CN1727338A - Compound in benzotriazole category possessing alkenyl ester type structure, and preparation method - Google Patents

Compound in benzotriazole category possessing alkenyl ester type structure, and preparation method Download PDF

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CN1727338A
CN1727338A CN 200410065921 CN200410065921A CN1727338A CN 1727338 A CN1727338 A CN 1727338A CN 200410065921 CN200410065921 CN 200410065921 CN 200410065921 A CN200410065921 A CN 200410065921A CN 1727338 A CN1727338 A CN 1727338A
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benzotriazole
formula
methyl
compound
hydroxy
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CN 200410065921
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Chinese (zh)
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徐俊伟
黄建
邓爱斌
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常州华钛化学有限公司
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Abstract

A benzotriazole compound with enylester structure, its preparing process and its application as optical stabilizer used for preventing ageing of polymer are disclosed.

Description

具有烯基酯式结构的苯并三唑类化合物及其制备方法 Having a benzotriazole-based compounds and methods of alkenyl esters of structure

技术领域 FIELD

:本发明涉及能有效吸收紫外线照射的2-(2-羟基苯基)苯并三唑类化合物的烯基酯式结构单元引入的结构修饰和制备方法。 : The present invention relates to 2 can effectively absorb ultraviolet radiation and a structural modification of the production method (2-hydroxyphenyl) alkenyl esters of benzotriazoles structure units incorporated. 另一方面本发明涉及新的引入烯基酯式结构的2-(2-羟基苯基)苯并三唑类化合物以及其作为紫外线吸收剂的用途。 Another aspect of the invention relates to 2- (2-hydroxyphenyl) benzotriazoles alkenyl esters introduction of a new structure and the use thereof as an ultraviolet absorber.

背景技术 Background technique

:在聚合物防老化技术中,2-(2-羟基苯基)苯并三唑化合物是一类重要的紫外线吸收剂。 : Anti-aging in the polymer art, 2- (2-hydroxyphenyl) benzotriazole compounds are an important class of UV absorbers. 为了适应复杂和苛刻的聚合物加工及使用条件,将苯并三唑类化合物进行化学结构修饰以达到改善其耐高温性、耐候性、持效性、挥发性和相容性的目的。 In order to adapt to the complex and the polymer processing and harsh conditions, the benzotriazole-based compound is chemically modified to achieve the structure to improve its high-temperature resistance, weather resistance, holding effect, volatility and compatibility purposes.

为了达到上述应用特性的要求,欧洲专利公开EP0738718A中描述了苯环3位进行α-枯基取代的修饰方法;美国专利6166218公开了在苯并环的5位引进-CF3修饰;美国专利6268505和6407254公开了在苯环的3位引入2,4-咪唑啉二酮-5,5-双取代结构。 In order to achieve the required properties of application, European patent publication EP0738718A describes α- cumyl phenyl substituted modification method 3; U.S. Patent No. 6,166,218 discloses a modification to introduce -CF3 benzo ring at position 5; and U.S. Patent No. 6,268,505 and 6,407,254 discloses the introduction of a 2,4-imidazolidinedione of the benzene ring at the 3-substituted 5,5-bis structure. 上述公开技术所涉及的各类2-(2-羟基苯基)苯并三唑类化合物多是结构上的简单延伸和基团替换,未涉及到烯基结构的基团。 Various types of 2- (2-hydroxyphenyl) benzotriazole compounds disclosed in the above art involved more than a simple extension of the structure and the replacement group, an alkenyl group is not related to the group structure.

美国专利6489486公开了针对苯环3位进行烷基化的方法,通过O-烷基化再进行重排的方式可能获得的某种烯基片段由于位阻效应等因素往往难以具有可反应特性。 Some alkenyl moiety U.S. Patent 6,489,486 discloses a process for the alkylation of the benzene ring 3, and then rearranged by O- alkylation manner might receive due to steric hindrance effects and other factors often difficult having response characteristics.

发明内容 SUMMARY

:为了解决常规2-(2-羟基苯基)苯并三唑类化合物在耐高温性、耐候性、持效性、挥发性和相容性等特性方面的局限,本发明公开了一种具有通式(I)的带有烯基酯式结构的苯并三唑以用作新型紫外线吸收剂,并提供关于此通式(I)的制备方法,具有反应条件温和、高选择性、低成本的优点。 : In order to solve the conventional 2- (2-hydroxyphenyl) benzotriazole compounds limitation in heat resistance, weather resistance, holding effect, volatility and compatibility characteristics and the like, the present invention discloses a formula (I) with an alkenyl ester of a benzotriazole structure to be used as ultraviolet absorbents, and to provide a method of this formula (I) with respect to, mild reaction conditions, high selectivity, low cost The advantages.

由于此2-(2-羟基苯基)苯并三唑的苯环3位带有烯基酯式结构,当其作为紫外线吸收剂施用于聚合物材料加工和使用的过程中时,可以使得光稳定活性片段和聚合物基材之间存在嫁接聚合效应;同时由于可聚合的反应特性,使得其挥发性极低。 Because of this 2- (2-hydroxyphenyl) benzotriazole benzene alkenyl esters having 3 structure, when the process is applied as an ultraviolet absorber and a polymer material used in the process may be such that the light grafting polymerization effect exists between the stable and active fragments polymeric substrate; the same time as the polymerizable reaction characteristics such that it low volatility. 同时由于通式(I)结构所具有的反应特性,使得聚合物的防老化特征具有更好的耐候性和持效性。 And because of the general structural formula (I) has the response characteristics, so that the aging characteristics of the polymer having better weather resistance and persistent action. 另外也是基于烯基酯式基团的结构修饰,通式(I)化合物可以和各种聚合基材有更好的相容性,包括涂层和塑料等。 Further structural modifications are based on the alkenyl ester group of the formula, a compound of formula (I) can be a variety of polymeric substrates have a better compatibility, including plastic coatings and the like.

