KR20020020774A - Aromatic Acrylic or Methacrylic Compounds and Process for Preparing the Same, Their Polymerisable Composition, and Method for Preparing a High Reflective Plastic Material - Google Patents

Aromatic Acrylic or Methacrylic Compounds and Process for Preparing the Same, Their Polymerisable Composition, and Method for Preparing a High Reflective Plastic Material Download PDF

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KR20020020774A
KR20020020774A KR1020020010931A KR20020010931A KR20020020774A KR 20020020774 A KR20020020774 A KR 20020020774A KR 1020020010931 A KR1020020010931 A KR 1020020010931A KR 20020010931 A KR20020010931 A KR 20020010931A KR 20020020774 A KR20020020774 A KR 20020020774A
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aromatic
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initiator
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김은경
이영준
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김충섭
한국화학연구원
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
    • C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
    • C07C69/54—Acrylic acid esters; Methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

PURPOSE: Provided are an aromatic acryl or methacryl compound and a preparation thereof, a polymerizable composition containing at least one of the compound, and a process for producing transparent plastic optical material excellent in refractivity, hardness, and heat-resistance by using the composition. CONSTITUTION: The aromatic acryl or methacryl compound is aromatic acrylate or methacrylate represented by the formula, wherein R1 is H or -CH3, n is 0-50, and X is -O-, -S-, -SO2, and etc. The aromatic acrylate or methacrylate represented by the formula is produced by a process comprising the steps of: stirring an aromatic diol, H2O, KOH, an organic solvent, and tetra butyl ammonium chloride(TBAC) as a catalyst; adding methacryloyl chloride(Mch) or ethylene oxy-substituted acrylate to the solution and reacting at -5 to 20deg.C for 5-16 hours; washing an organic solution layer repeatedly with distilled water and then eliminating the solvent. And the polymerizable composition contains the aromatic acrylate or methacrylate represented by the formula and an initiator. And the transparent plastic material with high refractivity is produced by polymerizing the composition in a mold.

Description

방향족 아크릴계 또는 메타아크릴계 화합물 및 그의 제조방법, 이들 화합물 하나 이상을 포함하는 중합성 조성물, 및 이로부터 고굴절 투명 플라스틱 소재를 제조하는 방법{Aromatic Acrylic or Methacrylic Compounds and Process for Preparing the Same, Their Polymerisable Composition, and Method for Preparing a High Reflective Plastic Material}Aromatic acrylic or methacrylic compounds and a method for producing the same, a polymerizable composition comprising one or more of these compounds, and a method for producing a high refractive transparent plastic material therefrom `` Aromatic Acrylic or Methacrylic Compounds and Process for Preparing the Same, Their Polymerisable Composition, and Method for Preparing a High Reflective Plastic Material}

본 발명은 안경 렌즈 및 각종 광학 렌즈등에 사용되는 내열성, 표면 경도 및 굴절율이 높은 방향족 아크릴계 또는 메타크릴계 화합물 및 그의 제조방법, 이들 화합물 하나 이상을 포함하는 중합성 조성물, 및 이로부터 고굴절 투명 플라스틱 소재를 제조하는 방법에 관한 것이다.The present invention is an aromatic acrylic or methacrylic compound having high heat resistance, surface hardness and refractive index used in spectacle lenses and various optical lenses, and a method for preparing the same, a polymerizable composition comprising at least one of these compounds, and a high refractive transparent plastic material therefrom. It relates to a method of manufacturing.

플라스틱 렌즈는 무기물 렌즈에 비하여 가볍고, 잘 깨어지지 않고 염색이 가능하기 때문에 최근에 안경용 렌즈로 주목을 받아 왔으며 디에틸렌 글리콜 비스카보네이트(이하 "CR39"로 약칭함)알릴계 중굴절율 단량체 "Copolex NK-55-C"(日本油脂株式會社, 이하 "NK55"로 약칭함)가 대량적으로 렌즈 생산에 사용되고 있으나 굴절율이 낮으므로 (CR39의 nD=1,50, NK35의 nD=1,55) 렌즈의 경량화를 위하여 높은굴절율을 가진 렌즈용 수지가 요망되고 있다.Plastic lenses have recently attracted attention as spectacle lenses because they are lighter, less fragile, and dyeable than mineral lenses. Diethylene glycol biscarbonate (abbreviated as "CR39") allyl-based medium refractive index monomer "Copolex NK-" 55-C "(日本油脂株式會社, hereinafter" NK55 "abbreviated to) a large amount, but since typically the refractive index is low, is used for the lens production (of CR39 n D = 1,50, n D = 1,55 in NK35) In order to reduce the weight of the lens, a lens resin having a high refractive index is desired.

80년대 초기 방향족과 브롬화 원자를 포함하는 광학 소재[機能材料 1998. 18(7). 33]를 덕산조달(德山曹達)에서 개발하였으나(nD=1,595, VD=32), 생산성과 색상의 문제점이 있었다. 80년대 후반기 미쯔이도오아쯔(三井東壓)사로부터 굴절율이 높은 렌즈용 소재로 폴리우레탄 계열 (이하 "MR 계열"로 약칭함)이 개발되었고, 이는 방향족을 포함한 이소시아네이트와 다관능기의 메르캅트기로 제조한 유황우레탄 계열로서 현재 고굴절, 초고굴절율 플라스틱 렌즈용 소재로 이용되고 있다. 그러나 고굴절 MR-6 (nD:1,594, VD:36, Tg 98℃) 및 초고굴절 MR-7(nD:1,660, VD:32, Tg 93℃)은 굴절율과 아벱수는 높으나 내열성이 낮으므로 렌즈의 염색이나 멀티코팅 및 열가공 등 생산성이 떨어지며 특히 표면경도가 낮아 성형 렌즈에 찰상이 잘 생기는 결함을 가지고 있다.Optical material containing aromatic and brominated atoms in the early 80's [機能 材料 1998. 18 (7). 33] was developed by Deoksan Procurement (n D = 1,595, V D = 32), but there were problems of productivity and color. In the late 80s, a polyurethane-based material (hereinafter referred to as "MR-based") was developed as a material for lenses with high refractive index by Mitsuido Oatsu Co., Ltd., which is a mercap group of an isocyanate containing polyaromatics and a polyfunctional group. Sulfur urethane is manufactured from high refractive index and ultra high refractive index plastic lens material. However, high refractive index MR-6 (n D : 1,594, V D : 36, Tg 98 ℃) and ultra high refractive MR-7 (n D : 1,660, V D : 32, Tg 93 ℃) have high refractive index and high number of Because of the low productivity, such as dyeing, multi-coating, and thermal processing of the lens, the productivity is low, and in particular, the surface hardness is low, and the molded lens has scratches that are easily generated.

예를 들면, 한국 특허 제96-13389호(발명자:나까다 데루유기), 동 제96-13390호(발명자:쓰요시오오꾸보), 일본국 특개평2-270859호, 특개평8-271702호, 특개평9-110955호 및 특개평9-110956호에 기재되어 있는 크실리렌 디이소시아네이트 화합물과 폴리티올 화합물과의 중합물로 이루어진 폴리우레탄 렌즈를 제안하고 있다. 비록 굴절율(nD:1,60∼1.66)과 아벱수(VD:33∼40)가 높고 내충격성이 뛰어났으나 내열성이 60∼90℃ 정도로 떨어졌다.For example, Korean Patent No. 96-13389 (Inventor: Terugi Nadada), 96-13390 (Inventor: Tsuyoshi Okubo), Japanese Patent Laid-Open No. 2-270859, Japanese Patent Laid-Open No. 8-271702, The polyurethane lens which consists of a polymer of the xylene diisocyanate compound and polythiol compound described in Unexamined-Japanese-Patent No. 9-110955 and 9-110956 is proposed. Although the refractive index (n D : 1,60-1.66) and the number of objects (V D : 33-40) were high and the impact resistance was excellent, the heat resistance dropped to about 60 to 90 ° C.

내열성을 향상시킬 목적으로 예를 들면 한국 특허 제133,656호(발명자:쓰요시오오꾸보), 동 제136,698호(발명자:코바야시 세이이치), 일본국 특개평7-118263호 및 특개평10-120676호에 기재 되어 있는 폴리티올의 올리고머와 폴리 이소시아네트의 반응물은 굴절율(nD:1,67∼1.68)과 아벱수(VD:34∼35)가 높을 뿐만 아니라 내열성도 110℃를 초과하였다. 그러나 표면경도가 비교적 낮아(연필경도 F급) 실용성이 떨어지게 된다.For the purpose of improving heat resistance, for example, it is described in Korean Patent No. 133,656 (Inventor: Tsuyoshi Ohokubo), Japanese Patent No. 136,698 (Inventor: Seichi Kobayashi), Japanese Patent Laid-Open No. 7-118263 and Japanese Patent Laid-Open No. 10-120676. The polythiol oligomer and the polyisocyanate reactant not only had a high refractive index (n D : 1,67-1.68) and an abundance (V D : 34-35) but also a heat resistance exceeded 110 ° C. However, the surface hardness is relatively low (pencil hardness F class), the practicality is inferior.

