합물 100 중량부에 대하여 0.5 중량부를 사용하여, 반응온도 80℃에서 70분간 중합시킨 후, 잔류 모노머를 제거하기 위하여 110℃에서 30분간 추가 중합을 실시하였다. 이때 사용된 플로오렌 구조의 가교성 단량체로는 Osaka gas chemical 사의 점도 2,000mPaㅇs의 OGSOL EA-F5003을 사용하였다.100 parts by weight of the monomer mixture of 95% by weight of methyl methacrylate and 5% by weight of methyl acrylate, 0.1 part by weight of AIBN as an initiator, 200 parts by weight of water, and 0.3 part by weight of an aqueous polyvinyl alcohol solution as a suspension. Input. As the chain transfer transfer agent, 0.5 parts by weight of normal octyl-mercaptan is used with respect to 100 parts by weight of the monomer mixture, and 0.5 parts by weight of the crosslinkable monomer having a fluorene structure is used based on 100 parts by weight of the monomer mixture. After the polymerization was carried out at a temperature of 80 ° C. for 70 minutes, further polymerization was performed at 110 ° C. for 30 minutes to remove residual monomers. In this case, OGSOL EA-F5003 having a viscosity of 2,000 mPa · s was used as a crosslinking monomer having a fluorene structure.

중합된 비드(bead)는 탈수기를 이동하여 세척하고, 건조기에서 24시간 건조하였다. 건조된 비드는 DSC(differential scanning calorimetery)를 이용하여 분당 10℃의 속도로 승온하여 수지의 유리전이온도(Tg)를 측정하였다.The polymerized beads were washed by moving the dehydrator and dried in a drier for 24 hours. The dried beads were heated at a rate of 10 ° C. per minute using differential scanning calorimeter (DSC) to measure the glass transition temperature (Tg) of the resin.

중합된 비드의 가교여부는 중합 비드를 아세톤에 넣어 용해 여부를 확인하였다.Whether the polymerized beads were crosslinked or not was checked by dissolving the polymerized beads in acetone.

실시예Example 2 2

상기 실시예 1에서 플루오렌 구조의 가교성 단량체로 Osaka gas chemical 사의 OGSOL EA0500을 사용하고, 메틸메타크릴레이트 100중량%를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.
Except that the OGSOL EA0500 of Osaka Gas Chemical Co., Ltd. and 100% by weight of methyl methacrylate were used as the crosslinkable monomer having a fluorene structure in Example 1, the same process as in Example 1 was carried out.

비교예Comparative example 1 One

상기 실시예 1에서 플루오렌계 가교성 단량체를 사용하지 않고, 실시예 1과 동일한 방법으로 폴리메틸메타크릴레이트 수지를 제조하였다.
In Example 1, a polymethylmethacrylate resin was prepared in the same manner as in Example 1 without using a fluorene-based crosslinkable monomer.

비교예Comparative example 2 2

상기 실시예 1에서 플루오렌계 가교성 단량체를 6 중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하였다.
Except for using 6 parts by weight of the fluorene-based crosslinkable monomer in Example 1 was carried out in the same manner as in Example 1.

비교예Comparative example 3 3

상기 실시예 2에서 플루오렌계 가교성 단량체를 사용하지 않고, 실시예 2와 동일한 방법으로 폴리메틸메타크릴레이트 수지를 제조하였다.
In Example 2, a polymethylmethacrylate resin was prepared in the same manner as in Example 2 without using a fluorene-based crosslinkable monomer.

비교예Comparative example 4 4

상기 실시예 2에서 플루오렌계 가교성 단량체를 6 중량부를 사용한 것을 제외하고는 실시예 2와 동일하게 실시하였다.
Except for using the fluorene-based crosslinkable monomer 6 parts by weight in Example 2 was carried out in the same manner as in Example 2.

실시예 1, 2 및 비교예 1 ~ 4에 따른 물성 측정결과는 아래 표 1에 제시하였다.Physical property measurement results according to Examples 1 and 2 and Comparative Examples 1 to 4 are shown in Table 1 below.