其中,X=3,4,5,6位取代的氢、卤素、烷基或烷氧基;R=烷基、环烷基、羧酸基、芳基或取代芳基;R1、R2和R3独立地是氢、烷基或链烯基;M为亚烃基。 Wherein, X = 3,4,5,6-substituted hydrogen, halogen, alkyl or alkoxy; R = alkyl group, a cycloalkyl group, a carboxylic acid group, an aryl group or a substituted aryl group; R1, R2 and R3 is independently hydrogen, alkyl or alkenyl group; M is a hydrocarbylene group.

在本发明中我们提供了三种可供选择的经济高效工艺方案来合成通式(I)化合物,其工艺设计如下。 In the present invention we provide a cost-effective scheme three alternative process to synthesize compounds of formula (I), which process is designed as follows.

工艺方案一:通过3-羟烷基取代的通式(II)化合物 A process scheme: (II) an alkyl-substituted compound of formula 3-hydroxybutyrate 和通式(IV)烯基甲酸 And formula (IV) alkenyl acid 进行醇酸酯化反应来制备通式(I)化合物。 For alkyd esterification of general formula (I) compound.

上述式II、IV中,X,R,R1,R2,R3,M的定义同通式I中的定义。 The above-described formula II, IV, the definition of X, R, R1, R2, R3, M is the same as defined in formula I.

工艺方案二:通过通式(II)化合物和通式(V)烯基甲酸低烷基酯 Process Scheme II: by formula (II) carboxylic acid lower alkyl alkenyl compound of formula (V) ester 进行酯交换化反应来制备通式(I)化合物。 A transesterification reaction of the compound of general formula (I).

上述式II、V中,X,R,R1,R2,R3,M的定义同通式I中的定义;R4是C1~C4烷基。 The above formula II, V, the definition of X, R, R1, R2, R3, M is the same as defined in formula I; R4 is C1 ~ C4 alkyl group.

工艺方案三:通过3-卤烷基取代或磺酰氧烷基取代的通式(III)化合物 Process Program III: (III) compound 3-halo-substituted alkyl or alkyl substituted sulfonyloxy formula 和通式(IV)烯基甲酸或者其碱金属盐反应来制备通式(I)化合物。 And alkenyl carboxylic acid or an alkali metal salt of the general formula (IV) to prepare a compound of formula (I).

上述式III、IV中,X,R,R1,R2,R3,M的定义同通式I中的定义;Y是卤素和磺酰氧基。 Formula III, IV, the definition of X, R, R1, R2, R3, M is the same as defined in formula I; Y is halogen and sulfonyloxy group.

在上述通式I化合物中,那些其中X、R、R1、R2、R3、M的定义与其在权利要求1中的定义相同的化合物是新化合物,其特性在于在苯环的3-位带有烯基酯式结构单元。 In the compounds of formula I, those wherein the definition of X, R, R1, R2, R3, M compound in its same as defined in claim 1 is a new compound that has characteristics in which the 3-position of the phenyl ring vinyl ester structural unit. 当R1、R2、R3中的一个或多个基团可以是为链烯基,则烯基酯式结构特性可以理解为多烯基特征的酯式结构。 When R1, R2, R3 one or more groups may be an alkenyl group, the alkenyl ester structure characteristic structure can be understood as an ester group wherein the polyene. 因而其也是本发明的目的。 Accordingly it is object of the present invention.

作为通式(I)的新化合物具体实例是:2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)苯并三唑 As the novel compounds of formula (I) Specific examples are: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) benzotriazole 2- (2'-hydroxy - 3 '- (α- methacryloyl oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (methacryloyloxyethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (methacryloyl oxyethyl alpha]) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (2 - butenoyl oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butenoyl yloxymethyl) -5' ) benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadiene acyl oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-t-butyl) benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyloxy methyl) -5'-tert-butyl ) benzotriazole 2- (2'-hydroxy-3 '- (2-butenoyl yloxymethyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy-3' - ( α- methyl-2-oxo-butenoyl) -5'-t-butyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Tessin ) benzotriazole

2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(丙烯酰基氧丙基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧丙基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰 2- (2'-hydroxy-3 '- (methacryloyloxyethyl methyl alpha]) -5' Texin Ji) benzotriazole 2- (2'-hydroxy-3' - (2-butene acyl oxymethyl) -5' Texin Ji) benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-yloxymethyl butenoyl) -5' Texin Ji ) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) benzotriazole 2- (2 ' - hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (1-methyl-1-phenylethyl)) benzotriazole 2- (2'-hydroxy-3'- (acryloyloxyethyl) -5 '- (1-methyl-1-phenylethyl)) benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyl oxyethyl ) -5 '- (1-methyl-1-phenylethyl)) benzotriazole 2- (2'-hydroxy-3' - (methacryloxypropyl) -5 '- (l-methyl 1-phenylethyl)) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl-oxopropyl) -5' - (1-methyl-1-phenyl-acetate yl)) benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadiene acyl oxymethyl) -5' - (1-methyl-1-phenylethyl)) benzene benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3' - ([alpha] - methacryloyloxy methyl) -5'-methyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy 氧乙基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-叔丁基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-叔丁基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基)) Oxoethyl) -5'-methyl) -5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxyethyl) -5'-methyl) - 5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (2-butenoyl oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (methyl-2-butenoyl alpha] oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (2-butenoyl yloxymethyl) -5 '- tert-butyl) -5-chloro-benzotriazole 2- (2'-hydroxy -3' - (α- methyl-2-oxo-butenoyl) -5'-t-butyl) - 5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Texin Ji) -5-chloro-benzotriazole 2- (2'-hydroxy 3 '- (methacryloyloxyethyl methyl alpha]) -5' Texin Ji) -5-chloro-benzotriazole, 2- (2'-hydroxy-3' - (2-oxo-butenoyl methyl) -5' Texin Ji) -5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-oxo-butenoyl) -5' Texin Ji) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) - 5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (1-methyl-1-phenylethyl)) --5 - chloro-benzotriazole 2- (2'-hydroxy-3 '- (methacryloyloxyethyl) -5' - (1-methyl-1-phenylethyl)) -5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))-5-氯代苯并三唑 -5-chlorobenzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxyethyl) -5' - (1-methyl-1-phenylethyl)) - 5-chloro-benzotriazole