일본국 특공평7-47605호에 기재된 디페닐옥시디알킬 에스테르는 굴절율과 아벱수가 낮은 것(nD:1,58∼1.60)이 단점이다.Diphenyloxydialkyl esters described in Japanese Patent Application Laid-Open No. 7-47605 have a disadvantage in that the refractive index and the number of atoms are low (n D : 1,58 to 1.60).

이에 따라 굴절율과 아벱수를 향상시키고 표면경도, 내열성, 내충격성 및 절삭, 연마성이 뛰어난 렌즈용 광학소재 개발이 절실히 요구되어 왔다.Accordingly, there is an urgent need for the development of optical materials for lenses that improve the refractive index and the number of objects, and have excellent surface hardness, heat resistance, impact resistance and cutting and polishing properties.

본 발명자들은 상기의 과제를 해결하기 위하여 신규 플라스틱 광학 소재용 단량체를 연구하던 중 특정 구조를 갖는 방향족 아크릴계 또는 메타크릴계 화합물을 하나 이상 포함하는 중합성 조성물로부터 중합된 렌즈가 투명성, 굴절률, 경도, 내열성이 우수함을 알아내고 본 발명을 완성하게 되었다.In order to solve the above problems, the inventors of the present invention studied a monomer for a new plastic optical material, and a lens polymerized from a polymerizable composition including at least one aromatic acrylic or methacrylic compound having a specific structure has transparency, refractive index, hardness, It was found that the heat resistance is excellent, and completed the present invention.

본 발명은 방향족 아크릴계 또는 메타크릴계 화합물 및 그의 제조방법, 이들 화합물 하나 이상을 포함하는 중합성 조성물, 그리고 이 조성물을 이용하여 투명성, 굴절률, 경도 및 내열성이 우수한 플라스틱 소재를 제조하는 방법을 제공한다.The present invention provides an aromatic acrylic or methacrylic compound and a method for producing the same, a polymerizable composition comprising one or more of these compounds, and a method for producing a plastic material having excellent transparency, refractive index, hardness and heat resistance using the composition. .

본 발명에 따른 방향족 아크릴레이트 또는 메타아크릴레이트는 하기 화학식(1)을 갖는다:Aromatic acrylates or methacrylates according to the invention have the general formula (1)

식중 X는 -O-, -S-, -SO2-,,또는 -CH2-기이고;Wherein X is -O-, -S-, -SO 2- , , Or a -CH 2 -group;

R1은 H 또는 -CH3이고;R 1 is H or —CH 3 ;

R2는또는이며;R 2 is or Is;

R3는 Cl, Br등의 할로겐 원소로 치환된 알킬기이며;R 3 is an alkyl group substituted with a halogen element such as Cl or Br;

n은 0∼50의 수이다.n is a number from 0 to 50.

상기 화학식(1)의 단량체는 폴리에틸렌글리콜 모노(메타)아크릴레이트와 디페닐옥시 비스카보닉클로라이드, 디페닐술퍼티드 비스카보닉클로라이드 혹은 디페닐술폰 비스카보닉클로라이드등과의 반응을 통하여 제조된다.The monomer of Formula (1) is prepared through the reaction of polyethylene glycol mono (meth) acrylate with diphenyloxy biscarnic chloride, diphenylsulfurized biscarnic chloride or diphenylsulfone biscarnic chloride.

예를들면, 4,4'-옥시비스(벤조일(2-메타아크릴로에틸)에스테르)는 하기의 방법으로 제조된다. 즉, 히드록시에틸메타크릴레이트(HEMA)와 트리에틸 아미드(TEAM)을 가하고 용매60mL에 용해시키면서 교반한 후 4,4'-옥시비스(벤조일클로라이드)(DEDCh)를 디클로메탄에 용해시킨 용액을 0oC에서 30분간 서서히 가하면서 교반하고, 반응용액을 실온에서 2시간 및 45oC에서 5시간 교반한 후 물로 세척 및 정제하여 4,4'-옥시비스(벤조일(2-메타아크릴로에틸)에스테르)가 제조된다.For example, 4,4'-oxybis (benzoyl (2-methacryloethyl) ester) is manufactured by the following method. In other words, hydroxyethyl methacrylate (HEMA) and triethyl amide (TEAM) were added and stirred while dissolving in 60 mL of solvent, 4,4'-oxybis (benzoyl chloride) (DEDCh) in dichloromethane solution Was stirred at 0 o C for 30 minutes, and the reaction solution was stirred at room temperature for 2 hours and at 45 o C for 5 hours, washed with water and purified to obtain 4,4'-oxybis (benzoyl (2-methacryl). Ethyl) ester) is prepared.

이때 사용되는 4,4'-옥시비스(벤조일클로라이드)(DEDCh)는 공지의 방법으로 4,4'-옥시(벤조산)을 티오닐 클로라이드로 염화시켜 제조된다. 상기 화학식(1)의 제조에는 4,4'-옥시비스(벤조일클로라이드)대신 4,4'-비스(벤조일클로라이드)술폰, 4,4'-비스(벤조일클로라이드)설파이드, 및 다양한 구조의 비스(벤조일클로라이드)유도체(acid chloride)가 사용될 수 있다.The 4,4'-oxybis (benzoyl chloride) (DEDCh) used at this time is prepared by chlorideing 4,4'-oxy (benzoic acid) with thionyl chloride by a known method. Formula (1) may be prepared by using 4,4'-bis (benzoyl chloride) sulfone instead of 4,4'-oxybis (benzoyl chloride), 4,4'-bis (benzoyl chloride) sulfide, and various structures of bis ( Benzoyl chloride) acid chloride may be used.

또한 불포화기로 치환된 알코올로서 분자량 100 이상의 폴리옥시에틸렌 메타크릴계 또는 아크릴계 화합물이 반응될 수있으며, 촉매로서 TBAB, BTAC, KOH, K2CO3, TEAM, 기타 아민 착화합물등이 이용될 수있다.In addition, a polyoxyethylene methacryl or acrylic compound having a molecular weight of 100 or more may be reacted as an alcohol substituted with an unsaturated group, and TBAB, BTAC, KOH, K 2 CO 3 , TEAM, and other amine complexes may be used as a catalyst.

용매로는 디클로메탄, 디클로로에탄, 클로로포름, 톨루엔, 벤젠, 물 등의 일반적인 유기 용매 및 수용액 또는 이들의 혼합물이 사용될 수 있다.As the solvent, general organic solvents such as dichloromethane, dichloroethane, chloroform, toluene, benzene, water, and aqueous solutions or mixtures thereof may be used.

반응온도는 -20oC∼150oC 로서 바람직하게는 산 클로라이드의 적하시 -5oC∼10oC 의 범위에서 교반하다가 적하 완결 후 환류시키는 조건(용매에 따라 30oC∼150oC)이 적합하다.The reaction temperature is -20 o o C~150 when Preferably the addition of the acid chloride as a -5 o C o C~10 conditions to reflux after completion of the dropwise addition while stirring in a range of C (depending on the solvent o C 30 o C~150 Is appropriate.

본 발명에 따른 또 다른 방향족 아크릴레이트 또는 메타아크릴레이트는 하기 화학식(2)을 갖는다:Another aromatic acrylate or methacrylate according to the invention has the formula (2)

식중 R1은 H 또는 -CH3이고, n은 0∼50의 수이다.Wherein R 1 is H or —CH 3 and n is a number from 0 to 50;

상기 화학식(2)의 단량체는 γ-이소프로페닐 α·α-디메틸 벤질 이소시아네이트로부터 제조된다.The monomer of formula (2) is prepared from γ-isopropenyl α-α-dimethyl benzyl isocyanate.

예를들면, 반응기에 3-이소프로페닐-디메틸벤질 이소시아네이트40.2g을 투입한후, 촉매로서 디부틸틴 디라우레이트0.402g을 투입하고, 분액 깔대기를 통하여 HEMA 26.16g을 상기 용액에 적하하면서 4.5시간 동안 교반하면, 수율 90%로 ND18=1.5260를 가지는 하기 화학식(1e)의 화합물이 제조된다.For example, 40.2 g of 3-isopropenyl-dimethylbenzyl isocyanate was added to the reactor, 0.402 g of dibutyltin dilaurate was added as a catalyst, and 26.16 g of HEMA was added dropwise to the solution through a separating funnel. Stirring for a time yields a compound of formula (Ie) having ND 18 = 1.5260 in 90% yield.

