KR20060115280A - Acrylate copolymer - Google Patents
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- KR20060115280A KR20060115280A KR1020050037751A KR20050037751A KR20060115280A KR 20060115280 A KR20060115280 A KR 20060115280A KR 1020050037751 A KR1020050037751 A KR 1020050037751A KR 20050037751 A KR20050037751 A KR 20050037751A KR 20060115280 A KR20060115280 A KR 20060115280A
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Abstract
Description
본 발명은 고내열성 및 고투과성을 갖는 아크릴 수지에 관한 것으로, 메틸메타크릴레이트(MMA)의 중합체인 폴리메틸메타크릴레이트(PMMA)의 현탁중합 조성물에 관한 것이다. The present invention relates to an acrylic resin having high heat resistance and high permeability, and to a suspension polymerization composition of polymethyl methacrylate (PMMA) which is a polymer of methyl methacrylate (MMA).
폴리메틸메타크릴레이트는 메틸메타크릴레이트 만을 단독으로 중합하거나 메틸메타크릴레이트와 다른 종류의 아크릴레이트 단량체를 공단량체로 하여 현탁 중합 공정으로 제조되는 수지이다. Polymethyl methacrylate is a resin which is polymerized by methyl methacrylate alone or prepared by a suspension polymerization process using methyl methacrylate and another kind of acrylate monomer as a comonomer.
폴리메틸메타크릴레이트는 투명성 및 내후성이 뛰어나고, 기계적 물성 등이 우수해 투명성을 요구하는 다양한 분야에서 사용되고 있는 대표적인 투명 수지이다. 특히 최근의 디스플레이 산업의 성장으로 이러한 투명한 소재에 대한 수요가 크게 신장되고 있어 큰 관심을 받고 있다. 특히 폴리메틸메타크릴레이트는 광투과율에 있어서 어떤 소재보다도 뛰어난 투과율을 지니고 있기 때문에 액정디스플레이 백라이트 소재인 도광판과 휴대전화의 전면판 등 다양한 광학 분야용 소재로 널리 사용되고 있다. 그런데, 이러한 높은 광투과율의 폴리메틸메타크릴레이트는 주로 괴상중합법에 의해 생산되고 있으며, 일반적인 현탁 중합에 의해 생산된 폴리메틸 메타크릴레이트의 광특성은 괴상 중합법으로 제조된 것에 비해 다수의 첨가제로 인해 다소 떨어지는 것으로 알려져 있다. 따라서 광학 소재 분야에서 사용되는 폴리메틸메타크릴레이트는 대부분 괴상중합법에 의한 것만 사용되고 있으나, 괴상중합 공정은 현탁공정에 비해 투자비용이 크게 들고, 공정상의 어려움이 존재한다. 그러나 현탁공정은 반응열의 제어가 용이하고, 투자비용이 적게 들어 경제적으로 더욱 유용한 생산방법이 된다. Polymethyl methacrylate is a typical transparent resin that is used in various fields that require transparency because of excellent transparency and weather resistance and excellent mechanical properties. In particular, the recent growth of the display industry has attracted great attention as demand for such transparent materials is greatly increased. In particular, polymethyl methacrylate is widely used as a material for various optical fields such as a light guide plate, which is a liquid crystal display backlight material, and a front plate of a mobile phone, because it has a transmittance superior to any material in light transmittance. By the way, these high light transmittance polymethyl methacrylate is mainly produced by the bulk polymerization method, the optical properties of the polymethyl methacrylate produced by the general suspension polymerization is a large number of additives compared to that produced by the bulk polymerization method It is known to fall somewhat. Therefore, the polymethyl methacrylate used in the optical material field is mostly used by the bulk polymerization method, but the bulk polymerization process has a large investment cost and difficulty in the process compared to the suspension process. However, the suspension process is easy to control the reaction heat, and the investment cost is low, making the production more economically useful.