2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧丙基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧丙基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2- 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (alpha] methacryloyloxy methyl) -5'-methyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (methacryloxypropyl) -5'-methyl ) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α--methacryloyloxy propyl) -5'-methyl) -5-trifluoromethyl-benzo triazole 2- (2'-hydroxy-3 '- (2-butenoyl oxymethyl) -5'-methyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (methyl-2-butenoyl alpha] oxymethyl) -5'-methyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (1,3 - pentadienoyl oxymethyl) -5'-methyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-t butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxy methyl) -5'-t-butyl) -5- trifluoromethanesulfonyloxy benzotriazole 2- (2'-hydroxy-3 '- (methacryloyloxyethyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy - 3 '- (α- methacryloyl oxyethyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (methyl acryloyloxyethyl ) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧 (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3'- (oxymethyl butenoyl) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butene acyl oxymethyl) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadiene acyloxy) -5 '- Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (acryloyloxy-methyl) -5 '- (1-methyl-1-phenyl-acetate yl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (1-methyl-1-phenyl ethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (2-butenoyl oxymethyl) -5' - (1-methyl-1-phenyl ethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butenoyl yloxymethyl) -5' - (l-methyl 1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadiene acyl oxymethyl) -5' - (1 - methyl-1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (methacryloyloxyethyl) -5' - (l-methyl 1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl 基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(2-丁烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基-2-丁烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(1,3-戊二烯酰基氧乙基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑另一方面,本发明涉及含有上述通式(I)的2-羟基苯基苯并三唑类化合物单独或和至少一种其它UV-A和/或UV-B掩遮剂的新的紫外线吸收剂,也称作光稳定剂。 Yl) -5 '- (1-methyl-1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (2-oxo acid butenoyl yl) -5 '- (1-methyl-1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3' - (α- methyl-2- butenoyl oxoethyl) -5 '- (1-methyl-1-phenylethyl)) - 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (1, 3- pentadienoyl oxoethyl) -5 '- (1-methyl-1-phenylethyl)) - 5-trifluoromethyl-benzotriazole another aspect, the present invention relates to the above-mentioned general formula comprising (I) a 2-hydroxyphenyl benzotriazole compound alone or in at least one other UV-a and / or a new ultraviolet absorbent UV-B Yanzhe agent, also known as light stabilizers. 最后,本发明涉及上文定义的通式(I)的新的2-羟基苯基苯并三唑类化合物用作光稳定剂的用途。 Finally, the present invention relates to novel 2-hydroxyphenyl phenyl as defined above formula (I) and the use of triazole compounds as light stabilizers.

特别优选的用作紫外线吸收剂的化合物是:2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧乙基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧乙基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-( Particularly preferred compounds are used as an ultraviolet absorber: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (methacryloyloxyethyl methyl alpha]) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (methacryloyloxyethyl) -5'-methyl) benzene benzotriazole 2- (2'-hydroxy-3 '- (methacryloyl oxyethyl alpha]) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (acryl oxymethyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxy methyl) -5'-t-butyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Texin Ji) benzotriazole 2- (2'-hydroxy-3' - (methacryloyloxyethyl methyl alpha] yl) -5' Texin Ji) benzotriazole 2- (2'-hydroxy-3 '- (methacryloyloxyethyl) -5' Texin Ji) benzotriazole 2- (2'- hydroxy-3 '- (methacryloyl oxyethyl alpha]) -5' Texin Ji) benzotriazole 2- (2'-hydroxy-3' - (acryloyloxy-methyl) -5' (1-methyl-1-phenylethyl)) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (l-methyl - 1-phenylethyl)) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) -5-chloro-benzotriazole 2- (2 '- hydroxy-3' - ( -甲基丙烯酰基氧甲基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-叔丁基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)-5-三氟甲基苯并三唑 - methacryloyloxy methyl) -5'-methyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-tert-butyl ) -5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxy methyl) -5'-t-butyl) -5-chloro-benzotriazole 2 - (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Texin Ji) -5-chloro-benzotriazole, 2- (2'-hydroxy-3' - (methyl alpha] acryloyl oxymethyl) -5' Texin Ji) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (l-methyl 1-phenylethyl)) - 5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (l-methyl - 1-phenylethyl)) - 5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) -5-trifluoromethyl benzene benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5'-methyl) -5-trifluoromethyl-benzotriazole