상기 화학식(2)의 제조에는 불포화기로 치환된 알코올로서 분자량 100이상의 펜타에리트리톨 트리아크릴레이트(PETA) 및 폴리(에틸글리콜)모노메타크릴레이트(분자량 100~3000)와 같은 폴리옥시에틸렌 메타크릴계 또는 아크릴계 화합물이 반응될 수 있으며, 분자량 50이상의 알코올 또는 글리콜이 사용될 수 있다.In the preparation of Chemical Formula (2), polyoxyethylene methacrylates such as pentaerythritol triacrylate (PETA) and poly (ethylglycol) monomethacrylate (molecular weight 100 to 3000) having a molecular weight of 100 or more as an alcohol substituted with an unsaturated group Alternatively, an acrylic compound may be reacted, and an alcohol or glycol having a molecular weight of 50 or more may be used.

상기 반응은 용매를 사용할 수도 있으며, 용매로는 디클로로메탄, 디클로로에탄, 클로로포름, 톨루엔, 벤젠 등의 일반적인 유기 용매가 사용될 수있다.The reaction may be a solvent, a general organic solvent such as dichloromethane, dichloroethane, chloroform, toluene, benzene may be used as the solvent.

반응온도는 -20oC∼150oC로서 바람직하게는 알코올의 적하시 -5oC∼30oC에서 교반하다가 적하 완결 후 알코올 및 용매에 따라 30oC∼150oC, 바람직하게는 50∼80oC로 제어하는 것이 적합하다. 반응시간은 30분∼24시간, 바람직하게는 2∼6시간이다.The reaction temperature is -20 o o C~150 when Preferably the addition of the alcohol as a -5 o C while stirring at C~30 o C after completion of the dropwise addition, depending on the alcohol and the solvent C~150 o 30 o C, preferably 50 be controlled by ~80 o C are suitable. The reaction time is 30 minutes to 24 hours, preferably 2 to 6 hours.

본 발명에 따른 또 다른 방향족 아크릴레이트 또는 메타아크릴레이트는 하기화학식(3)을 갖는다:Another aromatic acrylate or methacrylate according to the invention has the formula (3)

하기 화학식(3)의 방향족 아크릴레이트 또는 메타아크릴레이트:Aromatic acrylates or methacrylates of the general formula (3)

식중 R1은 H 또는 -CH3이고;In which R 1 is H or —CH 3 ;

n은 0∼50의 수이고;n is a number from 0 to 50;

X는 -O-, -S-, -SO2-,,또는 -CH2이고;X is -O-, -S-, -SO 2- , , Or -CH 2 ;

Y는혹은 직접 결합이다.Y is Or direct coupling.

상기 화학식(3)의 화합물은 (메타)아크릴클로라이드 혹은 폴리에틸렌글리콜모노(메타)아크릴 클로로폴메이트와 티오디페놀(4,4'-티오디페놀), 옥시비스페놀(4,4'-옥시비스페놀), 비스페놀A, 비스페놀S등과의 반응을 거쳐 제조된다.The compound of formula (3) is (meth) acrylic chloride or polyethylene glycol mono (meth) acryl chlorofolate And thiodiphenol (4,4'-thiodiphenol), oxybisphenol (4,4'-oxybisphenol), bisphenol A, bisphenol S, and the like.

예를들면, 반응기에 4.4'-디히드록시 디페닐에테르와 H2O를 투입하고, 이어서 KOH를 투입하여 교반 및 용해한후, 디클로로메탄과 촉매 벤질트리메틸암모늄 클로라이드(BTAC)11.15g을 투입하여 완전히 용해시킨 다음 반응기내 온도를 0∼5℃ 범위로 맞추고, 메타크릴로일 클로라이드(Mch)를 반응시키면, 화학식(3a)의 방향족메타크릴레이트가 제조된다. 디클로로메탄에 녹여 상기 용액에 서서히 적하 하면서 교반시키다가 적하 완료후 반응기 내부의 온도를 서서히 실온까지 올리면서 교반하여 5∼6시간후 세척 정제 시키면, 화학식(3a)의 방향족 메타크릴레이트가 제조된다. 상기 반응에서 디페놀계로서 4.4'-디히드록시 디페닐에테르대신 4.4'-티오디페놀(THOP)를 사용할 수 있으며, 산 클로라이드로서 아크릴클로라이드를 사용할 수도 있다.For example, 4.4'-dihydroxy diphenyl ether and H 2 O were added to the reactor, followed by stirring and dissolution by adding KOH, followed by 11.15 g of dichloromethane and the catalyst benzyltrimethylammonium chloride (BTAC). After dissolution, the temperature in the reactor is adjusted to a range of 0 to 5 ° C., and the methacryloyl chloride (Mch) is reacted to produce an aromatic methacrylate of formula (3a). After dissolving in dichloromethane and slowly dropwise addition to the solution, the mixture was stirred, and after completion of the dropwise addition, the temperature inside the reactor was gradually raised to room temperature, stirred and washed after 5-6 hours to prepare an aromatic methacrylate of formula (3a). In the reaction, 4.4'-thiodiphenol (THOP) may be used instead of 4.4'-dihydroxy diphenyl ether as the diphenol type, and acryl chloride may be used as the acid chloride.

용매로서는 디클로로메탄, 물, 알코올, 기타 유기 용매들이 사용될 수있으며, 촉매로서는 TBAB, BTAC, KOH, K2CO3, TEAM, 기타 아민 착화합물등이 이용될 수 있다.As the solvent, dichloromethane, water, alcohol, other organic solvents may be used, and as the catalyst, TBAB, BTAC, KOH, K 2 CO 3 , TEAM, other amine complexes, and the like may be used.

반응온도는 -20℃∼100℃로서 바람직하게는 산 클로라이드의 적하시 -5℃∼10℃에서 교반하다가 적하 완결 후 용매에 따라 실온 내지 60℃의 온도로 제어하는 것이 적합하다.The reaction temperature is preferably -20 ° C to 100 ° C, preferably stirred at -5 ° C to 10 ° C at the dropwise addition of the acid chloride, and then controlled to a temperature of room temperature to 60 ° C depending on the solvent after completion of the dropwise addition.

본 발명에 따른 방향족 메타아크릴계 또는 아크릴계 화합물(1, 2, 3) 중 하나 이상이 서로 혼합되어 중합성 조성물을 형성하며 , 이 조성물은 라디칼 개시제와 함께, 특히 주형중합시 플라스틱렌즈 또는 플라스틱 광학부품등을 제조하는 데 유용하게 사용된다.At least one of the aromatic methacrylic or acrylic compounds (1, 2, 3) according to the present invention is mixed with each other to form a polymerizable composition, which composition together with a radical initiator, in particular plastic lenses or plastic optical parts, etc. It is usefully used to make it.

예를들면, 실시예1에서 제조된 화학식(1)의 화합물과 실시예 8에서 제조되는 화학식(1e)의 화합물을 80/20 중량%의 비로 혼합 및 교반 한 후 α·α'아조비스(이소부티로니트릴)(AIBN)(2.5 중량%)를 가하면 중합성 조성물을 제조한다. 제조된조성물의 굴절률은 20℃에서 1.5337이다.For example, after mixing and stirring the compound of formula (1) prepared in Example 1 and the compound of formula (1e) prepared in Example 8 at a ratio of 80/20% by weight, αα azobis (iso Butyronitrile) (AIBN) (2.5 wt.%) Was added to prepare a polymerizable composition. The refractive index of the prepared composition is 1.5337 at 20 ° C.

개시제로는 AIBN, 벤조일퍼옥시드(BPO), 디이소프로필 퍼옥시 디카보네이트(IPP), 3차 부틸 히드로 퍼옥시드(TBPO), 기타 열 또는 광 개시제 또는 이들의 혼합물이 사용될 수 있다. 본 발명에 있어서 각 성분의 사용 비율은 0∼100%로서 사용 용도 및 렌즈 물성의 요구에 따라 적당히 조절한다. 또한 상기의 조성물에는 NK55, CR39, α-메틸스틸렌, 스티렌, 폴리에틸렌옥시메타아크릴레이트 또는 그의 아크릴레이트, 폴리에틸렌옥시디아크릴레이트, 알킬렌트리아크릴레이트, 기타 공지의 불포화기를 가지는 화합물 중에서 선택된 1종이상의 화합물을 첨가하여 제조될 수 있다.Initiators include AIBN, benzoyl peroxide (BPO), Diisopropyl peroxy dicarbonate (IPP), tertiary butyl hydroperoxide (TBPO), other thermal or photoinitiators or mixtures thereof may be used. In the present invention, the use ratio of each component is 0 to 100%, and is appropriately adjusted according to the use purpose and the lens physical properties. In the above composition, at least one compound selected from NK55, CR39, α-methylstyrene, styrene, polyethyleneoxy methacrylate or its acrylate, polyethyleneoxy diacrylate, alkylene triacrylate, and other known unsaturated groups It can be prepared by the addition of a compound.