특히, 도광판 중 사출성형에 의해 제조되는 도광판의 경우, 현탁중합에 의해 제조된 폴리메틸메타크릴레이트는 분자량의 저하로 인한 물성열화로 인하여 괴상중합에 의한 제품 대비 가공안정성이 크게 떨어지는 단점이 있다. 이러한 이유로 도광판 용도의 사출용 폴리메틸메타크릴레이트는 전량 괴상중합법에 의해 제조된 일본산 제품이 채용되고 있는 실정이다. In particular, in the light guide plate manufactured by injection molding of the light guide plate, polymethyl methacrylate prepared by suspension polymerization has a disadvantage in that processing stability is significantly lower than that of a product due to bulk polymerization due to deterioration of physical properties due to a decrease in molecular weight. For this reason, the polymethyl methacrylate for injection for light-guide plate use is the situation where the Japanese product manufactured by the mass polymerization method is employ | adopted.
일반적으로 압출, 사출성형 등의 열가공 시 열이력에 의해 수지의 열분해가 일어나며, 이는 수지의 광학적, 기계적 물성을 저하시키는 중요한 요인의 하나로 알려져 있다. 이러한 열이력에 의해 사출용도의 폴리메틸메타크릴레이트가 괴상중합 제품 대비 현탁 중합 제품이 더욱 쉽게 영향을 받으므로, 일반용도가 아닌 광학용으로 사용되기에는 한계를 갖고 있었다.In general, thermal decomposition of a resin occurs by thermal history during thermal processing such as extrusion, injection molding, etc., which is known as one of important factors to lower the optical and mechanical properties of the resin. Due to this thermal history, polymethyl methacrylate for injection use is more easily influenced by suspension polymerization products than bulk polymerization products, and thus has limitations in being used for optical rather than general use.
본 발명은 우수한 광투과율과 안정한 가공 열안정성을 지닌 메타크릴 수지 의 제조방법과 그 중합체를 제공함을 목적으로 한다.An object of the present invention is to provide a method for producing a methacryl resin having excellent light transmittance and stable processing heat stability and a polymer thereof.
또한, 본 발명은 현탁중합에 의하여 제조된 고내열성과 고투과성을 갖는 아크릴중합체를 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide an acrylic polymer having high heat resistance and high permeability prepared by suspension polymerization.
본 발명은 고내열성 및 고투과성을 갖는 아크릴 수지에 관한 것으로, 향상된 광투과율과 안정한 가공 열안정성을 지닌 메타크릴 수지 현탁중합체의 조성에 관한 것이다.The present invention relates to an acrylic resin having high heat resistance and high permeability, and to a composition of a methacryl resin suspension polymer having improved light transmittance and stable processing thermal stability.
본 발명의 조성은 단량체 혼합물 100중량부에 대하여 메틸메타크릴레이트 단독 또는 적어도 메틸메타크릴레이트가 80중량부 이상인 중합체를 현탁 중합함에 있어, 메틸메타크릴레이트 단독 또는 메틸메타크릴레이트 80~ 99.9 중량%와 공단량체 0.1 ~ 20 중량%, 바람직하게는 3 ~ 15 중량%로 구성되는 단량체 혼합물 100 중량부에 대하여 개시제를 1종 이상을 사용하여 0.01 내지 1, 바람직하게는 0.05 내지 0.2 중량부를 사용하며, 사슬고리이동제를 0.01 내지 1.0, 바람직하게는 0.1 내지 0.5 중량부를 사용하고, 가교제를 0.01 내지 2.0, 바람직하게는 0.02 내지 1.0 중량부를 사용하여 현탁중합 하는 것을 특징으로 한다.The composition of the present invention is methyl methacrylate alone or methyl methacrylate 80 to 99.9% by weight in the suspension polymerization of methyl methacrylate alone or a polymer of at least 80 parts by weight of methyl methacrylate relative to 100 parts by weight of the monomer mixture And 0.01 to 1, preferably 0.05 to 0.2 parts by weight, using one or more initiators, based on 100 parts by weight of the monomer mixture consisting of 0.1 to 20% by weight of comonomer, preferably 3 to 15% by weight, The chain transfer agent is characterized in that the suspension polymerization using 0.01 to 1.0, preferably 0.1 to 0.5 parts by weight and the crosslinking agent to 0.01 to 2.0, preferably 0.02 to 1.0 parts by weight.