2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)-5-三氟甲基苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-(1-甲基-1-苯基乙基))-5-三氟甲基苯并三唑最优选的通式(I)化合物如下:2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)-5-氯代苯并三唑2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-叔丁基 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-t-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - ([alpha] - methacryloyloxy methyl) -5'-t-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5' Texin Ji) -5-trifluoromethyl methyl-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) - 5-trifluoromethyl-benzene benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyloxyethyl) -5' - (1-methyl-1-phenylethyl)) - 5-trifluoromethyl- the most preferred compound of formula benzotriazole (I) as follows: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) benzotriazole 2- (2'- hydroxy -3 '- (α- methacryloyl oxymethyl) -5'-methyl) benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyloxy methyl) - 5'-tert-butyl) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5' Texin Ji) benzotriazole 2- (2' - hydroxy -3 '- (α- methacryloyl oxymethyl) -5'-methyl) -5-chloro-benzotriazole 2- (2'-hydroxy -3' - (α- methacryl acyl oxymethyl) -5'-tert-butyl )-5-氯代苯并三唑2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)-5-氯代苯并三唑本发明使用的术语烷基表示含有1-21个碳原子,优选含有1-8个碳原子的饱和直链或支链烷基,例如,甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、戊基、新戊基、己基、2-乙基-己基、特辛基。 ) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-term Texin Ji) -5-chloro-benzotriazole used in the present invention represents an alkyl group containing 1-21 carbon atoms, preferably a saturated straight or branched chain alkyl group having 1-8 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, sec-butyl , t-butyl, pentyl, neopentyl, hexyl, 2-ethyl - hexyl, Texin Ji. 类似地,术语烷氧基表示通过氧原子键合的含有1-21个碳原子,优选含有1-8个碳原子的饱和直链或支链烷基,例如,甲氧基、乙氧基、丙氧基、异丙氧基、丁氧基、仲丁氧基、叔丁氧基、戊氧基、新戊氧基、己氧基、2-乙基-己氧基、特辛氧基。 Similarly, the term alkoxy denotes an oxygen atom bonded by containing 1-21 carbon atoms, preferably a saturated straight or branched chain alkyl group having 1-8 carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, neo-pentyloxy, hexyloxy, 2-ethyl - hexyl group, Tessin group. 术语环烷基表示C5~C7的环烷基和2-21个碳原子取代环烷基。 The term cycloalkyl denotes a cycloalkyl group and 2-21 carbon atoms substituted C5 ~ C7 cycloalkyl. 术语羧酸基表示C2-21个碳原子羧酸和羧酸C1~C18烷基酯,例如甲酸基、乙酸基、丙酸基、丁酸基、戊酸基、甲酸甲酯基、丙酸乙酯基。 The term carboxylic acid group represented by C2-21 carbon atoms, carboxylic acids and carboxylic esters of C1 ~ C18 alkyl, e.g. formyloxy, acetoxy, propionyloxy, butyryloxy group, valeric acid group, methyl group, ethyl propionate ester group. 芳基表示苯基、杂环基,例如吡啶-2-基、呋喃基、噻吩基。 Aryl represents a phenyl group, a heterocyclic group, e.g. pyridin-2-yl, furyl, thienyl. 取代芳基表示上述烷基、烷氧基取代的芳基,烷基和烷氧基的界定如上述定义。 Aryl represents a substituted alkyl group described above, defining alkoxy-substituted aryl, alkyl and alkoxy as defined above. 术语链烯基表示含有至少一个双键和2-21个碳原子,优选含有2-8个原子的直链或支链烃基,所述链烯基的实例是丙烯-2-基、丙烯-3-基、丁烯-4-基、戊烯-4-基和戊烯-5-基。 The term alkenyl denotes containing at least one double bond and 2-21 carbon atoms, preferably a straight-chain or branched hydrocarbon group of 2-8 atoms, examples of the alkenyl group is propen-2-yl, propenyl -3 - yl, buten-4-yl, penten-4-yl and pent-5-yl. 术语卤素表示氟、氯、溴和碘。 The term halogen represents fluorine, chlorine, bromine and iodine. 术语磺酰氧基表示甲苯磺酰氧基、甲磺酰氧基。 The term & sulfonyloxy group represented toluenesulfonyloxy, methanesulfonyloxy group. 术语亚烃基表示C1~C18烷撑基,优选含有1-8个碳原子的饱和直链和支链烷撑基,例如甲撑、乙撑、丙撑、异丙撑、丁撑、仲丁撑、叔丁撑、戊撑、新戊撑、己撑、2-乙基-己撑、特辛撑。 The term alkylene denotes C1 ~ C18 alkylene group, preferably a saturated straight-chain and branched-chain alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, trimethylene, isopropyl support, butylene, sec-butylene , t-butylene, pentamethylene, new pentamethylene, hexamethylene, 2-ethyl - hexylene, Tessin support.

一组优选的通式(I)苯并三唑类化合物中R1是氢、甲基、乙基,最优选氢和甲基。 A preferred group of formula (I) benzotriazole compounds wherein R1 is hydrogen, methyl, ethyl, most preferably hydrogen and methyl. 而且优选R2、R3是氢、不超过5个碳原子的烷基及不超过5个碳原子的链烯基,更优选为氢和不超过3个碳原子的烷基和链烯基。 Further preferably R2, R3 are hydrogen, alkyl of not more than 5 carbon atoms and not more than 5 carbon atoms, an alkenyl group, and more preferably not more than hydrogen and alkyl and alkenyl group having 3 carbon atoms. 优选X为苯并环5位取代的氢、氯、三氟甲基,二氟一氯甲基、一氟二氯甲基,更选择为氢、氯。 Preferably X is a 5-substituted benzo ring of hydrogen, chloro, trifluoromethyl, a difluoromethyl, chloromethyl, dichloromethyl a fluorine, more selected hydrogen, chloro. 优选R是C1-C8的直链和支链烷基以及C1-C8取代的枯基,更选择是甲基、叔丁基、特辛基、α-枯基。 Preferably R is C1-C8 straight chain and branched alkyl groups and C1-C8 substituted cumyl group, more choice is methyl, t-butyl, Texin Ji, alpha] cumyl group. 优选M为C1-C4烷撑,更优选为甲撑和乙撑,最优选是甲撑。 M is preferably a C1-C4 alkylene, more preferably methylene and ethylene, most preferably methylene.

根据本发明的新方法,通式(I)化合物可以选择如下列化学反应式1-3所示来进行制备,其分别对应上述工艺方案1-3。 The new method of the present invention, compounds of formula (I) can be selected as shown in the following chemical formulas 1-3 to be prepared, which correspond to the above-described process scheme 1-3.

化学反应式一: A chemical formula: 在本工艺方案一中,利用苯环3位上的醇羟基和烯基酸来进行酯化反应。 In one embodiment of the present process, the esterification reaction is performed by using alcoholic hydroxyl group and an alkenyl group on the phenyl ring 3 acids. 通式II苯并三唑化合物和通式IV烯基酸的摩尔比选择1∶0.1~10,优选为1∶0.8~1.2,最优选为1∶0.9~1.1。 Molar ratio of benzotriazole compounds of formula II and an acid of formula IV alkenyl group selection 1:0.1 to 10, preferably from 0.8 to 1.2, and most preferably 0.9 to 1.1. 反应的催化剂可以选择硫酸、磷酸、链烷磺酸、芳基磺酸及多元无机酸,优选为硫酸和对甲苯磺酸,最优选是对甲苯磺酸。 The selected catalyst may be sulfuric acid, phosphoric acid, alkane sulfonic acids, aryl sulfonic acids and polybasic mineral acids, preferably sulfuric acid and p-toluenesulfonic acid, most preferably p-toluenesulfonic acid. 反应混合物中的催化剂浓度通常为0.5至10wt%,优选为1至5wt%,最优选是2至3wt%(按总混合物计)。 The catalyst concentration in the reaction mixture is usually from 0.5 to 10wt%, preferably from 1 to 5wt%, most preferably from 2 to 3wt% (based on the total mixture basis).

