KR101102373B1 - UV-absorber of reactive benzotriazoles and copolymer prepared by using the same - Google Patents
UV-absorber of reactive benzotriazoles and copolymer prepared by using the same Download PDFInfo
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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Abstract
본 발명은 수산기 혹은 카르복실기를 갖는 벤조트리아졸에 적용 및 활용에 관한 것이다. 기존 자외선 흡수제인 벤조트리아졸 [대표적으로 Tinuvin P, (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole]에 페닐에 붙어 있는 알킬체인 (R-CH3) 혹은 메틸기(R-CH3)를 산화제로 산화 시켜서 R-CH2OH, R-COOH로 치환하여 반응형 자외선 흡수제를 합성한다. 합성된 벤조트리아졸은 반응형 수산기가 존재함으로써 고분자 중합에 특히 폴리에스테르 반응에 참여 가능하여 고분자 주쇄 말단에 결합이 가능한 단량체이다. 즉 고분자량화 반응형 안정제라고도 할 수 있다. 기존 분자량 증대 혹은 hals계와는 다른 고분자량화 할 수 있는 성능이 우수한 자외선 흡수제 이다. 또는 수산기가 존재하므로 고분자 표면에 반응성이 있는 카르복실기나 알코올, 이소시아네이트와 그라프팅이 가능하며 주쇄에 결합하는 것보다 더 낳은 효과를 얻을 수 있다.The present invention relates to application and utilization to benzotriazoles having hydroxyl or carboxyl groups. Alkyl chain (R-CH 3 ) or methyl group (R-CH 3 ) attached to phenyl on the existing UV absorber benzotriazole [typically Tinuvin P, (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole] ) Is oxidized with an oxidizing agent to replace R-CH 2 OH and R-COOH to synthesize a reactive UV absorber Synthesized benzotriazole is particularly capable of participating in polyester polymerization in polymer polymerization by the presence of a reactive hydroxyl group. It is a monomer that can be attached to the terminal of the main chain, that is, it can also be called a high molecular weight reaction type stabilizer, an ultraviolet absorber with excellent performance to increase the molecular weight or to make a high molecular weight different from the hals system, or it has a hydroxyl group. It can be grafted with carboxyl groups, alcohols, isocyanates that are reactive with, and can achieve a better effect than binding to the main chain.
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Description
본 발명은 수산기 혹은 카르복실기를 갖는 벤조트리아졸계 자외선 안정제와 이를 이용한 고분자 중합체에 관한 것이다. 기존 자외선 흡수제인 벤조트리아졸 [대표적으로 Tinuvin P, (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole]의 페닐에 붙어 있는 알킬체인 (R-CH3) 혹은 메틸기(R-CH3)를 산화제로 산화 시켜서 R-CH2OH, R-COOH로 치환하여 반응형 자외선 흡수제를 합성한다. 본 발명에 따른 벤조트리아졸은 반응형 수산기가 존재함으로써 고분자 중합에 특히 폴리에스테르 반응에 참여 가능하여 고분자 주쇄 말단에 결합이 가능한 단량체이다. 즉 고분자량화 반응형 벤조트리아졸계 자외선 흡수제라고도 할 수 있다. 기존 분자량 증대 혹은 hals계와는 다른 고분자량화 할 수 있는 성능이 우수한 자외선 흡수제이다. 또는 수산기가 존재하므로 고분자 표면에 반응성이 있는 카르복실기나 알코올, 이소시아네이트와 그라프팅이 가능하며 주쇄에 결합하는 것보다 더 낳은 효과를 얻을 수 있다.The present invention relates to a benzotriazole-based ultraviolet stabilizer having a hydroxyl group or a carboxyl group and a polymer polymer using the same. Alkyl chain (R-CH 3 ) or methyl group (R-CH 3 ) attached to the phenyl of the existing UV absorber benzotriazole [typically Tinuvin P, (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole] ) Is oxidized with an oxidizing agent to replace R-CH 2 OH and R-COOH to synthesize a reactive UV absorber The benzotriazole according to the present invention can participate in a polyester reaction particularly in polymer polymerization by the presence of a reactive hydroxyl group Thus, it is a monomer capable of binding to the polymer main chain terminal, that is, it can be referred to as a high molecular weight reaction type benzotriazole-based ultraviolet absorber, or an ultraviolet absorber with excellent performance to increase the molecular weight or to make a higher molecular weight than the hals system. The presence of hydroxyl groups allows grafting with carboxyl groups, alcohols, isocyanates that are reactive on the surface of the polymer, and can achieve a better effect than binding to the main chain.