본 발명에서 상기 공단량체는 2 내지 8개의 탄소로 이루어진 알킬 아크릴레이트 또는 아크릴레이트를 사용하는 것이 바람직하다.In the present invention, the comonomer is preferably an alkyl acrylate or acrylate consisting of 2 to 8 carbons.
본 발명에서 사용한 중합 개시제로는 10시간 반감기가 60℃ 이하인 것을 사용하는 것을 특징으로 하는데, 이러한 개시제를 사용하는 경우 황변현상 등이 발생하지 않아 우수한 광투과율을 가지는 광학용 투명 수지를 제조할 수 있다. 상기 개 시제로는 예를 들면, 2,2'-아조비스2,4-디메틸-발레로니트릴(2,2'-Azobis(2,4-dimethyl- valeronitrile)), 2,2'-아조비스 4-메톡시-2,4-디메틸 발레로니트릴((2,2'-Azobis(4-methoxy-2,4-dimethyl valeronitrile)), α,α'-비스 네오데카노일 퍼옥시 디이소프로필 벤젠(α,α'-bis(neodecanoyl peroxy)diisopropyl benzene), 이소부티릴 퍼옥사이드(isobutyryl peroxide), 쿠밀 퍼옥시네오데카노에이트(Cumyl peroxyneodecanoate), 디-노르말-프로필 퍼옥시 디카보네이트(Di-normal-propyl peroxy dicarbonate), 디이소프로필 퍼옥시 디카보네이트(Diisopropyl peroxy dicarbonate), 1,1,3,3,-테트라메틸부틸 퍼옥시 네오데카노에이트(1,1,3,3,-tetramethylbuthyl peroxyneodecanoate), 1-시클로헥실-1-메틸에틸 퍼옥시 네오데카노에이트(1-cyclohexyl-1-methylethyl peroxyneodecanoate), 디-2-에톡시에틸 퍼옥시 디카보네이트(Di-2-ethoxyethyl peroxy dicarbonate), 디-2-에톡시헥실 디카보네이트(Di-2-ethoxyhexyl dicarbonate), 터셔리-헥실 퍼옥시 네오데카노에이트(tertiary-hexyl peroxyneodecanoate), 디메톡시부틸 퍼옥시 디카보네이트(Dimethoxybutyl peroxy dicarbonate), 비스 3-메틸-3메톡시부틸 퍼옥시 디카보네이트(Bis(3-methyl-3-methoxybutyl)peroxy dicarbonate), 터셔리-부틸 퍼옥시 네오테카노에이트(tertiary-butyl peroxyneodecanoate), 터셔리-헥실 퍼옥시피바레이트(tertiary-hexylperoxypivalate), 터셔리-부틸 퍼옥시피바레이트(tertiary-butylperoxypivalate), 3,5,5-트리메틸헥사노일 퍼옥사이드(3,5,5-trimethylhexanoyl peroxide)등이 사용 가능하다. The polymerization initiator used in the present invention is characterized by using a half-life of 60 hours or less for 10 hours, when using such an initiator does not occur yellowing phenomenon can be prepared an optical transparent resin having excellent light transmittance. . As the initiator, for example, 2,2'-azobis2,4-dimethyl-valeronitrile (2,2'-Azobis (2,4-dimethyl-valronitrile)), 2,2'-azobis 4-methoxy-2,4-dimethyl valeronitrile ((2,2'-Azobis (4-methoxy-2,4-dimethyl valeronitrile)), α, α'-bis neodecanoyl peroxy diisopropyl benzene (α, α'-bis (neodecanoyl peroxy) diisopropyl benzene), isobutyryl peroxide, cumyl peroxyneodecanoate, di-normal-propyl peroxy dicarbonate (Di-normal -propyl peroxy dicarbonate), Diisopropyl peroxy dicarbonate, 1,1,3,3, -tetramethylbutyl peroxy neodecanoate (1,1,3,3, -tetramethylbuthyl peroxyneodecanoate) 1-cyclohexyl-1-methylethyl peroxyneodecanoate, Di-2-ethoxyethyl peroxy dicarbonate, di- 2-ethoxyhex Di-2-ethoxyhexyl dicarbonate, tertary-hexyl peroxyneodecanoate, Dimethoxybutyl peroxy dicarbonate, bis 3-methyl-3methoxy Butyl peroxy dicarbonate (Bis (3-methyl-3-methoxybutyl) peroxy dicarbonate), tertiary-butyl peroxyneodecanoate, tertiary-hexylperoxypivalate , Tertiary-butylperoxypivalate, 3,5,5-trimethylhexanoyl peroxide (3,5,5-trimethylhexanoyl peroxide) and the like can be used.