对于聚合抑制剂,选择(例如)吩噻嗪、氢醌、氢醌单甲基醚或其化合物和可能的空气,更优选为吩噻嗪、氢醌单甲基醚或其化合物。 For the polymerization inhibitor, selected (e.g.) phenothiazine, hydroquinone, hydroquinone monomethyl ether, and possibly air or a compound thereof, more preferably phenothiazine, hydroquinone monomethyl ether, or a compound thereof. 聚合抑制剂用量选择为100至5000ppm,更优选为2000ppm至3000ppm(按反应混合物计)。 The amount of the polymerization inhibitor is selected from 100 to 5000ppm, more preferably 2000ppm to 3000 ppm of (press on the reaction mixture).

作为夹带剂,在本发明中可选择使用饱和烃(如环己烷)或芳烃(如甲苯);本发明中更优选的夹带剂为苯和甲苯。 As an entrainer, in the present invention, optionally a saturated hydrocarbon (e.g., cyclohexane) or an aromatic hydrocarbon (e.g. toluene); the present invention, more preferred are benzene and toluene entrainer.

反应器中的反应温度优选70至160℃,更优选为90至130℃。 The reaction temperature of the reactor is preferably from 70 to 160 ℃, more preferably from 90 to 130 ℃. 反应时间优选为1至10小时,更优选1至6小时。 The reaction time is preferably 1 to 10 hours, more preferably 1 to 6 hours.

反应可在大气压、低于大气压或高于大气压下连续或间隙进行,其中更选择为常压情况下间隙进行。 The reaction may be at atmospheric, subatmospheric or continuously carried out under atmospheric pressure or gap, wherein the gap is selected for more under atmospheric pressure conditions.

化学反应式二: Chemical reaction formula II: 在本工艺方案二中,利用苯环3位上的醇羟基和烯基酸低烷基酯来进行酯交换反应。 In this process scheme II, to a transesterification reaction with an alcohol hydroxyl group and a lower alkenyl acid alkyl ester 3 on the phenyl ring. R4是C1~C4烷基,优选为甲基、乙基,最优选为甲基。 R4 is C1 ~ C4 alkyl, preferably methyl, ethyl, most preferably methyl. 通式II苯并三唑化合物和通式V烯基酸低烷基酯的摩尔比选择1∶1~20,优选为1∶1~15,最优选为1∶1.2~10。 Molar ratio of benzotriazole compounds of formula II and of formula V lower alkenyl acid alkyl ester selected 1/1 to 20, preferably from 1/1 to 15, and most preferably from 1.2 to 10. 反应混合物包括至少一个聚合抑制剂,适合的聚合抑制剂包括二乙基羟基胺、对甲氧基酚、氢醌、吩噻嗪、4-羟基-2,2,6,6-四甲基哌啶基自由基(4-羟-TEMPO)、4-甲丙烯酰氧基-2,2,6,6-四甲基哌啶基自由基及它们的混合物。 The reaction mixture comprising at least one polymerization inhibitor, suitable polymerization inhibitors include diethylhydroxylamine, p-methoxyphenol, hydroquinone, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine piperidinyl free radical (4-hydroxy-TEMPO), 4- methacryloxy-2,2,6,6-tetramethyl piperidinyl free radical, and mixtures thereof. 基于通式II苯并三唑类化合物的重量,聚合抑制剂用量选择为10至10000ppm,优选100至5000ppm,最优选为200ppm至3000ppm。 Based on the weight of the general formula II benzotriazole-based compound, a polymerization inhibitor is used in an amount selected from 10 to 10000 ppm, preferably 100 to 5000 ppm of, and most preferably 200ppm to 3000ppm.

本发明中合适的酯交换催化剂包括C1-C3低烷基醇钠、氧化二丁基锡、二丁基锡甲醇盐、C4-C8烷基锌、碳酸锂、烯基酸C1-C4烷基季铵盐、氢氧化锂、甲醇镁甲基化物,优选氧化二丁基锡和氢氧化锂。 In the present invention, a suitable transesterification catalysts include C1-C3 lower alkyl alcohol, sodium, dibutyltin oxide, dibutyltin methoxide, C4-C8 alkyl zinc, carbonate, alkenyl, C1-C4 alkyl quaternary ammonium salts of the acid, hydrogen lithium oxide, magnesium methoxide methide, preferably dibutyltin oxide and lithium hydroxide. 酯交换催化剂浓度通常为0.1至10摩尔%,优选为0.5至7摩尔%,最优选是1至5摩尔%。 Transesterification catalyst concentration is generally 0.1 to 10 mol%, preferably 0.5 to 7 mol%, most preferably 1 to 5 mol%.

本发明的工艺方案二利用Oldershaw蒸馏塔,合适的Oldershaw蒸馏塔的塔板数为5至40,更优选为10至20。 The process of the invention using two Oldershaw distillation column, the appropriate plate number Oldershaw distillation column is 5 to 40, more preferably from 10 to 20. 回流比选择10~30。 A reflux ratio of 10 to 30 selection.

作为夹带剂,在本发明中可选择使用饱和烃(如环己烷、正己烷)或芳烃(如甲苯),本发明中优选加入夹带剂正己烷。 As the entrainer, optionally a saturated hydrocarbon (e.g., cyclohexane, hexane) or an aromatic hydrocarbon (e.g. toluene) in the present invention, the present invention is preferably added n-hexane entrainer.

反应器中的反应温度优选70至160℃,更优选为90至130℃。 The reaction temperature of the reactor is preferably from 70 to 160 ℃, more preferably from 90 to 130 ℃. 反应时间优选为1至20小时,更优选1至10小时。 The reaction time is preferably 1-20 hours, more preferably 1 to 10 hours.