본 발명은 반응형 벤조트리아졸계 자외선 흡수제 및 이의 용도에 대한 것이다.The present invention relates to a reactive benzotriazole-based ultraviolet absorber and uses thereof.
대표적으로 (2(2'-하이드록시-5'-메틸-페닐)벤조트리아졸)((2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole)골격의 페닐에 붙어 있는 메틸기를 산화 반응시켜 -CH2OH, 혹은 -COOH로 변화시켜 수산기를 갖게 한다. 이러한 반응형 수산기를 갖게 됨으로서 고분자에 단순첨가가 아닌 그라프팅 혹은 주쇄 말단에 반응하여 중합되게 함으로써 자외선 흡수제로써 단순첨가형보다 안전하고 저분자의 문제점을 해결한 우수한 내후성 고분자를 만들 수 있다.Typically, the methyl group attached to the phenyl of the (2(2'-hydroxy-5'-methyl-phenyl)benzotriazole)((2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole) skeleton is oxidized. It is changed to -CH 2 OH or -COOH to have a hydroxyl group. By having such reactive hydroxyl group, it is polymerized by reacting with grafting or main chain end rather than simple addition to the polymer. It is possible to make an excellent weather-resistant polymer that solves the problems of the.
자외선 안정제 중 성능면에서 우수하고 가장 많이 사용되는 구조가 벤조트리아졸이다. 벤조트리아졸류 중에서 가장 간단한 구조는 Tinuvin P이다. Tinuvin P의 화학명은 (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole 이고 분자량 225.3이다 성상은 담황색 결정성 분말로 융점이 128-133℃이며 최대흡수파장 340nm이다. 적용 용도는 경질, 연질-PU, 염화비닐수지, 불포화 폴리에스테르, 폴리스티렌, ABS, 폴리카보네이트, 아크릴계 수지, 천연·합성고무, 라텍스 등의 자외선 흡수제로 사용되고 있다. 이 물질은 시바가이기라는 외국기업에 의해 특허화 된 물질이며 현재 특허 완료 된 상태로 단순 첨가형으로 많이 적용되고 있다. 그러나 실외에서 장시간 사용시 기존 단순첨가형의 여러 가지 문제점이 발생하고 환경에 친화적이지 못한 부분이 많이 있다. 기존의 단순첨가형의 문제점은 대부분이 저분자 형태로서 해로운 VOC(Vaporized Organic Compound)를 발생시키고 쉽게 추출 되며 Processing 과정에서 분해되거나 고분자내에서 이동하여 'Blooming' 현상을 일으키는 등이 있다. 즉, 기존의 단순첨가형 자외선 흡수제는 첨가 후 고분자와의 상용성 및 사용 환경에 의해서 물리적인 결합이 약해져서 첨가제가 이탈하는 문제점을 가지므로 이를 극복하기 위해서 고분자에 그라프팅 시키거나 주쇄에 결합 또는 고분자에 표면에 고착 시켜주어야 한다.Among ultraviolet stabilizers, benzotriazole is the most used structure in terms of performance. The simplest structure among benzotriazoles is Tinuvin P. The chemical name of Tinuvin P is (2(2'-Hydroxy-5'-methyl-phenyl)benzotriazole, molecular weight 225.3. It is a pale yellow crystalline powder with a melting point of 128-133℃ and a maximum absorption wavelength of 340nm. It is used as a UV absorber for soft-PU, vinyl chloride resin, unsaturated polyester, polystyrene, ABS, polycarbonate, acrylic resin, natural/synthetic rubber, latex, etc. This material is patented by a foreign company called ShibaGigi It has been patented and has been applied as a simple addition type, but when used outdoors for a long time, there are many problems with the existing simple addition type and there are many parts that are not environmentally friendly. As a form, it generates harmful VOC (Vaporized Organic Compound), is easily extracted, decomposes in the process of processing, or moves in the polymer to cause a'blooming' phenomenon, that is, the existing simple addition type UV absorber is commercialized with the polymer after addition. Due to the weak physical bonds due to the sex and the use environment, there is a problem in that the additives are released, so to overcome this, grafting to the polymer or bonding to the main chain or fixing to the surface of the polymer is required.
