KR101102374B1 - Reactive UV-absorber and copolymer prepared by using the same - Google Patents

Abstract

The present invention relates to a reactive ultraviolet stabilizer having a novel hydroxyl group and to a method for producing a polyester copolymer having excellent durability. Reaction type groups are introduced into the benzotriazole of Formula 1, which is not a simple addition type of the existing low molecular type, and are added to polymer polymerization to polymerize a polymer having an ultraviolet stabilizer in the main chain. By copolymerizing a monomer having a UV absorber in the form of a diol can obtain an ultraviolet stabilizing effect, and relates to a method for producing a polymer having excellent durability.

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 Responsive, UV Absorber, Benzotriazole

Description

Reactive UV-absorber and copolymer prepared by using the same}

The present invention relates to a benzotriazole-based reactive ultraviolet absorber, and relates to a reactive ultraviolet absorber having an ultraviolet stabilizing effect by copolymerizing a small amount of such ultraviolet absorber during polyester polymerization. The reactive ultraviolet absorber according to the present invention has a diol or diacid type reactor in the benzotriazole type having an ultraviolet absorber, so it is added to the ester polymerization process and has excellent durability in which a UV stabilizer is bonded to the polymer backbone. It is possible to synthesize polyester and polyurethane.

Among UV stabilizers, UV absorbers have many disadvantages such as low molecular weight, generating harmful VOC (Vaporized Organic Compound), easily extracting them, and decomposing during processing or moving in polymers to cause 'Blooming' phenomenon. . UV stabilizers are commercially available. Many products were developed more than 20 years ago, and most of them are Tinuvin and Chimassorb. Sivagai group is a benzotriazole type-Tinuvin by attaching an alkyl group, benzene ring or Cl to R ₁ , R ₂ , R ₃ position in basic benzotriazole basic (2-hydroxy-phenyl) benzotriazole to compensate for the low molecular weight of UV stabilizer. By changing the molecular weight of 225 to 447, the molecular weight is increased to increase the MP to 141 ℃ (Tinuvin 234). Moreover, the product which raised the molecular weight 659 and MP to 195 degreeC by dimerizing an ultraviolet absorber is also marketed. However, they also cause problems such as 'blooming' due to volatilization or movement in the polymer when mixed with a high melting temperature polymer, and TGA thermal analysis shows a 5-10% weight loss at a melting temperature of 260 degrees or higher. Shows. Among them, Tinuvin 234 shows a 2% weight loss at 290 ° C as a result of thermal analysis, and is mainly used for polyester, a polymer having high melting point (PET of PET is about 260 ° C).

UV stabilizer used in polyester is benzotriazole-based in terms of performance, so as a way to compensate for the problems occurring in low molecules, new research and development to increase the molecular weight by grafting on the polymer backbone by increasing the molecular weight or making it reactive It is done. Among them, benzophenone-based was developed as a polyester-based high molecular weight ultraviolet absorber. (Special Publication No. 56-92, 914, USP 3,676,471) In USP 3,676,471, a 2-Hydroxyl position is not reactive and a stabilizer with an Ethoxy group attached only to the 4-Hydroxyl position is disclosed.

In Japan, by introducing a methachloroyl group into benzophenone or benzotriazole, the copolymer 'PUVA' with MMA and styrene is commercially available at high concentrations for the radical polymerization, namely 'RUVA-93' and various plastic formulations. (JP Special 38-25,036 KR 10-2007-7028303, USP 5,714,134) Patents are applied to polarizing plate protective films used in polarizing plates and liquid crystal display devices. In addition, there is a case of producing a polyester which is a ring-opened polymerization of lactone by attaching a hydroxyl group to benzotriazole (KR Patent Publication 10-1998-0032674) PET recently released in 2004 by Chivas Specialty The case applied to the container is a patent to pay attention to, but the contents of the patent (JP Patent Application Publication No. 10-2004-0096559) are the addition reaction type UV stabilizer which introduced allyl which has ester group in benzotriazole.

In the present patent, a monomer that is a reactive ultraviolet absorber having a hydroxyl group (-OH) of R ₁ , R ₂ , and R ₃ in the following general formula (1) of the benzotriazole skeleton is synthesized. This monomer is added to a polyester polymerization step to ester-react with terephthalic acid (TPA) or dimethylphthalate (DMT) and ethylene glycol (EG) to synthesize a polyester having an ultraviolet stabilizer. That is, copolymerization is performed using a benzotriazole-based reactive ultraviolet absorber having a diol during polyester polymerization to prepare a polymer having excellent durability. By using the reactive ultraviolet absorber according to the present invention to compensate for the various disadvantages that appear in the existing low-molecular simple addition type and to prepare a durable polymer having excellent polymer properties.