反应可在大气压、低于大气压或高于大气压下连续或间隙进行,其中更选择为略减压情况下间隙进行。 The reaction may be at atmospheric, subatmospheric or continuously carried out under atmospheric pressure or gap, wherein the gap is even more the case where the selection is slightly reduced pressure.

化学反应式三: Chemical reaction formula III: 在本工艺方案三中,利用通式III苯环3位取代基团上的易离去基团Y和与通式IV结构的羧酸基或者羧酸盐在碱性条件下缩合制备通式I化合物。 In this process scheme III the benzene ring of formula III using three substituent leaving group Y and a carboxylic acid group or a carboxylic acid salt of Formula IV is prepared by condensing the structure of formula I under basic conditions in the group compound. Y优选可以是氯、甲磺酰氧基。 Y may preferably be chlorine, methanesulfonyloxy. 作为碱性物的化合物可选择NaOH、KOH、LiOH,更优选为NaOH。 Alternatively a compound of caustic NaOH, KOH, LiOH, more preferably NaOH. 本工艺优选步骤为两步,第一步是通过酸碱中和制备得到干燥的通式IV所对应的羧酸盐化合物;第二步继续和通式III缩合制备目标化合物I。 This step is preferably a two-step process, the first step is dried to give the carboxylate compounds of Formula IV and the corresponding acid prepared by; and a second step of continuing condensation of Formula III was prepared the title compound I.

通式IV和碱性氢氧化物的摩尔比选择1∶0.8~4,优选为1∶0.9~1.1。 The molar ratio of formula IV and alkali hydroxide selected from 0.8 to 4, preferably from 0.9 to 1.1. 碱性氢氧化物可以是固体物,也可以是10%以上的水溶液体系。 Alkaline hydroxide may be a solid, may be 10% or more aqueous systems. 中和反应的温度选择0~100℃,选择为25~60℃。 The reaction temperature and the choice of 0 ~ 100 ℃, is selected to 25 ~ 60 ℃. 所得羧酸盐需经过脱水处理,常用的脱水方法都可以选择,优选方法为喷雾干燥法。 The resulting carboxylate subject to dehydration treatment, the usual method of dehydration can be selected, the preferred method is spray drying.

在步骤二中需要选择相转移催化剂来提高反应速率,合适的催化剂可以是季铵盐,最优选为四甲基氯化铵,其用量相对通式IV的羧酸盐而言为0.1摩尔%~3摩尔%,优选为0.3~1摩尔%。 In step two need to select a phase transfer catalyst to increase the reaction rate, a suitable catalyst may be quaternary ammonium salts, most preferably tetramethylammonium chloride, salts of carboxylic acids in an amount relative to the general formula IV is 0.1 mol% in terms of 3 mol%, preferably 0.3 to 1 mol%. 反应混合物包括至少一个聚合抑制剂,适合的聚合抑制剂包括二乙基羟基胺、对甲氧基酚、氢醌、吩噻嗪、4-羟基-2,2,6,6-四甲基哌啶基自由基(4-羟-TEMPO)、4-甲丙烯酰氧基-2,2,6,6-四甲基哌啶基自由基及它们的混合物,优选为吩噻嗪。 The reaction mixture comprising at least one polymerization inhibitor, suitable polymerization inhibitors include diethylhydroxylamine, p-methoxyphenol, hydroquinone, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine piperidinyl free radical (4-hydroxy-TEMPO), 4- methacryloxy-2,2,6,6-tetramethyl piperidinyl free radical, and mixtures thereof, preferably phenothiazine. 聚合抑制剂用量相对通式IV的羧酸盐而言选择为0.05~1摩尔%,优选0.1至0.5摩尔%。 The amount of the polymerization inhibitor relative carboxylates of formula IV and the selectivity for 0.05 to 1 mol%, preferably 0.1 to 0.5 mol%. 通式III苯并三唑化合物和通式IV羧酸的摩尔比选择1∶1~10,优选为1∶1~5,最优选为1∶1~2。 Molar ratio of benzotriazole compounds of formula III and carboxylic acids of formula IV selection 1/1 to 10, preferably from 1/1 to 5, and most preferably from 1/1 to 2.

步骤二缩合反应的反应温度优选70至160℃,更优选为90至120℃。 The reaction temperature of the two step condensation reaction preferably 70 to 160 ℃, more preferably from 90 to 120 ℃. 反应时间优选为1至20小时,更优选1至10小时。 The reaction time is preferably 1-20 hours, more preferably 1 to 10 hours. 反应可以在有溶剂或者无溶剂的条件下进行,可以选择的溶剂包括DMF、DMSO、NMP等等。 The reaction may be carried out under conditions of a solvent or without a solvent may be selected solvents include DMF, DMSO, NMP and the like.

下述实例将详细说明本发明,但无论如何不限制本发明范围。 The following examples of the present invention will be described in detail, but in no way limit the scope of the present invention.

按照已有的合成报道,通式II的苯环3位羟烷基取代苯并三唑化合物可以通过相应的重氮盐和2,6-5双(羟烷基)-对烷基酚进行偶合,在偶联时由于一个羟烷基脱离,可以得到如通式II的化合物。 According to the prior reported synthesis, the phenyl ring of formula II 3 hydroxyalkyl group substituted benzotriazole compounds by diazonium salts and the corresponding 2,6-5-bis (hydroxyalkyl) - alkylphenol of the coupling , upon coupling a hydroxyalkyl disengaged due, such as the compounds of formula II can be obtained.

当2-(2-羟基苯基)苯并三唑苯环3位为H时,在苯环的3位的C原子上可以进行亲电子取代反应,通过常规的卤烷基化或者磺酰烷基化方法可以得到通式III的化合物。 When 2- (2-hydroxyphenyl) benzotriazole benzene ring 3 is H, in the 3-position of the benzene ring C atoms electrophilic substitution reaction can be carried out by conventional alkylation or sulfonyl alkyl halides group of compounds of formula III can be obtained.