또한 상기 개시제로 70℃ 이상에서 반감기가 10시간인 고온 개시제를 함께 사용하는 것도 가능하다.It is also possible to use a high temperature initiator having a half life of 10 hours at 70 ° C or more as the initiator.
본 발명에서는 폴리메틸메타크릴레이트의 분자량 조절과 열안정성 향상을 위하여 사슬 전이 이동제(Chain transfer agent)를 사용하였다. 분자량은 개시제의 양으로도 조절이 가능하나, 사슬 전이 이동제에 의해 중합반응이 정지되면 사슬의 말단이 제이탄소 구조가 되어 사슬 전이 이동제를 사용하지 않았을 때 불균등화에 의해 이중결합을 갖는 사슬의 말단보다 결합강도가 강하므로 열에 더 안정적인 구조를 가지게 되어 메틸메타크릴레이트 수지의 광특성을 향상시키는 효과가 있다. In the present invention, a chain transfer agent was used for molecular weight control and thermal stability improvement of polymethylmethacrylate. The molecular weight can be controlled by the amount of the initiator, but when the polymerization reaction is stopped by the chain transfer agent, the end of the chain becomes the second carbon structure, and when the chain transfer agent is not used, the end of the chain having a double bond by disproportionation is not used. Since the bond strength is stronger than that, it has a more stable structure against heat, thereby improving the optical properties of the methyl methacrylate resin.
사용 가능한 사슬 전이 이동제로는 알킬기의 탄소개수가 1 내지 12개이고 하나의 티올관능기를 가지는 알킬 메르캡탄(alkyl mercaptan), 또는 2개 이상의 티올관능기를 가지는 폴리티올 메르캡탄이 적합하다. 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.
알킬 메르캡탄으로는 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 사용 가능하다. Alkyl mercaptans include isopropyl mercaptan, normal butyl mercaptan, tertiary butyl mercaptan, normal-amyl mercaptan, and normal-octyl Normal-octyl mercaptan, normal-dodecyl mercaptan and the like can be used.
폴리티올 메르캡탄은 다음과 같이 화학식 1로 대표할 수 있으며, Polythiol mercaptan can be represented by the formula (1),
[화학식 1][Formula 1]
(HS-Y)n-X (HS-Y) n-X
(상기 식에서, HS는 티올 관능기, n은 2 내지 6의 정수이며 X를 중심그룹, Y를 결합그룹이라 하며, 바람직한 중심그룹 X로는 최소한 글리세롤(glycerol), 소르 비톨(sorbitol), 펜타에리트리톨(pentaerythritol), 디펜타에리트리톨(di-pentaerythritol), 트리펜타에리트리톨(tri-pentaerythritol), 트리메틸올에탄(tri-methylolethane), 트리메틸올프로판(tri-methylolpropane), 펜타히드록시펜탄(pentahydroxypentane), 트리퀴노일(tri-quinoyl) 및 이노시톨(inositol)에서 선택되는 어느 하나이고, 결합그룹 Y로는 탄소개수 2 내지 5개의 알킬레이트이다.)Wherein HS is a thiol functional group, n is an integer of 2 to 6, X is a central group, Y is a bonding group, and preferred central group X is at least glycerol, sorbitol, pentaerythritol ( pentaerythritol, di-pentaerythritol, tri-pentaerythritol, tri-methylolethane, tri-methylolpropane, pentahydroxypentane, tree And one selected from tri-quinoyl and inositol, and the bonding group Y is an alkylate having 2 to 5 carbon atoms.)