본 발명에 있어서는 중합반응의 촉진을 위한 중합 촉매, 내후성 개량을 위한 자외선 흡수제 및 착색 방지제등을 필요에 따라 적당히 첨가해도 된다.In the present invention, a polymerization catalyst for promoting the polymerization reaction, an ultraviolet absorber for improving weather resistance, a coloring inhibitor, and the like may be appropriately added as necessary.

특히 본 발명의 화합물 중 황 함유 디페닐 술파이드의 에스테르 화합물은 라디칼 중합성을 부여하며, 고굴절율 저분산용으로 적합하며, 우레탄 폴리(메타)아크릴계 에스테르의 조성물은 내충격성 표면경도가 뛰어나게 하며, 무색 투명하고 경량이며 내후성이 뛰어난 특징을 가지고 있어 플라스틱 안경 렌즈, 카메라 렌즈등 광학 소자 재료로 바람직하다.In particular, the ester compound of sulfur-containing diphenyl sulfide among the compounds of the present invention imparts radical polymerizability, is suitable for high refractive index low dispersion, the composition of the urethane poly (meth) acrylic ester has excellent impact resistance surface hardness, It is colorless, transparent, lightweight, and has excellent weather resistance. It is suitable for optical element materials such as plastic glasses lenses and camera lenses.

상기의 조성물은 유리판, ITO, 실리콘 웨이퍼, 기타 지지체 위에 코팅될 수 있으며, 또한 다양한 재질의 몰드에 넣어 열경화 및/또는 광경화를 통하여 성형될 수 있다. 열경화 조건은 실온 내지 120℃에서 이루어지며, 프로그램된 오븐을 사용하여 개시제의 종류에 따라 일정 시간 간격과 온도 간격으로 경화시키는 것이 바람직하다. 일례로 상기 조성물을 AIBN 혹은 BPO 개시제를 사용하여 주형 중합하는 경우 하기의 반응조건을 선택하여 고경도, 고굴절율 플라스틱 광학렌즈가 제조되며, 무색투명하고 내열성, 가공성이 뛰어난 렌즈용 광학소재가 제조된다:The composition may be coated on a glass plate, ITO, silicon wafer, other support, and may also be molded into a mold of various materials through thermosetting and / or photocuring. Thermosetting conditions are made at room temperature to 120 ℃, it is preferable to cure at a predetermined time interval and temperature intervals according to the type of initiator using a programmed oven. For example, when the composition is polymerized using an AIBN or BPO initiator, a high hardness, high refractive index plastic optical lens is prepared by selecting the following reaction conditions, and a colorless, transparent, heat resistant and workable optical material for the lens is prepared. :

실온 ―(60분)→ 60℃ ―(180분)→ 60℃―(60분)→75℃―(180분)→ 75℃ ―(120분)→ 90℃ ―(120분)→ 90℃ ―(120분)→ 120℃ ―(120분)→ 120℃―(자연냉각)→60℃.Room temperature-(60 minutes) → 60 ° C-(180 minutes) → 60 ° C-(60 minutes) → 75 ° C-(180 minutes) → 75 ° C-(120 minutes) → 90 ° C-(120 minutes) → 90 ° C- (120 minutes) → 120 ° C-(120 minutes) → 120 ° C-(natural cooling) → 60 ° C.

실시예Example

상기 설명한 바와 같은 본 발명의 특징 및 기타 장점은 후술하는 실시예를 통해 보다 상세히 설명되지만, 본 발명의 범위가 하기 실시예에 의해 한정되는 것은 아니다. 또한 실시예중에 중량부를 표시하고 성능평가는 이하의 시험법으로 한다.Features and other advantages of the present invention as described above are described in more detail through the following examples, but the scope of the present invention is not limited by the following examples. In addition, the weight part is shown in an Example, and the performance evaluation shall be the following test methods.

내열성은 TGA(Thermo Gravimetry Analysis)와 DSC(Differential Scanning Calorimetry)의 열분석으로 평가한다. 표면경도는 연필 긁기 시험기를 사용해서 연필경도를 측정하였다. 굴절율 압베수는 ATAGO사 제품 "DR-A1" 굴절기를 사용하여 20℃에서 측정하였다.Heat resistance is evaluated by thermal analysis of TGA (Thermo Gravimetry Analysis) and DSC (Differential Scanning Calorimetry). Surface hardness measured the pencil hardness using the pencil scraping tester. The refractive index Abbe's number was measured at 20 ° C using a "DR-A1" refractor manufactured by ATAGO.

내마모성은 강선(steel wool)을 사용하여 마찰시킴으로써 측정한다. 측정에서 사용되는 강선의 종류는 #0(1), #00(2), #000(3) 또는 #0000(4)의 표시로 나타내고, 내마모성 실험의 결과는 하기와 같이 A, B 및 C로 구분하여 나타낸다.Wear resistance is measured by rubbing using steel wool. The type of steel wire used in the measurement is indicated by the indication of # 0 (1), # 00 (2), # 000 (3) or # 0000 (4), and the results of the abrasion resistance test were A, B and C as follows. It is shown separately.

A는 강력한 마찰에 의해서도 손상이 없음을 표시하고,A indicates no damage even by strong friction,

B는 강력한 마찰에 의해 손상이 있음을 말하며,B is damaged by strong friction,

C는 약간의 마찰에 의해 손상이 있음을 표시한다.C indicates damage by slight friction.

즉, A1, A2, A3 및 A4는, 각각 강선 #0, #00, #000 또는 #0000로 마찰하였을 때(일정무게 (4 lb)의 무게로 10회) 손상이 없는 경우를 의미하고,That is, A1, A2, A3, and A4 mean no damage when rubbed with steel wires # 0, # 00, # 000 or # 0000, respectively (10 times with a weight of 4 lb),

B1, B2, B3 및 B4는, 각각 강선 #0, #00, #000 또는 #0000로 마찰하였을 때(일정무게 (4 lb)의 무게로 10회) 손상이 있는 경우를 의미하며,B1, B2, B3 and B4 refer to the case where there is damage when rubbed with steel wires # 0, # 00, # 000 or # 0000 (10 times with a weight of 4 lb),

C1, C2 C3 및 C4는, 각각 강선 #0, #00, #000 또는 #0000로 마찰하였을 때(일정무게 (1 lb)의 무게로 3회) 손상이 있는 경우를 의미한다.C1, C2 C3 and C4 refer to the case where there is damage when rubbed with steel wires # 0, # 00, # 000 or # 0000 (three times with a weight of 1 lb).

외관 : 눈으로 보고 관찰 하였다.Appearance: Observed by eye.

흡수율 : 제작한 시험편을 실온에서 물속에 48시간 침지시키고 그 후의 중량 변화로부터 흡수율을 측정하였다.Absorption rate: The prepared test piece was immersed in water at room temperature for 48 hours, and the water absorption rate was measured from the weight change thereafter.

투과율은 두께 2mm의 시험편을 제작하여 UV/Vis스펙트로 400∼800nm의 투과율을 측정하였다. 투과율값은 600 nm의 투과율을 정리하였다.The transmittance | permeability produced the test piece of thickness 2mm, and measured the transmittance | permeability of 400-800 nm by UV / Vis specification. The transmittance values summarized the transmittance of 600 nm.

합성예1: 4,4'-옥시비스(벤조일클로라이드)(DEDCh)의 제조 Synthesis Example 1 Preparation of 4,4′-oxybis (benzoyl chloride) (DEDCh)

교반기, 분액 깔대기, 온도계 및 냉각기를 갖춘 500ml 용량의 4구 내압 유리제 반응기에 용매로서 디클로로에탄300ml을 투입하고 4,4'-옥시(벤조산)129.1g, 촉매 LiCl 0.85g 및 피리딘5ml를 투입하고 20분간 교반한다. 상기 용액에 티오닐 클로라이드 148.6g(91.1ml)을 반응온도 60℃로 맞추어 분액 깔대기를 통하여 천천히 투입한다. 80℃에서 계속 반응시키면서 PH의 검출을 통하여 산성이 거의 나타나지 않을 정도에서 과량의 티오닐 클로라이드와 용매를 회수하면 고형의 4,4'-옥시비스(벤조일클로라이드)가 제조된다. 수득된 고체를 디클로로메탄에 용해시키고 재결정시키면 124g(수율 84 %)의 정제된 4,4'-옥시비스(벤조일클로라이드)가 제조된다. 융점(mp) 87∼89℃.Into a 500 ml four-bar pressure glass reactor equipped with a stirrer, a separatory funnel, a thermometer and a cooler, 300 ml of dichloroethane was added as a solvent, 129.1 g of 4,4'-oxy (benzoic acid), 0.85 g of catalyst LiCl, and 5 ml of pyridine were added. Stir for minutes. 148.6 g (91.1 ml) of thionyl chloride was slowly added to the solution through a separating funnel at a reaction temperature of 60 ° C. Solid 4,4'-oxybis (benzoyl chloride) is prepared by recovering excess thionyl chloride and solvent to the extent that acidity is hardly observed through the detection of PH while continuing to react at 80 ° C. The resulting solid was dissolved in dichloromethane and recrystallized to afford 124 g (84% yield) of purified 4,4'-oxybis (benzoylchloride). Melting point (mp) 87-89 degreeC.