具体实施方式 detailed description

:制备实施例一:(工艺方案一)[2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑的制备] : Example Preparation of a process scheme :( a) [2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) benzotriazole] (目标化合物1)将255.3g 2-(2'-羟基-3'-羟甲基-5'-甲基)苯并三唑以及1000ml苯加入到2000ml的反应容器中,加热使其溶解均匀。 (Target Compound 1) 255.3g 2- (2'- hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole, and benzene was added to 1000ml 2000ml reaction vessel and heated to dissolve uniformly. 在上述混合物中加入0.8g吩噻嗪、75g丙烯酸,升温到缓慢回流状态,分批次10g对甲苯磺酸,保持回流状态。 To the above mixture was added 0.8g of phenothiazine, 75g of acrylic acid, was slowly heated to reflux, p-toluenesulfonic acid 10g batches, maintaining reflux. 搅拌反应4小时以后,注意观察油水分离器中收集的水量。 After the reaction was stirred for 4 hours to observe the amount of water collected in the water separator.

通过油水分离装置,当分离出的水接近18ml时间,即可停止反应。 By oil-water separation means when the separated water 18ml close time, to stop the reaction. 同时在反应接近结束阶段可以通过高效液相色谱(HPLC)进行分析。 At the same time it can be analyzed by high performance liquid chromatography (HPLC) towards the end of the reaction stage. 作为反应原料的2-(2'-羟基-3'-羟甲基-5'-甲基)苯并三唑的消失以及2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑的生成得到证实。 As the reaction raw material 2- (2'-hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole, and the disappearance of 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methylphenyl) benzotriazole generated was confirmed.

反应完成后将反应混合物进行水洗,萃取处理。 After completion of the reaction the reaction mixture was washed with water, extraction process. 有机层减压移除溶剂苯后残留物进行淋洗、脱色、真空干燥处理。 The residue was subjected to solvent was removed under reduced pressure after the organic layer was rinsed with benzene, decolorized, dried in vacuo. 淋洗液选择50%乙醇水溶液,脱色处理选择利用活性炭吸附。 Select eluent 50% aqueous ethanol, decolorized using activated carbon adsorption selected. 处理后的纯品产物经HPLC分析,其含量≥98.0%。 Pure product was processed by HPLC analysis, the content thereof is ≥98.0%. 干燥处理后可以得到281.5g纯品浆状物,产率为91%。 After the drying process can be obtained pure product slurry was 281.5g, 91% yield.

通过1HNMR、13CNMR及MS测试,说明目标产物符合2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-甲基)苯并三唑的结构特性。 By 1HNMR, 13CNMR and MS Test, described in line with the desired product 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5'-methyl) benzotriazole structural characteristics. 具体的元素分析情况如下:实测值(计算值)C65.99%(66.02%);H4.81%(4.85%);N13.60(13.59%)。 Specific Elemental analysis is as follows: Found (calcd) C65.99% (66.02%); H4.81% (4.85%); N13.60 (13.59%).

制备实施例二:(工艺方案一)[2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑的制备] [- Preparation of 5'-methyl) benzotriazole 2- ((α--methacryloyloxy-2'-hydroxy-methyl-3 ')]) :( one case two process schemes Preparation (目标化合物2)采用与实施例一相同的方法,用90g甲基丙烯酸替代丙烯酸,用10g浓硫酸代替对甲苯磺酸,在这种情况下,反应时间延长到8小时,反应得率为87%。 (The title compound 2) in the same manner as in Example one embodiment, instead of 90g acrylic acid with methacrylic acid, p-toluenesulfonic acid, in this case, the reaction time was extended to 8 hours with concentrated sulfuric acid in place of 10g, the reaction yield was 87 %. 1HNMR、13CNMR及MS确证了目标化合物的结构。 1HNMR, 13CNMR and MS confirmed the structure of the target compound. 具体的元素分析情况如下:实测值(计算值)C66.80%(66.87%);H5.19%(5.26%);N13.06(13.00%)。 Specific Elemental analysis is as follows: Found (calcd) C66.80% (66.87%); H5.19% (5.26%); N13.06 (13.00%).

制备实施例三:(工艺方案二)[2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑的制备]在2000ml装备有温度计、搅拌器、气体导入管以及带有回流控制装置的蒸馏塔的反应容器中加入255.3g 2-(2'-羟基-3'-羟甲基-5'-甲基)苯并三唑、600ml正己烷、0.5g对甲氧基苯酚,加热溶解均匀。 ) Di :( Example Three Preparation process scheme [2- (2'-hydroxy -3 '- (α--methacryloyloxy-methyl) -5'-methyl) benzotriazole] Equipment in 2000ml with a thermometer, a stirrer, a gas inlet pipe and a reaction vessel equipped with a reflux apparatus to control the distillation column was added 255.3g 2- (2'- hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole , 600ml n-hexane, 0.5g of p-methoxyphenol, heated and dissolved uniformly. 在上述混合物中加入1.0g氧化二丁基锡、500g甲基丙烯酸甲酯,在300mmHg压力下升温到回流状态,此时釜底温度70℃。 To the above mixture was added 1.0g of dibutyltin oxide, 500 g of methyl methacrylate was heated to reflux at 300mmHg pressure, wherein the bottoms temperature of 70 ℃. 控制回流比10~30,塔顶温度为38~55℃。 Controlling a reflux ratio of 10 to 30, top temperature 38 ~ 55 ℃. 甲醇将被作为共沸物的形式被移出。 Methanol been removed as an azeotrope. 反应4小时后,釜底温度升高到74℃,而塔顶温度再不可能维持在55℃或者更低的温度水平。 After 4 hours, kettle bottom temperature was raised to 74 deg.] C, and the overhead temperature was maintained at or less possible temperature level 55 ℃. 通过HPLC取样分析,可以得知2-(2'-羟基-3'-羟甲基-5'-甲基)苯并三唑的转化率已≥99.5%。 Sampling and analysis by HPLC, can be known 2- (2'-hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole conversion rate ≥99.5%.