현재 외국 기업이 개발 한 아릴(AIIYL)기가 있는 부가반응형 그라프팅 형태가 주를 이루고 있으며 국내 연구개발은 아주 저조한 형태이다. 가장 많이 사용되고 성능면에서 우수한 벤조트리아졸에 반응형 기를 도입한 아릴기는 시바가이기에 의해 특허화 되었으나 일부 한정된 분야에서만 적용이 되고 있다.Currently, the addition reaction type grafting type with aryl (AIIYL) group developed by foreign companies is dominant, and the domestic research and development is very poor. The aryl group, which is the most commonly used and has a reactive group in benzotriazole, which is excellent in terms of performance, has been patented by Shivagai, but is only applied in some limited fields.
본 발명에서는 벤조트리아졸 기본골격에 반응성기인 수산기(-OH)를 갖는 반응형 벤조트리아졸 자외선 흡수제를 제공한다.
또한 본 발명은 반응형 벤조트리아졸 자외선 흡수제는 단량체로 고분자 중합체 제조의 중합공정에 첨가하여 자외선 안정기를 갖는 고분자 중합체를 제공한다.
또한 본 발명은 반응형 벤조트리아졸 자외선 흡수제는 단량체로 첨가하여 자외선 안정기를 갖는 고분자 중합체의 제조방법을 제공한다.
고분자 중합시 반응형 벤조트리아졸계 자외선 흡수제를 포함하여 공중합시킴으로서 내구성이 우수한 고분자 중합체를 제조한다. 기존의 저분자형태의 단순첨가형에서 나타나는 여러 가지 단점을 보완하고 고분자의 물성이 우수한 내구성 고분자를 만든다.The present invention provides a reactive benzotriazole ultraviolet absorber having a hydroxyl group (-OH) which is a reactive group in the basic skeleton of benzotriazole.
In addition, the present invention provides a polymer polymer having a UV stabilizer by adding a reactive benzotriazole ultraviolet absorber as a monomer to a polymerization process for preparing a polymer polymer.
In addition, the present invention provides a method for preparing a polymer polymer having an ultraviolet stabilizer by adding a reactive benzotriazole ultraviolet absorber as a monomer.
A polymer polymer having excellent durability is prepared by copolymerizing a polymerized polymer by including a reactive benzotriazole-based ultraviolet absorber. It compensates for the various shortcomings of the existing low-molecular type simple addition type and makes a durable polymer with excellent polymer properties.
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본 발명은 반응형 벤조트리아졸계 자외선 흡수제, 이를 중합에 사용하는 제조되는 고분자 중합체 및 이의 제조방법을 제공한다.
본 발명에 따른 반응형 벤조트리아졸계 자외선 흡수제는 하기 화학식 1로 표시된다.
[화학식 1]
[상기 화학식 1 에서,
R은 카르복시기 또는 하이드록시메틸기이다.]
또한 본 발명은 상기 화학식 1로 표시되는 반응형 벤조트리아졸계 자외선 흡수제와 중합 또는 그라프팅하여 제조되는 고분자 중합체를 제공한다.