가교여부Bridge 유리전이온도(Tg)Glass transition temperature (Tg) 실시예 1Example 1 미가교Micah 115115 실시예 2Example 2 미가교Micah 124124 비교예 1Comparative Example 1 미가교Micah 110110 비교예 2Comparative Example 2 가교Bridge 110110 비교예 3Comparative Example 3 미가교Micah 120120 비교예 4Comparative Example 4 가교Bridge 120120

표 1에 의하면, 비교예 1과 3의 경우 플루오렌계 가교성 단량체를 사용하지 않음으로 인하여 Tg가 실시예 1과 2보다 낮게 측정되었으며, 비교예 2와 4의 경우, 플루오렌계 가교성 단량체를 너무 많이 사용함에 따라 가교반응으로 인하여 사용이 불가능하고 Tg의 상승효과도 발현되지 않았다. According to Table 1, Tg was measured lower than Examples 1 and 2 due to not using the fluorene-based crosslinkable monomer in Comparative Examples 1 and 3, and in the case of Comparative Examples 2 and 4, fluorene-based crosslinkable monomer Too much of the use was not possible due to the crosslinking reaction, and no synergistic effect of Tg was expressed.

따라서, 본 발명에 따른 조성물 및 제조방법을 이용할 경우, 내열성이 개선된 폴리메틸메타크릴레이트 수지를 얻을 수 있는 것을 알 수 있다.Therefore, when using the composition and the manufacturing method according to the present invention, it can be seen that the polymethyl methacrylate resin with improved heat resistance can be obtained.

본 발명에 의해 제조된 폴리메틸메타크릴레이트 수지 조성물은 우수한 내열 특성이 요구되는 다양한 산업 분야에 적용될 수 있다.The polymethylmethacrylate resin composition prepared by the present invention can be applied to various industrial fields requiring excellent heat resistance properties.

Claims (7)

메틸메타크릴레이트 단독 또는 메틸메타크릴레이트 60~99.9중량%와 공단량체 0.1~40 중량%를 혼합한 단량체 혼합물 100 중량부에 대해서, 개시제 0.01 ~ 1 중량부, 사슬전이 이동제 0.1 ~ 5.0 중량부, 플루오렌 구조의 작용기를 가진 가교성 단량체 0.1 ~ 5 중량부를 중합반응시키는 것을 포함하는 내열성이 향상된 폴리메틸메타크릴레이트 수지의 제조 방법.0.01 to 1 part by weight of an initiator, 0.1 to 5.0 parts by weight of a chain transfer agent, based on 100 parts by weight of methyl methacrylate alone or 60 to 99.9 weight% of methyl methacrylate and a monomer mixture of 0.1 to 40 weight% of comonomers, A method for producing a polymethyl methacrylate resin having improved heat resistance, comprising polymerizing 0.1 to 5 parts by weight of a crosslinkable monomer having a fluorene structure functional group. 제 1항에 있어서,
상기 공단량체는 가공성 향상을 위한 알킬기가 1 내지 8개의 탄소를 포함하는 알킬 아크릴레이트, 보다 높은 내열성을 얻기 위한 알파 메틸 스타이렌, 사이클로 헥실 말레이미드를 포함한 말레이미드계 단량체를 사용하는 것을 특징으로 하여 내열성이 향상된 폴리메틸메타크릴레이트 수지의 제조 방법.The method of claim 1,
The comonomer is characterized by using a maleimide monomer including an alkyl acrylate containing 1 to 8 carbons, an alpha methyl styrene to obtain higher heat resistance, and a cyclohexyl maleimide to improve processability. Method for producing a polymethyl methacrylate resin having improved heat resistance. 제 1항에 있어서,
상기 사슬전이 이동제는 알킬기의 탄소수가 1 내지 12개이고 하나의 티올관능기를 가지는 알킬 메르캡탄(alkyl mercaptan), 또는 2개 이상의 티올관능기를 가지는 폴리티올 메르캡탄을 사용하는 것을 특징으로 하여 내열성이 향상된 폴리메틸메타크릴레이트 수지 제조 방법. The method of claim 1,
The chain transfer agent is an alkyl mercaptan having 1 to 12 carbon atoms and having one thiol functional group, or a polythiol mercaptan having two or more thiol functional groups. Methyl methacrylate resin manufacturing method. 제 3항에 있어서,
상기 알킬 메르캡탄으로서는 이소프로필 메르캡탄(Isopropyl mercaptan), 노르말 부틸 메르캡탄(normal butyl mercaptan), 터셔리-부틸 메르캡탄(tertiary butyl mercaptan), 노르말-아밀 메르캡탄(normal amyl mercaptan), 노르말-옥틸 메르캡탄(normal-octyl mercaptan), 노르말-도데실 메르캡탄(normal-dodecyl mercaptan)에서 선택되는 어느 하나 이상을 사용하는 것을 특징으로 하여 내열성이 향상된 폴리메틸메타크릴레이트 수지 제조방법.The method of claim 3, wherein
Examples of the alkyl mercaptan include isopropyl mercaptan, normal butyl mercaptan, tertiary butyl mercaptan, normal-amyl mercaptan, and normal-octyl. Method for producing a polymethyl methacrylate resin having improved heat resistance, characterized in that using at least one selected from mercaptan (normal-octyl mercaptan), normal-dodecyl mercaptan (normal-dodecyl mercaptan). 제 1항에 있어서,
플루오렌계 가교성 단량체는 하기 화학식의 화합물 인 것을 특징으로 하여 내열성이 향상된 폴리메틸메타크릴레이트 수지 제조방법:
Figure pat00002