이러한 폴리티올 메르캡탄의 적합한 예로는, 트리메틸올에탄 트리스(3-메르캡토프로피오네이트)(trimethylolethane tris(3-mercaptopropionate)), 펜타에리트리톨 테트라(3-메르캡토프로피오네이트)(pentaerythritol tetra(3-mercaptopropionate)), 펜타에리트리톨 테트라티오글리콜레이트(pentaerythritol tetrathioglycolate), 트리메틸올에탄 트리티오글리콜레이트(trimethylolethane trithioglycolate), 트리메틸올프로판트리스(3-메르캡토프로피오네이트)(trimethylolpropane tris(3-mercaptopropionate)), 트리메틸올 프로판트리글리콜레이트(trimethylpropane trithioglycolate)가 포함된다.Suitable examples of such polythiol mercaptans include trimethylolethane tris (3-mercaptopropionate) and pentaerythritol tetra (pentaerythritol tetra). 3-mercaptopropionate)), pentaerythritol tetrathioglycolate, trimethylolethane trithioglycolate, trimethylolpropane tris (3-mercaptopropionate tris (3-mercaptopropionate) ), Trimethylol propane triglycolate.
그러나 다량의 사슬고리 이동제를 첨가하게 되면 사슬의 길이가 지나치게 짧아지는 되는데, 이는 기계적 물성의 저하를 유발하게 된다. 따라서 사슬전이 이동제의 역할을 유지하면서도, 기계적 물성이 저하되지 않도록 하기 위하여 신규한 방법을 고안하고자 하였으며, 그 결과 가교제를 사용하기로 하였다. However, when a large amount of chain transfer agent is added, the length of the chain becomes too short, which causes a decrease in mechanical properties. Therefore, to maintain the role of the chain transfer agent, while trying to devise a new method in order not to lower the mechanical properties, as a result of using a crosslinking agent.
본 발명에서 사용된 가교제는 유용성 가교제로 사용할 수 있는 통상의 다관능성 가교제를 사용할 수 있다. 가교제로는 디비닐 벤젠(Divinyl benzene), 에틸렌글리콜디메타크릴레이트(Ethylene glycol dimethacrylate), 디에틸렌글리콜디메타 크릴레이트(diethylene glycol dimethacrylate), 트리에틸렌글리콜디메타크릴레이트(Triethylene glycol dimethacrylate), 1,3-부틸렌글리콜디메타크릴레이트(1,3-butylene glycol dimethacrylate), 아릴메타크릴레이트(aryl methacrylate), 1,3-부틸렌글리콜디아크릴레이트(1,3-butylene glycol diacrylate) 중에서 선택되는 1종 이상을 0.01~2.0 중량부로 사용하고, 바람직하게는 0.02~1.0 중량부 사용하는 것이 바람직하다.The crosslinking agent used in the present invention may use a conventional multifunctional crosslinking agent which can be used as an oil-soluble crosslinking agent. Divinyl benzene, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1 Choose from 1,3-butylene glycol dimethacrylate, aryl methacrylate and 1,3-butylene glycol diacrylate It is preferable to use at least 1 type by 0.01-2.0 weight part, Preferably it uses 0.02-1.0 weight part.
이하의 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들만으로 본 발명이 한정되는 것은 아니다. The present invention will be described in more detail with reference to the following examples and comparative examples. However, the Examples are provided to illustrate the present invention and the present invention is not limited thereto.