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[상기 화학식 1 에서,
R₁, R₂ 및 R₃는 서로 독립적으로 수소, 히드록시기, 히드록시기가 치환된 메톡시기 또는 히드록시기가 치환된 에톡시기이다.]
또한 본 발명은 상기 화학식 1로 표시되는 반응형 자외선 흡수제와 중합체를 형성하여 제조되는 고분자 중합체를 제공한다.
상기 제조되는 고분자 중합체는 본 발명에 따른 반응형 자외선 흡수제가 총고분자 중합체에 0.2~20중량%로 포함될 수 있다.
또한 상기 제조되는 고분자 중합체는 한정이 있는 것은 아니나 폴리에스테르 또는 폴리우레탄일 수 있으며 수평균분자량이 20000-30000일 수 있다.
또한 본 발명은 테레프탈산 또는 다이메틸부탈레이트; 에틸렌글리콜; 및 상기 화학식 1로 표시되는 반응형 자외선 흡수제;와 중합하여 제조되는 폴리에스테르의 제조방법을 제공한다.
본 발명에 따라 제조된 반응형 자외선 흡수제를 단량체는 폴리에스테르 중합시 소량 첨가하여 폴리에스테르 공중합을 한다. 보다 구체적으로 폴리에스테르 중합시 본 발명에 따른 반응형 자외선 흡수제를 0.2-20중량% 첨가하여 내구성이 우수한 고분자 중합체를 합성한다. The present invention relates to a reactive ultraviolet absorber, and more particularly, to a benzotriazole-based reactive ultraviolet absorber used for copolymerization in preparing a polymer.
Reactive ultraviolet absorbent according to the present invention is represented by the following formula (1).
[Formula 1]

[In Formula 1,
R ₁ , R ₂ and R ₃ is independently hydrogen, a hydroxy group, a methoxy group substituted with a hydroxy group or an ethoxy group substituted with a hydroxy group.]
In another aspect, the present invention provides a polymer polymer prepared by forming a polymer with a reactive ultraviolet absorber represented by the formula (1).
The prepared polymer may include 0.2 to 20% by weight of the reactive UV absorber according to the present invention in the total polymer.
In addition, the prepared polymer is not limited, but may be polyester or polyurethane, and the number average molecular weight may be 20000-30000.
In another aspect, the present invention is terephthalic acid or dimethyl butyrate; Ethylene glycol; And it provides a method for producing a polyester prepared by polymerization with a reactive ultraviolet absorber represented by the formula (1).
The reactive ultraviolet absorber prepared according to the present invention is a small amount of monomer is added during the polymerization of the polyester to the polyester copolymerization. More specifically, 0.2-20% by weight of the reactive ultraviolet absorber according to the present invention is added to the polyester polymerization to synthesize a polymer having excellent durability.

Since the ultraviolet absorption range of the reactive UV absorber synthesized in the present invention is 285-365 nm, it particularly includes 310-330 nm, which is a photolysis wavelength range of polyester. Therefore, the benzotriazole-based reactive ultraviolet absorber according to the present invention can be used as a polymer monomer for polyester or polyurethane in the form of diol. Reactive UV absorber according to the present invention generates harmful VOC (Vaporized Organic Compound) when the existing low molecular weight UV absorber is simply added, and is easily extracted and 'Blooming' generated by decomposition or processing in the polymer during processing. 'Solve the problem such as phenomenon, and since the polymer backbone has ultraviolet absorbing functional groups can be a semi-permanent ultraviolet absorber. That is, in this respect, the polymer polymer prepared with monomers of the reactive ultraviolet absorber according to the present invention having a benzotriazole-based characteristic and having a terminal group having a diol (Diol) having a hydroxyl group has an advantage that it can be used in a plastic that requires an additional UV stabilizer. .

Hereinafter, an example of preparation of a reactive UV absorber according to the present invention will be described in detail, but this does not limit the present invention. Synthesis Formula 1, 2, 3 and derivatives thereof.