상기 화학식에서,
R1은 탄소수 1개 내지 8개의 알킬기를 나타내고;
R2는 수소원자 또는 메틸기를 나타낸다.The method of claim 1,
Method for producing a polymethyl methacrylate resin having improved heat resistance, characterized in that the fluorene-based crosslinkable monomer is a compound of the following formula:
Figure pat00002

In the above formulas,
R 1 represents an alkyl group having 1 to 8 carbon atoms;
R 2 represents a hydrogen atom or a methyl group. 제 1항 내지 제 5항 중의 어느 한 항에 따른 방법에 의해 제조된 폴리메틸메타크릴레이트 수지 조성물.A polymethyl methacrylate resin composition prepared by the method according to any one of claims 1 to 5. 제 6항에 따른 폴리메틸메타크릴레이트 수지 조성물을 포함하는 내열성 광학 필름.A heat resistant optical film comprising the polymethyl methacrylate resin composition according to claim 6.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20190112976A (en) * 2018-03-27 2019-10-08 엘지엠엠에이 주식회사 Acrylic optical film and manufacturing method thereof
US10816712B2 (en) 2016-06-22 2020-10-27 Lg Chem, Ltd. Optical film and polarization plate comprising the same
CN112625168A (en) * 2019-09-24 2021-04-09 中国石油化工股份有限公司 Polymethyl methacrylate monomer high-molecular polymer and preparation method thereof
CN112745617A (en) * 2020-12-28 2021-05-04 安徽金亮新型材料有限公司 Heat insulation type acrylic plate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10816712B2 (en) 2016-06-22 2020-10-27 Lg Chem, Ltd. Optical film and polarization plate comprising the same
KR20190112976A (en) * 2018-03-27 2019-10-08 엘지엠엠에이 주식회사 Acrylic optical film and manufacturing method thereof
CN112625168A (en) * 2019-09-24 2021-04-09 中国石油化工股份有限公司 Polymethyl methacrylate monomer high-molecular polymer and preparation method thereof
CN112625168B (en) * 2019-09-24 2022-05-24 中国石油化工股份有限公司 Polymethyl methacrylate high molecular polymer and preparation method thereof
CN112745617A (en) * 2020-12-28 2021-05-04 安徽金亮新型材料有限公司 Heat insulation type acrylic plate

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