[실시예 1]Example 1
메틸메타크릴레이트 95 중량%와 메틸 아크릴레이트 5 중량%로 이루어진 단량체 혼합물 100 중량부에 대하여, 개시제로 2,2'-아조비스 2,4-디메틸-발레로니트릴(2,2'-Azobis(2,4-dimethyl-valeronitrile) 0.1 중량부, 물을 200중량부, 현탁제로 메틸메타크릴레이트-메타크릴산의 공중합체를 NaOH로 중화시킨 중합체(데구사, Rohagit Smv)0.9 중량부, 완충염으로 소듐 디히드로겐 포스페이트와 디소듐 히드로겐 포스페이트를 중량비 2:1로 하여 총 0.15 중량부를 투입하였다. 사슬전이 이동제로 노르말옥틸메르캡탄(normal-octylmercaptan)을 단량체 혼합물 100 중량부에 대하여 0.3 중량부를 사용하고, 가교제로 에틸렌글리콜디메타크릴레이트(EDGMA)를 0.025 중량부를 넣고, 반응온도 65℃로 60분간 반응시킨 후 잔류 모노머의 제거를 위해 120℃까지에서 15분간 추가 중합을 실시하였다. With respect to 100 parts by weight of the monomer mixture consisting of 95% by weight of methyl methacrylate and 5% by weight of methyl acrylate, 2,2'-azobis 2,4-dimethyl-valeronitrile (2,2'-Azobis ( 2,4-dimethyl-valeronitrile) 0.1 part by weight, 200 parts by weight of water, 0.9 parts by weight of a polymer (Degussa, Rohagit Smv) which neutralized a copolymer of methyl methacrylate-methacrylic acid with NaOH as a suspending agent 0.15 parts by weight of sodium dihydrogen phosphate and disodium hydrogen phosphate were added at a weight ratio of 2: 1. Normal-octylmercaptan was added 0.3 parts by weight to 100 parts by weight of the monomer mixture as a chain transfer agent. 0.025 parts by weight of ethylene glycol dimethacrylate (EDGMA) was used as a crosslinking agent, the reaction was carried out at a reaction temperature of 65 ° C. for 60 minutes, and further polymerization was performed at 120 ° C. for 15 minutes to remove residual monomers.
중합된 비드는 탈수기를 이용하여 세척하고 건조기에서 24시간 건조를 하였다. 분자량은 표준시료로 폴리메틸메타크릴레이트를 사용한 겔투과크로마토그래피(GPC)를 이용하여 측정하였다.The polymerized beads were washed with a dehydrator and dried in a drier for 24 hours. Molecular weight was measured by gel permeation chromatography (GPC) using polymethyl methacrylate as a standard sample.
유리전이온도와 열분해온도는 Perkin-Elmer사의 Pyris 6 시차주사열분석기(DSC)와 열중량분석기(TGA)를 이용하여 측정하였다. The glass transition and pyrolysis temperatures were measured using a Pyris 6 differential scanning thermal analyzer (DSC) and a thermogravimetric analyzer (TGA).
투과율은 현탁중합 비드(beads)를 압출 후 펠릿(pellet)으로 만든 후 이를 150mm시편으로 사출하여 전광선투과율을 측정하였다. The transmittance was measured by total light transmittance by extruding suspension polymerized beads into pellets and extruding them into 150 mm specimens.
[실시예 2]Example 2
실시예 1과 동일하나 단량체 혼합물 100 중량부에 대하여 사슬전이 이동제로 노르말옥틸메르캡탄을 0.3 중량부, 에틸렌글리콜디메타크릴레이트를 0.05 중량부를 사용하여 실시예 1과 동일 조건에서 중합을 실시하였다.The polymerization was carried out under the same conditions as those of Example 1, using 0.3 parts by weight of normal octyl mercaptan and 0.05 parts by weight of ethylene glycol dimethacrylate as the chain transfer agent with respect to 100 parts by weight of the monomer mixture.
[실시예 3] Example 3
실시예 1에서 단량체 혼합물 100 중량부에 대하여 사슬전이 이동제로 노르말옥틸메르캡탄을 0.3 중량부, 에틸렌글리콜디메타크릴레이트를 0.15 중량부를 사용한 것을 제외하고 실시예 1과 동일 하게 중합을 실시하였다. The polymerization was carried out in the same manner as in Example 1, except that 0.3 parts by weight of normal octyl mercaptan and 0.15 parts by weight of ethylene glycol dimethacrylate were used as a chain transfer agent in 100 parts by weight of the monomer mixture.
[실시예 4] Example 4
실시예 1에서 단량체 혼합물 100 중량부에 대하여 메틸메타크릴레이트 90 중량부, 메틸 아크릴레이트 10 중량부를 사용한 것을 제외하고 실시예 1과 동일 하게 중합을 실시하였다. The polymerization was carried out in the same manner as in Example 1, except that 90 parts by weight of methyl methacrylate and 10 parts by weight of methyl acrylate were used based on 100 parts by weight of the monomer mixture.