합성예2: 4,4'-비스(벤조일클로라이드)술폰(DSDCh)의 제조 Synthesis Example 2 Preparation of 4,4'-bis (benzoylchloride) sulfone (DSDCh)

상기 방법에서 4,4'-옥시(벤조산)대신 4,4'-비스(벤조산)술폰으로 바꾸어 반응시키면 수율90%로 4,4'-비스(벤조일클로라이드)술폰이 제조된다.In the above method, 4,4'-bis (benzoyl chloride) sulfone is produced in a yield of 90% by changing to 4,4'-bis (benzoic acid) sulfone instead of 4,4'-oxy (benzoic acid).

실시예 1:4,4'-옥시비스(벤조일(2-메타아크릴로에틸)에스테르)의합성(화학식 1a) Example 1 Synthesis of 4,4′-oxybis (benzoyl (2-methacryloethyl) ester) (Formula 1a)

반응용기에 HEMA 28.64g, TEAM 30.27mL을 가하고 용매로서 메틸렌 클로라이드(MC) 60mL에 용해시키면서 교반한다. 상기 용액에 DEDCh 29.5g을 디클로메탄 60mL에 용해시킨 용액을 0℃에서 30분간 서서히 가하면서 교반한다. 반응용액을 실온에서 2시간 교반한 후, 45℃에서 5시간 교반 후 물로 세척한다. 유기 용액층을 건조 시킨 후 용매를 제거하여 47.48g의 4,4'-옥시비스(벤조일(2-메타아크릴로에틸)에스테르)를 제조한다(수율 98%).28.64 g HEMA and 30.27 mL of TEAM are added to the reaction vessel, and the solution is stirred while dissolving in 60 mL of methylene chloride (MC) as a solvent. The solution in which 29.5 g of DEDCh was dissolved in 60 mL of dichloromethane was slowly added to the solution while stirring at 0 ° C. for 30 minutes. The reaction solution was stirred at room temperature for 2 hours, and then stirred at 45 ° C. for 5 hours and washed with water. After drying the organic solution layer, the solvent was removed to prepare 47.48 g of 4,4'-oxybis (benzoyl (2-methacryloethyl) ester) (yield 98%).

IR(KBr) : 2958. 1453. 1369cm-1(-CH3)IR (KBr): 2958. 1453. 1369 cm -1 (-CH 3 )

2924. 1453. 745cm-1(-CH2-)2924.1453.745 cm -1 (-CH 2- )

1720cm-1(C=O)1720cm -1 (C = O)

1637cm-1(C=C)1637cm -1 (C = C)

1596. 1500cm-1(C-O)1596. 1500cm -1 (CO)

1163. 1099cm-1(C-O-C)1163.1099 cm -1 (COC)

1H-NMR(300Mz, COCl3, PPM) 1 H-NMR (300Mz, COCl 3 , PPM)

1.87(S, -CCH 3 =CH2, 6H)1.87 (S, -CC H 3 = CH 2 , 6H)

4.40∼4.51(m, -CH2 CH 2 -, 8H)4.40 to 4.51 (m, -CH 2 CH 2- , 8H)

5.51∼5.52 [d, -CCH2=CH 2 (Cis), 2H]5.51 to 5.52 [d, -CCH 2 = C H 2 (Cis), 2H]

5.52∼6.07 [d, -CCH3=CH 2 (Trans), 2H]5.52 to 6.07 [d, -CCH 3 = C H 2 (Trans), 2H]

6.97∼7.00 (d,,4H) 7.96∼7.99 (d,, 4H)6.97-7.00 (d, , 4H) 7.96-7.99 (d, , 4H)

실시예 2∼4Examples 2-4

실시예 1에서 산 클로라이드 및 촉매, 용매, 알코올을 표1과같이 바꾸어 다양한 방향족(메타)아크릴계 단량체를 제조하였다.In Example 1, acid chlorides, catalysts, solvents, and alcohols were changed as shown in Table 1 to prepare various aromatic (meth) acrylic monomers.

화학식 (1)의 화합물의 합성제조Synthesis of Compounds of Formula (1) 실시예Example 산 염화물Acid chloride 알코올Alcohol 용매menstruum 촉매catalyst 반응조건Reaction condition 수율yield 비 고Remarks 1One DEDCh(29.5g)DEDCh (29.5 g) HEMA (28.64g)HEMA (28.64 g) MC/120mlMC / 120ml TEAM (30.7ml)TEAM (30.7ml) Reflux/5hrReflux / 5hr 98.4%(47.48g)98.4% (47.48 g) 화학식 1aFormula 1a 22 DEDCh (14.76g)DEDCh (14.76g) PG(39.6g)PG (39.6 g) MC/100mlMC / 100ml TEAM (15.35ml)TEAM (15.35ml) Reflux/24hrReflux / 24hr 45.9%(29.17g)45.9% (29.17 g) 화학식 1bFormula 1b 33 DSCh(15.5g)DSCh (15.5 g) HEMA (14.32g)HEMA (14.32g) EC/100mlEC / 100ml TEAM (15ml)TEAM (15ml) 70℃/7.5hr70 ℃ / 7.5hr 57.5%(15.23g)57.5% (15.23 g) 화학식 1cFormula 1c 44 DECh(29.51g)DECh (29.51 g) GMA(34.12g)GMA (34.12 g) TOl/150mlTOl / 150ml TBAB (3.86g)TBAB (3.86g) 80~90℃/6.5hr80 ~ 90 ℃ / 6.5hr 87.3%(26.2g)87.3% (26.2 g) 화학식 1dFormula 1d

(화학식 1의 합성)(Synthesis of Chemical Formula 1)

1.4.4' DEDCh : 1. 4.4 'DEDCh:

2.4.4' DSDCh : 2. 4.4 'DSDCh:

3.HEMA : 2-히드록시에틸메타크릴레이트: 3. HEMA: 2- hydroxyethyl methacrylate:

4.PG360: 폴리(에틸글리콜)모노메타크릴레이트(평균분자량 360) 4. PG360: poly (ethyl glycol) monomethacrylate (average molecular weight 360)

5.MC : 메틸렌 클로라이드(CH2Cl2) 5. MC: methylene chloride (CH 2 Cl 2)

6.TOL : 톨루엔 (C6H5CH3) 6. TOL: toluene (C 6 H 5 CH 3)

7.EC : 1,2-에틸렌 클로라이드(ClCH2CH2Cl) 7. EC: 1,2- ethylene chloride (ClCH 2 CH 2 Cl)

8.TBAB : 테트라부틸암모늄 브로마이드 [CH3(CH2)3]4NBr 8. TBAB: Tetrabutylammonium bromide [CH 3 (CH 2 ) 3 ] 4 NBr

9.BTAc : 벤질트리메틸암모늄 클로라이드[C6H5CH2N(CH3)3Cl] 9. BTAc: benzyltrimethylammonium chloride [C 6 H 5 CH 2 N (CH 3 ) 3 Cl]

10.TEAM : 트리에틸 아미드[(C2H5)3N] 10. TEAM: triethyl amide [(C 2 H 5 ) 3 N]

11.GMA : 글리시딜 메타크릴레이트. 11. GMA: glycidyl methacrylate.