상기 고분자 중합체는 상기 화학식 1로 표시되는 반응형 자외선 흡수제를 고분자 중합체에 0.2~20중량%로 포함될 수 있다.
상기 화학식 1로 표시되는 반응형 벤조트리아졸계 자외선 흡수제를 포함하여 제조되는 고분자 중합체는 한정이 있는 것은 아니나 바람직하게 폴리에스테르 또는 폴리우레탄일 수 있으며 제조된 고분자 중합체의 고유점도는 0.55 내지 0.65 dl/g일 수 있다.
또한 본 발명은 테레프탈산 또는 디메틸프탈레이트; 에틸렌글리콜; 및 상기 화학식 1로 표시되는 반응형 자외선 흡수제;를 중합하여 고분자 중합체를 합성하는 방법을 제공한다.The present invention provides a reactive benzotriazole-based ultraviolet absorber, a polymer polymer prepared using the same for polymerization, and a method for manufacturing the same.
The reactive benzotriazole-based ultraviolet absorber according to the present invention is represented by the following Chemical Formula 1.
[Formula 1]
[In the formula 1,
R is a carboxy group or a hydroxymethyl group.]
In addition, the present invention provides a polymer polymer prepared by polymerization or grafting with a reactive benzotriazole-based ultraviolet absorber represented by Chemical Formula 1.
The polymer polymer may include 0.2 to 20% by weight of the polymer having a reactive UV absorber represented by Chemical Formula 1.
The polymer polymer prepared by including the reactive benzotriazole-based ultraviolet absorber represented by Formula 1 is not limited, but may be preferably polyester or polyurethane, and the intrinsic viscosity of the prepared polymer polymer is 0.55 to 0.65 dl/g Can be
In addition, the present invention is terephthalic acid or dimethyl phthalate; Ethylene glycol; And it provides a method for synthesizing a polymer polymer by polymerizing; and a reactive UV absorber represented by the formula (1).
본 발명에 따라 제조된 반응형 벤조트리아졸계 자외선 흡수제의 자외선 흡수범위는 285-365nm이므로 특히 폴리에스터의 광분해 파장범위인 310-330nm를 포함한다. 따라서 본 발명에 따른 반응형 벤조트리아졸계 자외선 흡수제는 -OH, -COOH 형태로 폴리에스테르나 폴리우레탄용 중합 단량체로 사용이 가능한 자외선 흡수제이다. 또는 고분자에 그라프팅이 가능하여 여러 용도로의 적용이 가능하다.
본 발명에 따른 반응형 벤조트리아졸계 자외선 흡수제는 기존 저분자 단순 첨가시 발생되는, 저분자 형태로서 해로운 VOC(Vaporized Organic Compound)를 발생시키고 쉽게 추출되며 Processing 과정에서 분해 되거나 고분자내에서 이동하여 'Blooming' 현상과 같은 문제점을 해결하고, 고분자 주쇄에 자외선 흡수 작용기가 있으므로 반영구적인 자외선 흡수제이다.
또한 본 발명에 따른 반응형 벤조트리아졸계 자외선 흡수제는 벤조트리아졸골격 구조에 수산기가 있는 화합물로 단량체로서 자외선 안정제가 별도로 필요한 플라스틱과 같은 고분자에 사용이 가능한 장점이 있다.Since the ultraviolet absorption range of the reactive benzotriazole-based ultraviolet absorber prepared according to the present invention is 285-365 nm, it particularly includes the photodegradation wavelength range of polyester, 310-330 nm. Therefore, the reactive benzotriazole-based ultraviolet absorber according to the present invention is an ultraviolet absorber that can be used as a polymerization monomer for polyester or polyurethane in the form of -OH and -COOH. Alternatively, grafting is possible on the polymer, so it can be applied for various purposes.