[실시예 5]Example 5
실시예 4에서 단량체 혼합물 100 중량부에 대하여 사슬전이 이동제로 노르말옥틸메르캡탄을 0.3 중량부, 에틸렌글리콜디메타크릴레이트를 0.15 중량부를 사용한 것을 제외하고 실시예 4와 동일 하게 중합을 실시하였다.The polymerization was carried out in the same manner as in Example 4, except that 0.3 parts by weight of normal octyl mercaptan and 0.15 parts by weight of ethylene glycol dimethacrylate were used as a chain transfer agent in 100 parts by weight of the monomer mixture.
[실시예 6]Example 6
실시예 4에서 사슬전이 이동제로 노르말옥틸메르캡탄을 0.35 중량부, 에틸렌글리콜디메타크릴레이트를 0.025 중량부를 사용한 것을 제외하고 실시예 4와 동일하게 중합을 실시하였다. In Example 4, polymerization was carried out in the same manner as in Example 4, except that 0.35 part by weight of normal octyl mercaptan and 0.025 part by weight of ethylene glycol dimethacrylate were used as the chain transfer agent.
[실시예 7]Example 7
실시예 1에서 사슬전이 이동제로 노르말옥틸메르캡탄을 0.4 중량부, 에틸렌글리콜디메타크릴레이트를 0.15 중량부를 사용한 것을 제외하고 실시예 1과 동일하게 중합을 실시하였다. In Example 1, polymerization was carried out in the same manner as in Example 1 except that 0.4 part by weight of normal octyl mercaptan and 0.15 part by weight of ethylene glycol dimethacrylate were used as the chain transfer agent.
실시결과는 표1과 같다.The results are shown in Table 1.
[비교예 1]Comparative Example 1
메틸메타크릴레이트 96 중량%, 메틸 아크릴레이트 4 중량%로 구성된 단량체 혼합물 100 중량부에 대하여, 개시제로 2,2'-아조비스 2,4-디메틸-발레로니트릴[(2,2'-Azobis(2,4-dimethyl-valeronitrile)](ADVN) 0.1 중량부, 물을 200중량부, 현탁제로 메틸메타크릴레이트-메타크릴산의 공중합체를 NaOH로 중화시킨 중합체(데구사, Rohagit Smv) 0.9 중량부, 완충염으로 소듐 디히드로겐 포스페이트와 디소듐 히드로겐 포스페이트를 중량비 2:1로하여 총 0.15 중량부를 투입하였다. 사슬전이 이동제로 노르말옥틸메르캡탄을 단량체 혼합물 100 중량부에 대하여 0.3 중량부를 사용하고, 반응온도 65℃로 60분간 반응시킨 후 잔류모노머의 제거를 위해 120℃까지에서 15분간 추가 중합을 실시하였다. 2,2'-azobis 2,4-dimethyl-valeronitrile [(2,2'-Azobis) as an initiator based on 100 parts by weight of a monomer mixture composed of 96% by weight of methyl methacrylate and 4% by weight of methyl acrylate (2,4-dimethyl-valeronitrile)] (ADVN) 0.1 part by weight, 200 parts by weight of water, a polymer obtained by neutralizing the copolymer of methyl methacrylate-methacrylic acid with NaOH (Degussa, Rohagit Smv) 0.9 as a suspending agent. A total of 0.15 parts by weight of sodium dihydrogen phosphate and disodium hydrogen phosphate were added in a weight ratio of 2: 1 by weight and a buffer salt, 0.3 parts by weight of normaloctyl mercaptan, based on 100 parts by weight of the monomer mixture, as a chain transfer agent. The reaction was carried out at a reaction temperature of 65 ° C. for 60 minutes and further polymerization was performed at 120 ° C. for 15 minutes to remove residual monomer.
중합된 비드는 탈수기를 이용하여 세척하고 건조기에서 24시간 건조를 하였다. The polymerized beads were washed with a dehydrator and dried in a drier for 24 hours.
[비교예 2]Comparative Example 2
실시예1에서 가교제로 펜타에리스리톨(Pentaerythritol)을 0.025 중량부를 사용한 것을 제외하고는 실시예 1과 동일하게 중합을 실시하였다. 실시 결과는 표1과 같다.The polymerization was carried out in the same manner as in Example 1, except that 0.025 parts by weight of pentaerythritol was used as the crosslinking agent in Example 1. The results are shown in Table 1.