1kg 5-methoxy-2-nitrobenzenamine을 3.5L 진한 HCl 용액에 0 - 5 ℃를 유지시키면서 잘 분산시킨다. 분산된 혼합 용액에 7 kg의 얼음과 7L의 물을 넣고 1.4L NaNO₂ 5N 농도의 용액을 적가 한다. 이 용액을 0℃를 유지하면서 맑게 녹을 때 까지 저어준다. 이 용액을 10％ NaOH 수용액에 740g 4-methoxyphenol을 녹인 수용액에 5 ℃를 유지하면서 적가 한다. 이 혼합 용액을 1시간 이상 0 ℃에서 잘 저어 주고, 실온에서 갈색의 침전물이 생길때까지 저어준다. 침전물이 충분히 생길 때 까지 저어주고 이 첨전물을 걸러 모아서 건조한다. 만들어진 중간체를 10L의 4N NaOH 수용액에 분산 시키고, 7.5 kg의 Formamidinessulphinic acid를 넣고 1시간 이상 가열한다. 용액 색깔이 갈색에서 노란색으로 바뀌면, 실온으로 식혀주고, 20L 얼음물에 부어 준다. 이 용액에 염산을 이용하여 산처리 후(pH = 6), 침전물을 거른다. 불순물을 뜨거운 메탄올로 제거해 준다.
② 2-(5-hydroxy-2H-benzo[d][1,2,3]triazol-2-yl)benzene-1,4-diol의 제조

4-methoxy-2-(5-methoxy-2H-benzo[d][1,2,3]triazol-2-yl)phenol 1kg을 MC(15L)에 녹인 후, 1M BBr₃ 용액 14L를 -78 ℃에서 서서히 넣어 준다. 이 혼합 용액을 하루 동안 실온에서 반응 시키고, 반응이 끝난 후, 물로 씻어 준다. 용매를 감압하에서 제거하고, 관 크로마토그래피를 이용하여 분리한다. (MC : MeOH)
③ 5-(2-hydroxyethoxy)-2-(5-(2-hydroxyethoxy)-2H-benzo[d][1,2,3]triazol-2-yl)phenol의 제조

1kg의 4-(5-hydroxy-2H-benzo[d][1,2,3]triazol-2-yl)benzene-1,3-diol와 460g의 수산화 칼슘을 5L의 물에 녹인다. 700g의 ethylene chlorohydrin을 넣어 준 후, 90 - 95℃에서 5시간 동안 환류 시킨다. 다시 실온에서 하루 밤 동안 반응 시켜 준다. 얻어진 고체 화합물을 재결정 방법으로 정제한다.
[실시예2](화학식 2) 2,4-bis(2-hydroxyethoxy)-6-(2H-benzo[d][1,2,3]triazol-2-yl)phenol

[실시예3](화학식 3) 2,4-bis(5-(2-hydroxyethoxy)-2H-benzo[d][1,2,3]triazol-2-yl)-5-hydroxybenzene-1,3-diol

[실시예4]
폴리에스터는 1kg이 만들려면 중합 공정에서 TPA 0.8640 kg 대비 EG는 0.3416 kg이 필요하다. 위에서 합성된 타입 별로 EG와 혼합 하여 폴리에스터 중합한다. 일반적으로 자외선 안정제가 폴리머 대비 0.5％ 사용되므로 본 개발에서는 폴리에스터 1kg 생산량 대비 0.2％ - 20％ part 까지 조성 변화를 주어 중합한다. 고분자 중합도는 IV ～0.6dl/g으로 수평균분자량 20,000-30,000 정도 되게 중합을 조절 한다.Example 1 Preparation of 5- (2-hydroxyethoxy) -2- (5- (2-hydroxyethoxy) -2H-benzo [d] [1,2,3] triazol-2-yl) phenol
① Preparation of 4-methoxy-2- (5-methoxy-2H-benzo [d] [1,2,3] triazol-2-yl) phenol

1 kg 5-methoxy-2-nitrobenzenamine is well dispersed in a 3.5L concentrated HCl solution while maintaining 0-5 ° C. 7 kg of ice and 7 L of water are added to the dispersed mixed solution and 1.4 L NaNO ₂ 5N solution is added dropwise. Stir this solution until it is clear that it is kept at 0 ° C. This solution is added dropwise while maintaining 5 ° C in an aqueous solution of 740 g 4-methoxyphenol dissolved in 10% NaOH solution. Stir the mixed solution well at 0 ° C. for at least 1 hour and stir at room temperature until a brown precipitate is formed. Stir until enough precipitate is formed, filter out the additives and dry. The prepared intermediate is dispersed in 10 L of 4N NaOH aqueous solution, and 7.5 kg of Formamidinessulphinic acid is added and heated for at least 1 hour. When the solution color changes from brown to yellow, allow it to cool to room temperature and pour into 20L ice water. After acid treatment (pH = 6) with hydrochloric acid, the precipitate is filtered. Remove impurities with hot methanol.
② Preparation of 2- (5-hydroxy-2H-benzo [d] [1,2,3] triazol-2-yl) benzene-1,4-diol