The reactive benzotriazole-based UV absorber according to the present invention generates a harmful VOC (Vaporized Organic Compound) as a low-molecular form that is generated when simple addition of existing low-molecules, is easily extracted, decomposes in the process of processing, or moves in the polymer to'bloom' phenomenon It solves the problems as described above, and is a semi-permanent UV absorber because it has a UV absorbing functional group in the polymer backbone.
In addition, the reactive benzotriazole-based UV absorber according to the present invention is a compound having a hydroxyl group in the benzotriazole skeleton structure and has the advantage of being usable for polymers such as plastics, which require a separate ultraviolet stabilizer.
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(대표적인 합성방법)(Representative synthesis method)
실험 1. 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid 합성 2-(2H-benzo[d][1,2,3]triazol-2-yl)-4-methylphenol (TINUVIN P) 1mol에 아세트산 및 무수아세트산, 진한 황산를 넣고 15℃를 유지하면서 교반한다. 여기에 CrO3을 과량 가하여 산화 시킨다. 30분후 얼음물을 가하여 격렬히 교반하여 여과 정제한다. 고형물을 ether로 정제 건조 한다.Experiment 1. Synthesis of 3-(2H-benzo[d][1,2,3]triazol-2-yl)-4-hydroxybenzoic acid 2-(2H-benzo[d][1,2,3]triazol-2 Acetic acid, acetic anhydride and concentrated sulfuric acid are added to 1 mol of -yl)-4-methylphenol (TINUVIN P) and stirred while maintaining 15°C. To this, CrO3 is added in excess to oxidize. After 30 minutes, ice-water was added and stirred vigorously to purify and filter. Purify and dry the solid with ether.
실험 2. 고분자에 적용Experiment 2. Applied to polymer
테레프탈산(TPA) 와 에틸렌글리콜(EG)를 주원료로하여 에스테르화 반응 및 축중합 반응을 거쳐 중합도가 약 100 전후 수준의 기본수지로 제조한다 이 수지의 고점도는 약 0.6 dl/g의 중합체가 된다. 추가로 이소프탈산, 프탈산, 디에틸렌글리콜(DEG), 비스페놀 유도체를 사용한다.Terephthalic acid (TPA) and ethylene glycol (EG) are used as the main raw materials to produce a basic resin with a degree of polymerization of about 100 or so through an esterification reaction and a condensation polymerization reaction. The high viscosity of this resin is a polymer of about 0.6 dl/g. In addition, isophthalic acid, phthalic acid, diethylene glycol (DEG), bisphenol derivatives are used.
중합 촉매로 안티몬이 사용 되면 열안정제로 인화합물을 에틸렌글리콜과 함께 조제하여 사용하고 색상 개선을 위해 코발트, 주석 화합물을 보조촉매로 사용 한다.When antimony is used as a polymerization catalyst, a phosphorus compound is used together with ethylene glycol as a heat stabilizer, and cobalt and tin compounds are used as cocatalysts to improve color.
위 실험 1에서 제조된 벤조트리아졸계를 에틸렌글리콜과 혼합 후 반응 EP 첨가 하여 주쇄에 결합 하도록 중합한다.The benzotriazole system prepared in Experiment 1 above is mixed with ethylene glycol and then added to the reaction EP to polymerize to bind to the main chain.
에스테르화 반응단계에서는 상압내지 1.0kg/㎠ 전후의 가압하에서 245 내지 265℃ 범위내에서 반응시켜 중합도 3-10 정도의 올리고머를 형성 시킨다. 축중합단계에서는 275-290℃에서 1Torr 이하의 고진공조건으로 반응 시켜 고유점도 0.55 내지 0.65 dl/g의 용융중합체를 제조한다.In the esterification reaction step, the reaction is carried out within a range of 245 to 265°C under normal pressure to about 1.0 kg/cm 2 to form an oligomer having a degree of polymerization of about 3-10. In the condensation polymerization step, a molten polymer having an intrinsic viscosity of 0.55 to 0.65 dl/g is prepared by reacting at 275-290°C under a high vacuum condition of 1 Torr or less.