실시예 5: 화학식 1e의 합성 Example 5 Synthesis of Formula 1e

교반기, 분액 깔대기 및 온도계를 구비한 500ml 용량의 3구 내압 유리제 반응기에 3-이소프로페닐-디메틸벤질 이소시아네이트40.2g을 투입한후, 촉매로서 디부틸틴 디라우레이트0.402g을 투입한다. 분액 깔대기를 통하여 HEMA 26.16g을 상기 용액에 적하하면서 교반한다. 반응온도를 65℃∼70℃범위에서 제어하였으며 반응중 용액을 일정시간 간격마다 취하여 IR분석을 통해 반응의 정도를 확인한다. 4.5시간 후 반응이 완결되면, 냉각 및 정제 하여 화학식(1e)의 화합물이 제조된다(수율 90%). ND18=1.526040.2 g of 3-isopropenyl - dimethylbenzyl isocyanate was introduced into a 500 ml three-bar pressure glass reactor equipped with a stirrer, a separating funnel and a thermometer, followed by adding 0.402 g of dibutyltin dilaurate as a catalyst. Stir with 26.16 g HEMA dropwise into the solution through a separatory funnel. The reaction temperature was controlled in the range of 65 ° C. to 70 ° C. The solution was taken at regular intervals and the degree of reaction was confirmed by IR analysis. After 4.5 hours, when the reaction is complete, the compound of formula 1e is prepared by cooling and purification (yield 90%). ND 18 = 1.5260

IR(KBr) : 3358. 1523cm-1(-NH-), 2975. 1456. 1385cm-1(-CH3)IR (KBr): 3358 1523 cm -1 (-NH-), 2975 1456. 1385 cm -1 (-CH3)

2924. 745cm-1(-CH2-), 1719cm-1(C=O), 1636cm-1(C=C)2924.745 cm -1 (-CH2-), 1719 cm -1 (C = O), 1636 cm -1 (C = C)

1601. 1578cm-1(C=Car), 1320. 1298. 1253(C-O)1601.1578 cm -1 (C = Car), 1320.1298.1253 (CO)

1169. 1095cm-1(C-O-C)1169.1095 cm -1 (COC)

1H-NMR(300Mz. COCl3. PPM) 1 H-NMR (300 Mz. COCl 3 .PPM)

1.69(S,, 6H), 1.96(S, CH2=, 3H), 2.17(S,1.69 (S, , 6H), 1.96 (S, CH 2 = , 3H), 2.17 (S,

CH2=, 3H)CH 2 = , 3H)

3.37∼3.38(t, -OCH2CH2O-, 2H), 4.27∼4.31(t, -OCH 2 CH2O-, 2H)3.37 to 3.38 (t, -OCH 2 CH 2 O-, 2H), 4.27 to 4.31 (t, -OC H 2 CH 2 O-, 2H)

5.09, 5.10(S,, 1H), 5.29(S,, 1H),5.09, 5.10 (S, , 1H), 5.29 (S, , 1H),

5.29, 6.14(S,, 1H), 7.28∼7.33(m,, 3H)5.29, 6.14 (S, , 1H), 7.28 to 7.33 (m, , 3H)

7.51(S,, 1H)7.51 (S, , 1H)

실시예 6∼9Examples 6-9

실시예 5에서 시아네이트와 알코올, 촉매, 반응온도 등을 표 2와 같은 방법으로 바꾸면 다양한 구조를 갖는 화학식(2)의 화합물이 제조된다.In Example 5, the compound of formula (2) having various structures is prepared by changing the cyanate with alcohol, catalyst, reaction temperature, and the like in Table 2.

화학식(2)의 화합물의 합성Synthesis of Compound of Formula (2) 실시예Example 시아네이트Cyanate 알코올Alcohol DBTDLDBTDL 반응조건Reaction condition 외관Exterior 비 고Remarks 55 40.2g40.2 g HEMA 26.16gHEMA 26.16 g 0.402g0.402 g 65℃∼70℃/4.5hr65 ℃ -70 ℃ / 4.5hr 무색투명transparent 화학식 2aFormula 2a 66 30.19g30.19 g PETA 44.75gPETA 44.75 g 0.45g0.45 g 60℃/4hr60 ℃ / 4hr 백색고형물White solid 화학식 2bFormula 2b 77 41.26g41.26 g TEG 15.02gTEG 15.02 g 0.54g0.54 g 60℃/4hr60 ℃ / 4hr 백색 고형물White solids 화학식 2cFormula 2c 88 20.13g20.13 g Ien 16.62gIen 16.62 g 0.45g0.45 g 60℃/4hr60 ℃ / 4hr 백색 고형물White solids 화학식 2dFormula 2d 99 20.13g20.13 g PG200 20gPG200 20g 0.45g0.45 g 60℃/4hr60 ℃ / 4hr 백색 고형물White solids 화학식 2eFormula 2e

1. 3-IPDBI : 3-이소프로페닐-디메틸벤질이소시아네이트1.3-IPDBI: 3-isopropenyl-dimethylbenzyl isocyanate

2. DBTDL : 디부틸틴 디라우레이트2.DBTDL: Dibutyltin Dilaurate

[CH3(CH2)10COO]2Sn[(CH2)3CH3]2 [CH 3 (CH 2 ) 10 COO] 2 Sn [(CH 2 ) 3 CH 3 ] 2

3. HEMA : 2-히드록시에틸 메타크릴레이트3.HEMA: 2-hydroxyethyl methacrylate

4. PETA : 펜타에리트리톨 트리아크릴레이트4.PETA: Pentaerythritol triacrylate

(H2C=CHCOOCH2)3CCH2OH(H 2 C = CHCOOCH 2 ) 3 CCH 2 OH

5. TEG : 트리에틸렐글리콜5. TEG: Triethylellol

HO-(CH2CH2O)2-CH2CH2OHHO- (CH 2 CH 2 O) 2 -CH 2 CH 2 OH

6. Ien : 이소유게놀6. Ien: Isoeugenol

CH3O-C6H3-(CH2=CH-CH3)OHCH 3 OC 6 H 3- (CH 2 = CH-CH 3 ) OH

7. PG200 : 폴리(에틸렌글리콜)(200) 모노메타크릴레이트7.PG200: Poly (ethylene glycol) (200) monomethacrylate

실시예 10: 화학식3의 화합물의 합성 Example 10 Synthesis of Compound of Formula 3

교반기, 분액깔대기 및 온도계를 구비한 500ml 용량의 3구 내압 유리 반응기에 4.4'-디히드록시디페닐에테르80.8g 및 H2O 200ml를 투입하고 1.6mol의 KOH를 투입하여 교반 및 용해한 후, 150ml의 MC, 촉매 BTAC (Benzyl trimethyl ammonium chloride) 11.15g (0.06mol)을 투입하여 완전히 용해시킨다. 반응기내 온도를 0∼5℃ 범위로 맞추고, 분액 깔대기에 50ml의 디클로로메탄을 가한 다음, 0.84mol의 Mch을 혼합하여 서서히 적하한다. 적하 완료후 반응기 내부의 온도를 서서히 실온까지 올리면서 교반하여 반응을 계속 진행한다. 반응시간을 일반적으로 5∼6시간으로 하고 투명한 반응물이 되었을 때 증류수로 반복적으로 세척하여 중화시킨다. 이후 활성탄으로 탈색후 무수 황산마그네슘으로 건조시키고, 여과한 모액의 디클로로메탄을 증발시키면 화학식(3a)의 방향족 메타크릴레이트가 제조된다.Into a 500 ml three-bar pressure glass reactor equipped with a stirrer, a separatory funnel and a thermometer, 80.8 g of 4.4'-dihydroxydiphenyl ether and 200 ml of H 2 O were added, 1.6 mol of KOH was added thereto, stirred and dissolved, and 150 ml. MC, 11.15g (0.06mol) of BTAC (Benzyl trimethyl ammonium chloride) was added to dissolve completely. The temperature in the reactor is adjusted to 0 to 5 ° C, 50 ml of dichloromethane is added to the separating funnel, and 0.84 mol of Mch is mixed and slowly added dropwise. After completion of the dropping, the reaction was continued by stirring while gradually raising the temperature in the reactor to room temperature. The reaction time is generally 5 to 6 hours, and when it becomes a transparent reactant, it is repeatedly washed with distilled water and neutralized. After decolorizing with activated carbon, dried over anhydrous magnesium sulfate, and dichloromethane of the filtered mother liquor is evaporated to produce an aromatic methacrylate of formula (3a).

융점(mp):90∼91℃, 원소분석 : C20H18O5(338.3)Melting point (mp): 90-91 ° C, elemental analysis: C 20 H 18 O 5 (338.3)

이론계산치 : C 70.99%, H 5.36%, O 23.64%Theoretical calculations: C 70.99%, H 5.36%, O 23.64%

측 정 치 : C 70.50%, H 5.40%, O 22.27%Measured value: C 70.50%, H 5.40%, O 22.27%

IR(KBr) : 29.53, 1454, 1380cm-1(-CH3), 1730cm-1(-C=O)IR (KBr): 29.53, 1454, 1380 cm -1 (-CH 3 ), 1730 cm -1 (-C = O)

1635cm-1(>C=C<), 1600, 1498cm-1(>C=C<ar)1635cm -1 (> C = C <), 1600, 1498cm -1 (> C = C <ar)

1320, 1296, 1250cm-1(∋C-O-C∈)1320, 1296, 1250cm -1 (∋COC∈)

1H-NMR(300Mz, COCl3, PPM) 1 H-NMR (300Mz, COCl 3 , PPM)

2.04(S, -CCH3=CH2, 6H), 5.73(d,cis, 2H),2.04 (S, -CCH 3 = CH 2 , 6H), 5.73 (d, cis, 2H),

6.32(d,trans, 2H) 6.98∼7.01(d,, 4H),6.32 (d, trans, 2H) 6.98 to 7.01 (d, , 4H),

7.04∼7.08(d,, 4H)7.04 to 7.08 (d, , 4H)

실시예 11∼13Examples 11-13

실시예 10에서 디페놀과 산 클로라이드, 용매 및 기타 반응조건을 표 3에 정리한바와같이 바꾸면 화학식(3b∼3d)의 방향족 아크릴레이트 또는 메타크릴레이트가 제조된다.In Example 10, diphenols, acid chlorides, solvents, and other reaction conditions were changed as shown in Table 3 to prepare aromatic acrylates or methacrylates of the formulas (3b to 3d).