[표1]Table 1
(주)분해온도는 TGA 분해곡선에서 미분값의 꼭지점을 기준으로 정의함.Note: The decomposition temperature is defined based on the vertex of the derivative in the TGA decomposition curve.
상기 표 1에서 보이는 바와 같이, 본 발명에 따른 실시예는 분해온도가 375℃이상, 투과율이 89%이상이며, 분자량이 9만 이상의 매우 높은 분자량을 얻을 수 있어 기계적 물성을 향상시킬 수 있는 효과를 동시에 가지는 것이다.As shown in Table 1, the embodiment according to the present invention has a decomposition temperature of 375 ° C. or more, a transmittance of 89% or more, and a molecular weight of 90,000 or more to obtain a very high molecular weight, thereby improving mechanical properties. At the same time.
특히, 광학 특성과 분해온도를 향상시켜 내열성을 가지는 중합체를 생성할 수 있다.In particular, it is possible to produce a polymer having heat resistance by improving optical properties and decomposition temperature.
본 발명은 종래의 기술에 비해 열안정성과 광특성이 우수하며 높은 분자량의 중합체를 얻을 수 있어 기계적 물성을 향상시킬 수 있는 메틸메타아크릴 수지 현탁중합체의 제조방법을 제공한다. The present invention provides a method for producing a methyl methacrylic resin suspension polymer which is excellent in thermal stability and optical properties compared to the prior art and can obtain a high molecular weight polymer to improve mechanical properties.
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KR100890172B1 (en) * | 2006-12-18 | 2009-03-25 | 엘지엠엠에이 주식회사 | Coating material |
KR101494495B1 (en) * | 2011-03-23 | 2015-02-23 | 주식회사 엘지화학 | Pressure sensitive adhesive composition for an optical film |
KR20190112995A (en) * | 2018-03-27 | 2019-10-08 | 엘지엠엠에이 주식회사 | Acrylic optical film and manufacturing method thereof |
KR102498071B1 (en) | 2022-07-11 | 2023-02-10 | 주식회사 엘엑스엠엠에이 | High heat-resistance unpainted polymethyl methacrylate compound resin for car exterior parts |
KR102498072B1 (en) | 2022-09-05 | 2023-02-10 | 주식회사 엘엑스엠엠에이 | Resin composition for unpainted automobile exterior and molded article including same |
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KR101652257B1 (en) | 2015-08-20 | 2016-09-09 | 엘지엠엠에이 주식회사 | Reduction method of Silver streak defects of polymethylmethacrylate resin for back light unit for in-plane switching mode liquid crystal display device |
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JP3293702B2 (en) * | 1993-11-09 | 2002-06-17 | 三菱瓦斯化学株式会社 | Method for producing methyl methacrylate polymer |
JPH09174676A (en) * | 1995-12-25 | 1997-07-08 | Mitsubishi Rayon Co Ltd | Manufacture of acrylic product |
KR100441798B1 (en) * | 2001-10-16 | 2004-07-27 | 주식회사 엘지화학 | Process for preparing discoloration resistant PMMA having high transparency |
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KR100890172B1 (en) * | 2006-12-18 | 2009-03-25 | 엘지엠엠에이 주식회사 | Coating material |
KR101494495B1 (en) * | 2011-03-23 | 2015-02-23 | 주식회사 엘지화학 | Pressure sensitive adhesive composition for an optical film |
KR20190112995A (en) * | 2018-03-27 | 2019-10-08 | 엘지엠엠에이 주식회사 | Acrylic optical film and manufacturing method thereof |
KR102498071B1 (en) | 2022-07-11 | 2023-02-10 | 주식회사 엘엑스엠엠에이 | High heat-resistance unpainted polymethyl methacrylate compound resin for car exterior parts |
KR102498072B1 (en) | 2022-09-05 | 2023-02-10 | 주식회사 엘엑스엠엠에이 | Resin composition for unpainted automobile exterior and molded article including same |
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