After dissolving 1 kg of 4-methoxy-2- (5-methoxy-2H-benzo [d] [1,2,3] triazol-2-yl) phenol in MC (15L), 14L of 1M BBr ₃ solution was added to -78 ° C. Slowly put in. The mixed solution is allowed to react at room temperature for one day, and after the reaction, it is washed with water. The solvent is removed under reduced pressure and separated using column chromatography. (MC: MeOH)
③ Preparation of 5- (2-hydroxyethoxy) -2- (5- (2-hydroxyethoxy) -2H-benzo [d] [1,2,3] triazol-2-yl) phenol

Dissolve 1 kg of 4- (5-hydroxy-2H-benzo [d] [1,2,3] triazol-2-yl) benzene-1,3-diol and 460 g of calcium hydroxide in 5 L of water. 700g of ethylene chlorohydrin was added and refluxed at 90-95 ° C for 5 hours. Let it react overnight at room temperature. The obtained solid compound is purified by the recrystallization method.
Example 2 2,4-bis (2-hydroxyethoxy) -6- (2H-benzo [d] [1,2,3] triazol-2-yl) phenol

Example 3 2,4-bis (5- (2-hydroxyethoxy) -2H-benzo [d] [1,2,3] triazol-2-yl) -5-hydroxybenzene-1,3 -diol

Example 4
1 kg of polyester requires 0.3416 kg of EG compared to 0.8640 kg of TPA in the polymerization process. Polyester polymerization is performed by mixing with EG for each type synthesized above. In general, the UV stabilizer is used 0.5% compared to the polymer, so in the present development, the composition is polymerized by varying the composition from 0.2% to 20% part of 1kg of polyester production. Polymerization degree is controlled to IV ~ 0.6dl / g to the number average molecular weight 20,000-30,000.

The benzotriazole-based reactive ultraviolet absorber according to the present invention can polymerize a polymer having excellent durability for polyester or polyurethane in the form of diol. Among them, the most recent UV absorber for polyester (PET) used Tinuvin 234 of Shivagaigi, a simple addition of low molecular weight. Melting point of Tinuvin 234 is easy to generate harmful VOC after extraction at 141 degree, and it has many disadvantages such as 'Blooming' phenomenon by decomposing or moving in polymer during high melting temperature processing. UV stabilizers, which are in the spotlight nowadays, are ultraviolet scavengers (typically referred to as HALS) in the form of polymers. In order to make up for the shortcomings of the low molecular form, products having a hydroxyl group in the reactive benzophenone series or an allyl form as a reactor in the benzotriazole have been developed. . In particular, UV stabilizers, which have excellent stability, remain a challenge, and PET, a polymer, will grow as a growth industry.

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Claims (10)

delete delete delete delete Reactive ultraviolet absorber represented by the following formula (1). [Formula 1]

[In Formula 1, R ₁ , R ₂ and R ₃ is independently hydrogen, a hydroxy group, a methoxy group substituted with a hydroxy group or an ethoxy group substituted with a hydroxy group.] A polymer prepared by forming a polymer with a reactive ultraviolet absorber represented by Formula 1 below. [Formula 1]

[In Formula 1, R ₁ , R ₂ and R ₃ independently of one another is hydrogen, hydroxy group, methoxy group, ethoxy group or ethoxy group substituted with hydroxy group.] The method of claim 6, Polymeric polymer that the reactive UV absorber is contained in the total polymer polymer 0.2 to 20% by weight. The method of claim 6, The polymer polymer is polyester or polyurethane. The method of claim 6, The polymer is a polymer having a number average molecular weight of 20000-30000. Terephthalic acid or dimethylbutalate; Ethylene glycol; And a reactive ultraviolet absorber represented by Formula 1 below. [Formula 1]

[In Formula 1, R ₁ , R ₂ and R ₃ is independently hydrogen, a hydroxy group, a methoxy group substituted with a hydroxy group or an ethoxy group substituted with a hydroxy group.]

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