1.DDPE: 4.4'-디히드록시디페닐에테르 1. DDPE: 4.4'- dihydroxydiphenyl ether

2.DDPS: 4.4'-비스(4-히드록시페닐)술폰 2. DDPS: 4.4'-bis (4-hydroxyphenyl) sulfone

3.THOP: 4.4'-티오디페놀 3. THOP: 4.4'- thiodiphenol

4.Mch: 메타크릴로일 클로라이드 4. Mch: Methacryloyl chloride

5.Ach: 아크릴로일 클로라이드 5. Ach: Acryloyl chloride

6.MC: 메틸 클로라이드 CH2Cl2 6. MC: Methyl chloride CH 2 Cl 2

7.TBAC: 테트라부틸암모늄 클로라이드 [CH3(CH2)3]4·NCl 7. TBAC: tetrabutylammonium chloride [CH 3 (CH 2 ) 3 ] 4 NCl

8.TBAB: 테트라부틸암모늄 브로마이드 [CH3(CH2)3]·NBr 8. TBAB: Tetrabutylammonium bromide [CH 3 (CH 2) 3 ] · NBr

9.BTAC: 벤질트리에틸암모늄 클로라이드 C6H5CH2N(CH3)3.·Cl4 9. BTAC: benzyltriethylammonium chloride C 6 H 5 CH 2 N ( CH 3) 3. · Cl 4

화학식3a∼3dChemical Formulas 3a to 3d

실시예 14.: 플라스틱 렌즈용 조성물의 제조 Example 14 Preparation of Composition for Plastic Lens

실시예1에서 제조된 화학식(1a)의 화합물과 화학식(1e)의 화합물을 80% : 20%의 중량비로 혼합 및 교반 한 후, AIBN(2.5중량%)를 가하여 주형 중합성 조성물을 제조한다. 제조된 조성물의 굴절률은 20℃에서 1.5337이다.After mixing and stirring the compound of Formula 1a and the compound of Formula 1e prepared in Example 1 in a weight ratio of 80%: 20%, AIBN (2.5% by weight) is added to prepare a template polymerizable composition. The refractive index of the prepared composition is 1.5337 at 20 ° C.

실시예 15∼34(플라스틱 렌즈용 조성물의 제조) Examples 15-34 (Preparation of Composition for Plastic Lens)

실시예 14에서 조성물의 성분을 하기 표4와같이 바꾸어 조성물을 제조한다. 각 조성물의 용액은 구성 성분에 따라 굴절률 nD를 1.52∼1.59로 변경시킬 수있다. In Example 14 to change the components of the composition as shown in Table 4 to prepare a composition. The solution of each composition can change the refractive index n D to 1.52-1.59 according to a component.

실시예 35Example 35

실시예 23에서 제조된 조성물을 유리 몰드와 실리콘 가스켓으로된 몰드 형에 넣고 프로그램된 오븐에서 중합시킨다. 이때 중합 온도 제어를 다음과 같은 방법으로 진행 시키면 투명하고 평활성이 우수한 플라스틱 수지가 제조된다:The composition prepared in Example 23 is placed in a mold with a glass mold and a silicone gasket and polymerized in a programmed oven. At this time, the polymerization temperature control is carried out in the following manner to produce a transparent and smooth plastic resin:

실온 ―(60분)→60℃―(180분)→ 60℃ ―(60분)→ 75℃―(180분)→ 75℃ ―(120분)→ 90℃ ―(120분)→ 90℃ ―(120분)→ 120℃ ―(120분)→ 120℃ ―(자연냉각)→ 60℃Room temperature-(60 minutes) → 60 ° C-(180 minutes) → 60 ° C-(60 minutes) → 75 ° C-(180 minutes) → 75 ° C-(120 minutes) → 90 ° C-(120 minutes) → 90 ° C- (120 minutes) → 120 ° C-(120 minutes) → 120 ° C-(natural cooling) → 60 ° C

제조된 플라스틱 렌즈는 굴절률이 1.6045이며, 600nm 에서의 투과율이 94%이며, 흡수율은 0.21%, 연필경도는 6H 이상으로 나타났다. 특히 유리전이온도(Tg)은 125℃이상이며, 5%중량손실의 온도는 259℃이상으로 나타났으며, 내마모성은 B4급, 아베수는 35.8로서 투명 고굴절 렌즈로 적합한 것으로 나타났다.The manufactured plastic lens had a refractive index of 1.6045, a transmittance of 94% at 600 nm, an absorption rate of 0.21%, and a pencil hardness of 6H or more. In particular, the glass transition temperature (Tg) was more than 125 ℃, the temperature of 5% weight loss was more than 259 ℃, wear resistance B4 grade, Abbe number 35.8 was found to be suitable as a transparent high refractive lens.

실시예 36∼55Examples 36-55

실시예 35에서 조성물을 표 5에 정리된 바와같이 바꾸고 유리 몰드와 실리콘 가스켓으로된 몰드에 투입하였다. 중합시키면 구성 성분에 따라 굴절률 1.5648∼1.6573의 플라스틱 광학수지가 제조된다. 표5에서 개시제에 따라 중합 조건을 다음과 같이 설정 한다.In Example 35 the composition was changed as summarized in Table 5 and placed in a mold of glass mold and silicone gasket. Upon polymerization, plastic optical resins having a refractive index of 1.5648 to 1.6573 are produced depending on the constituents. According to the initiator in Table 5, the polymerization conditions are set as follows.

1)AIBN 혹은 BPO 개시제를 사용할 경우 :1) When using AIBN or BPO initiators:

실온 ―(60분)→60℃―(180분)→ 60℃ ―(60분)→ 75℃ ―(180분)→ 75℃ ―(120분)→ 90℃ ―(120분)→ 90℃ ―(120분)→ 120℃ ―(120분)→ 120℃ ―(자연냉각)→ 60℃Room temperature-(60 minutes) → 60 ° C-(180 minutes) → 60 ° C-(60 minutes) → 75 ° C-(180 minutes) → 75 ° C-(120 minutes) → 90 ° C-(120 minutes) → 90 ° C- (120 minutes) → 120 ° C-(120 minutes) → 120 ° C-(natural cooling) → 60 ° C

2)IPP 개시제를 사용한 경우2) When using an IPP initiator

실온 ―(30분)→ 40℃ ―(120분)→ 40℃ ―(120분)→60℃―(180분)→ 60℃ ―(180분)→ 85℃ ―(180분)→ 85℃ ―(120분)→ 120℃ ―(180분)→ 120℃―(자연냉각)→60℃Room temperature-(30 minutes) → 40 ° C-(120 minutes) → 40 ° C-(120 minutes) → 60 ° C-(180 minutes) → 60 ° C-(180 minutes) → 85 ° C-(180 minutes) → 85 ° C- (120 minutes) → 120 ° C-(180 minutes) → 120 ° C-(natural cooling) → 60 ° C

60℃에서 몰드를 이형시킨 플라스틱 렌즈를 120℃에서 120분간 재 경화시켜 투명하고 경도가 높은 플라스틱 렌즈를 제조할 수 있다.The plastic lens released from the mold at 60 ° C. may be re-cured at 120 ° C. for 120 minutes to produce a transparent and high hardness plastic lens.

표 5에 비교된 본 발명의 광학 수지는 CR39로부터 제조된 광학 렌즈보다 굴절률이 높고 경도가 높다.The optical resin of the present invention compared to Table 5 has a higher refractive index and higher hardness than the optical lens made from CR39.

본 발명의 방향족 아크릴계 또는 메타아크릴계 화합물은 라디칼 개시제를 이용하는 주형 중합을 포함하여 열중합, 광중합 등의 반응에 사용되며, 스티렌, 알파메틸스티렌, CR39 및 기타 불포화 단량체에서 선택된 1종이상의 화합물과 공중합 반응에의해 고굴절 투명 플라스틱 소재가 제공된다. 구성 성분에 따라 넓은 범위의 굴절률을 제어할 수 있으며, 경도, 투과도, 내마모성 등이 뛰어나 가볍고, 고집적화된 광학 부품에 사용가능하다.The aromatic acrylic or methacrylic compounds of the present invention are used in the reaction of thermal polymerization, photopolymerization and the like, including mold polymerization using a radical initiator, and copolymerization with one or more compounds selected from styrene, alphamethylstyrene, CR39 and other unsaturated monomers. Provided is a high refractive transparent plastic material. It is possible to control a wide range of refractive index according to the component, it is excellent in hardness, transmittance, wear resistance, etc. can be used for light, highly integrated optical parts.