(적용 방법)(Application method)
1. 폴리에스터에 축중합 : 폴리에스터는 1kg이 만들려면 중합 공정에서 TPA 0.8640 kg 대비 EG는 0.3416 kg이 필요하다. 일반적으로 자외선 안정제가 폴리머 대비 0.2-0.5중량％ 사용되므로 본 개발에서는 폴리에스터 1kg 생산량 대비 0.2중량％ - 1중량％ 까지 조성 변화를 주어 중합한다. 고분자 중합도는 IV ～0.6dl/g으로 수평균분자량 20,000-30,000 정도 되게 중합한다. 1. Condensation polymerization on polyester: In order to make 1kg of polyester, it requires 0.3416 kg of EG compared to 0.8640 kg of TPA in the polymerization process. In general, since the UV stabilizer is used 0.2-0.5% by weight compared to the polymer, in this development, polymerization is given by changing the composition from 0.2% to 1% by weight compared to 1kg of polyester. Polymerization degree is IV ~ 0.6dl/g, and polymerizes to a number average molecular weight of 20,000-30,000.
용융중합체 물성 ( 자외선 안정제 0.2part 첨가 시 )Melt polymer properties (when 0.2part of UV stabilizer is added)
2. 폴리우레탄에 디올 대신 일부 첨가 한다.2. Polyurethane is partially added instead of diol.
3. 그라프팅 반응 : 벤조트리아졸 구조에 수산기(-OH)가 있으므로 그라프팅이 가능하므로 고분자 표면에 그라프팅시켜 단순첨가형의 문제점을 해결할 수 있다.3. Grafting reaction: Since there is a hydroxyl group (-OH) in the benzotriazole structure, grafting is possible, so grafting on the polymer surface can solve the problem of simple addition.
본 발명에서는 수산기를 갖는 반응형 벤조트리아졸 자외선 흡수제에 대한 것으로 폴리에스테르, 폴리우레탄, 폴리카보네이트, 폴리올, 등 수산기을 갖는 단량체 대신에 적용 가능하며 수산기를 하나만 가지고 있으므로 반응에서의 종말을 유도할 수 있다. 혹은 적용방법에서 고분자용융 후 무수물 혹은 이소시아네이트등과 함께 첨가 하여 그라프팅 시킬 수도 있다.In the present invention, for a reactive benzotriazole ultraviolet absorber having a hydroxyl group, it can be applied in place of a monomer having a hydroxyl group such as polyester, polyurethane, polycarbonate, polyol, and the like, and has only one hydroxyl group, so that it can induce the end of the reaction. . Alternatively, it can be grafted by adding it together with anhydride or isocyanate after polymer melting in the application method.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322841A (en) * | 1998-05-08 | 1999-11-26 | Otsuka Chem Co Ltd | Weather resistant polyolefin resin, its production, and weather resistant resin composition |
| US20030139499A1 (en) * | 2001-11-26 | 2003-07-24 | Joseph Suhadolnik | Photo-cured and stabilized coatings |
| KR20040096558A (en) * | 2002-02-19 | 2004-11-16 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | Containers or films comprising hydroxyphenylbenzotriazole UV absorbers for protecting contents against the effects of UV radiation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11322841A (en) * | 1998-05-08 | 1999-11-26 | Otsuka Chem Co Ltd | Weather resistant polyolefin resin, its production, and weather resistant resin composition |
| US20030139499A1 (en) * | 2001-11-26 | 2003-07-24 | Joseph Suhadolnik | Photo-cured and stabilized coatings |
| KR20040096558A (en) * | 2002-02-19 | 2004-11-16 | 시바 스폐셜티 케미칼스 홀딩 인코포레이티드 | Containers or films comprising hydroxyphenylbenzotriazole UV absorbers for protecting contents against the effects of UV radiation |
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