본 발명에서 제공되는 방향족 아크릴계 또는 메타아크릴계 화합물, 이들을 포함하는 중합성 조성물과 박막은 기능성 광학 렌즈, 표시 소자나 광집적 소자, 접착제, 복합재, 광디스크 또는 광학 기록 매체에 응용될 수 있다.The aromatic acrylic or methacrylic compounds provided in the present invention, the polymerizable composition and the thin film containing the same may be applied to a functional optical lens, a display element or an optical integrated element, an adhesive, a composite material, an optical disc or an optical recording medium.

Claims (7)

하기 화학식(3)의 방향족 아크릴레이트 또는 메타아크릴레이트:Aromatic acrylates or methacrylates of the general formula (3) (3) (3) 식중 R1은 H 또는 -CH3이고;In which R 1 is H or —CH 3 ; n은 0∼50의 수이고;n is a number from 0 to 50; X는 -O-, -S-, -SO2-,,또는 -CH2이고;X is -O-, -S-, -SO 2- , , Or -CH 2 ; Y는혹은 직접 결합이다.Y is Or direct coupling. 방향족 디올과 H2O, KOH, 제3항의 유기용매, 제3항의 촉매 또는 테트라 부틸암모늄 클로라이드(TBAC)로 이루어진 군에서 선택된 1종이상의 촉매를 투입용해 시킨후 분액 깔대기로 메타 크릴로일 클로라이드(Mch) 또는 에틸렌 옥시기로 치환된 아크릴레이트를 -5℃ ~ 20℃에서 5내지 16시간 반응시켜 유기용액층을 증류수로 반복세척한 후 용매를 제거하여 상기 화학식(3)의 방향족 아크릴레이트 또는 메타 아크릴레이트를 제조하는 방법.After dissolving an aromatic diol and at least one catalyst selected from the group consisting of H 2 O, KOH, the organic solvent of claim 3, the catalyst of claim 3 or tetrabutylammonium chloride (TBAC), methacryloyl chloride ( Mch) or an acrylate substituted with an ethylene oxy group is reacted for 5 to 16 hours at -5 ° C ~ 20 ° C and the organic solution layer is repeatedly washed with distilled water and then the solvent is removed to remove the aromatic acrylate or metaacryl Method of manufacturing the rate. 제2항에 있어서, 하기 화학식(4)의 방향족 디올이 4.4'-디히드록시 디페닐에테르(DDPE), 4.4'-비스(4-히드록시 페닐)술폰(DDPS) 또는 4.4'-티오디페놀(THOP)이고, 메타크릴로일 클로라이드(Mch) 대신에 아크릴로일 클로라이드(Ach) 또는 폴리에틸렌 글리콜 모노(메타) 아크릴클로로폴메이트3. The aromatic diol of formula (4) according to claim 2, wherein the aromatic diol of formula (4) is 4.4'-dihydroxy diphenyl ether (DDPE), 4.4'-bis (4-hydroxy phenyl) sulfone (DDPS) or 4.4'-thiodiphenol (THOP) and instead of methacryloyl chloride (Mch) acryloyl chloride (Ach) or polyethylene glycol mono (meth) acrylchloropolmate (, 여기서 n은 0∼50의 수임)를 사용하는, 상기 화학식(3)의 방향족 아크릴레이트 또는 메타아크릴레이트의 제조방법:( Wherein n is a number from 0 to 50). (4) (4) 하기 화학식 3의 화합물과 개시제를 포함하는 중합성 조성물:A polymerizable composition comprising a compound of formula 3 and an initiator: (3) (3) 식중 R1은 H 또는 -CH3이고;In which R 1 is H or —CH 3 ; n은 0∼50의 수이고;n is a number from 0 to 50; X는 -O-, -S-, -SO2-,,또는 -CH2이고;X is -O-, -S-, -SO 2- , , Or -CH 2 ; Y는혹은 직접 결합이다.Y is Or direct coupling. 제 4항에 있어서, NK55, CR39, α-메틸스틸렌, 스티렌, 폴리에틸렌옥시메타아크릴레이트 또는 그의 아크릴레이트, 폴리에틸렌옥시디아크릴레이트, 알킬렌트리아크릴레이트, 기타 공지의 불포화기를 가지는 화합물 중에서 선택된 1종이상의 화합물을 첨가하는 중합성 조성물.The compound according to claim 4, wherein one selected from NK55, CR39, α-methylstyrene, styrene, polyethyleneoxy methacrylate or its acrylate, polyethyleneoxy diacrylate, alkylene triacrylate, and other compounds having a known unsaturated group A polymerizable composition to which a compound of the phase is added. 제 5항에 있어서, 개시제의 양이 조성물 총중량에 대하여 0.1∼10중량%인 중합성 조성물.The polymerizable composition according to claim 5, wherein the amount of initiator is 0.1 to 10% by weight based on the total weight of the composition. 제1항에 따른 화학식 3의 화합물과 개시제를 몰드에 넣고 다음과 같은 조건에서 중합시킴으로써 고굴절 투명 플라스틱 소재를 제조하는 방법:A method of preparing a high refractive index transparent plastic material by placing a compound of formula 3 according to claim 1 and an initiator in a mold and polymerizing under the following conditions: 개시제가 IPP인 경우, 실온 ―(120분)→ 40℃ ―(120분)→ 40℃―(120분)→60℃―(180분)→ 60℃ ―(180분)→ 85℃ ―(180분)→ 85℃ ―(120분)→ 120℃ ―(120분)→ 120℃―(자연냉각)→60℃이고,When the initiator is IPP, room temperature-(120 minutes) → 40 ° C-(120 minutes) → 40 ° C-(120 minutes) → 60 ° C-(180 minutes) → 60 ° C-(180 minutes) → 85 ° C-(180 Minute) → 85 ° C .— (120 minutes) → 120 ° C .— (120 minutes) → 120 ° C .— (natural cooling) → 60 ° C., 개시제가 AIBN인 경우, 실온 ―(120분)→60℃―(180분)→ 60℃ ―(120분)→ 75℃―(180분)→ 75℃ ―(120분)→ 90℃ ―(120분)→ 90℃ ―(120분)→ 120℃ ―(120분)→ 120℃ ―(자연냉각)→ 60℃임.When the initiator is AIBN, room temperature-(120 minutes) → 60 ° C-(180 minutes) → 60 ° C-(120 minutes) → 75 ° C-(180 minutes) → 75 ° C-(120 minutes) → 90 ° C-(120 Min) → 90 ° C .— (120 min) → 120 ° C .— (120 min) → 120 ° C .— (natural cooling) → 60 ° C.
KR1020020010931A 2002-02-28 2002-02-28 Aromatic Acrylic or Methacrylic Compounds and Process for Preparing the Same, Their Polymerisable Composition, and Method for Preparing a High Reflective Plastic Material KR20020020774A (en)

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KR20040010865A (en) * 2002-07-25 2004-02-05 한국화학연구원 Acryl or methacryl compounds containing sulfur atom, and high refractive transparent plastic material manufactured from polymerizable composition comprising same

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JPH06157415A (en) * 1992-11-17 1994-06-03 Nippon Zeon Co Ltd Acrylic acid-based ester derivative
KR960006257A (en) * 1994-07-29 1996-02-23 이형도 Tuner High Frequency Input Signal Intensity Control Circuit
JPH10158374A (en) * 1996-11-26 1998-06-16 Nippon Steel Chem Co Ltd Polyfunctional ester acrylate and curing resin composition
JPH11116534A (en) * 1997-10-14 1999-04-27 Asahi Denka Kogyo Kk Di(meth)acrylate compound

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JPH06157415A (en) * 1992-11-17 1994-06-03 Nippon Zeon Co Ltd Acrylic acid-based ester derivative
KR960006257A (en) * 1994-07-29 1996-02-23 이형도 Tuner High Frequency Input Signal Intensity Control Circuit
JPH10158374A (en) * 1996-11-26 1998-06-16 Nippon Steel Chem Co Ltd Polyfunctional ester acrylate and curing resin composition
JPH11116534A (en) * 1997-10-14 1999-04-27 Asahi Denka Kogyo Kk Di(meth)acrylate compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040010865A (en) * 2002-07-25 2004-02-05 한국화학연구원 Acryl or methacryl compounds containing sulfur atom, and high refractive transparent plastic material manufactured from polymerizable composition comprising same

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