立即结束反应后加入对甲苯磺酸钠以使得催化剂失活,改回流控制装置为蒸馏装置,减压到100mmHg蒸出过量的甲基丙烯酸甲酯和夹带溶剂。 Immediately after the completion of the reaction toluene sulfonate was added so that the catalyst is deactivated, the control means change at reflux a distillation apparatus was distilled off under reduced pressure to 100mmHg excess methyl methacrylate and entrained solvent. 反应完成后将反应混合物进行水洗,萃取处理。 After completion of the reaction the reaction mixture was washed with water, extraction process. 未反应的痕量苯并三唑反应物和其它副产品可以淋洗的方式加以洗脱。 Benzotriazole trace of unreacted reactants and other by-products can be eluted rinsed manner. 残留物继续进行脱色、真空干燥处理。 The residue was decolorized continued, vacuum drying. 淋洗液选择50%乙醇水溶液,脱色处理选择利用活性炭吸附。 Select eluent 50% aqueous ethanol, decolorized using activated carbon adsorption selected. 处理后的纯品产物经HPLC分析,其含量≥98.0%。 Pure product was processed by HPLC analysis, the content thereof is ≥98.0%. 干燥处理后可以得到297.2g纯品浆状物,产率为92%。 After the drying process can be obtained pure product slurry was 297.2g, 92% yield. 通过1HNMR、13CNMR及MS测试,说明目标产物符合2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑的结构特性。 By 1HNMR, 13CNMR and MS Test, described in line with the desired product 2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5'-methyl) benzotriazole structural characteristics. 具体的元素分析情况如下:实测值(计算值)C66.90%(66.87%);H5.21%(5.26%);N13.12(13.00%)。 Specific Elemental analysis is as follows: Found (calcd) C66.90% (66.87%); H5.21% (5.26%); N13.12 (13.00%).

制备实施例四:(工艺方案二)[2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)苯并三唑的制备] B) :( Example Four Preparation process scheme [2- (2'-hydroxy -3 '- (α--methacryloyloxy-methyl) benzotriazole 5'Texin Ji)] (目标化合物3)采用与实施例三相同的方法,用339.3g2-(2'-羟基-3'-羟甲基-5'-特辛基)苯并三唑为原料,其余的保持不变,此时反应时间需要5小时,产率为90%。 (Title compound 3) using the same method of the third embodiment, with 339.3g2- (2'- hydroxy-3'-hydroxymethyl-5'Texin Ji) benzotriazole starting material remaining unchanged In this case the reaction time required for 5 hours in 90% yield. 1HNMR、13CNMR及MS确证了目标化合物的结构。 1HNMR, 13CNMR and MS confirmed the structure of the target compound. 具体的元素分析情况如下:实测值(计算值)C70.80%(70.76%);H7.10%(7.13%);N10.26(10.32%)。 Specific Elemental analysis is as follows: Found (calcd) C70.80% (70.76%); H7.10% (7.13%); N10.26 (10.32%).

制备实施例五:(工艺方案二)[2-(2'-羟基-3'-(丙烯酰基氧甲基)-5'-特辛基)苯并三唑的制备] [- Preparation of 5'Texin Ji) benzotriazole 2- ((methyl-acryloyloxy-2'-hydroxy-3 ')] b) Preparation process scheme according to a fifth embodiment :( (目标化合物4)采用与实施例四相同的方法,催化剂改为0.5g氢氧化锂,丙烯酸甲酯用量调整到900g同时不使用夹带剂。 (Title compound 4) using the same method as in Example IV catalyst was changed to 0.5g lithium hydroxide, to adjust the amount of methyl acrylate 900g without entrainer. 在这种情况下,反应时间延长到7小时,反应得率为83%。 In this case, the reaction time was extended to 7 hours, the reaction yield was 83%. 1HNMR、13CNMR及MS确证了目标化合物的结构。 1HNMR, 13CNMR and MS confirmed the structure of the target compound. 具体的元素分析情况如下:实测值(计算值)C70.40%(70.23%);H6.79%(6.87%);N10.76(10.69%)。 Specific Elemental analysis is as follows: Found (calcd) C70.40% (70.23%); H6.79% (6.87%); N10.76 (10.69%).

制备实施例六:(工艺方案三)[2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑的制备]将119.5g甲基丙烯酸甲酯和55.5g氢氧化钠进行中和,通过喷雾干燥的方式可以得到150.0g无水甲基丙烯酸钠盐。 Example Preparation process scheme six :( c) [2- (2'-hydroxy -3 '- (α--methacryloyloxy-methyl) -5'-methyl) benzotriazole] A 119.5g methyl methacrylate and 55.5g of sodium hydroxide and can be obtained 150.0g anhydrous sodium salt of methacrylic acid by spray drying. 在装备有温度计、搅拌器和冷凝器的反应容器中加入上述无水钠盐、380g2-(2'-羟基-3'-氯甲基-5'-甲基)苯并三唑、1000mlDMF、0.9g四甲基氯化铵以及0.6g吩噻嗪,110℃下搅拌反应4小时。 Anhydrous sodium salt was added to the reaction vessel equipped with a thermometer, a stirrer and a condenser, 380g2- (2'- hydroxy-3'-chloro-5'-methyl) benzotriazole, 1000mlDMF, 0.9 g tetramethylammonium chloride and 0.6g of phenothiazine was stirred for 4 hours at 110 ℃. 通过HPLC取样分析,可以得知2-(2'-羟基-3'-氯甲基-5'-甲基)苯并三唑的转化率已≥99.5%。 Sampling and analysis by HPLC, can be known 2- (2'-hydroxy-5'-methyl-3'-chloro-methyl) benzotriazole conversion rate ≥99.5%. 反应结束后所生成的氯化钠盐可以通过过滤方式加以滤除。 The generated sodium chloride salt can be filtered off after the completion of the reaction by filtration. 在10mmHg减压条件下移除DMF后。 After removal of DMF under reduced pressure 10mmHg. 反应完成后将反应混合物进行水洗,萃取处理。 After completion of the reaction the reaction mixture was washed with water, extraction process. 未反应的微量苯并三唑反应物和其它副产品可以淋洗的方式加以洗脱。 Benzotriazole trace of unreacted reactants and other by-products can be eluted rinsed manner. 残留物继续进行脱色、真空干燥处理。 The residue was decolorized continued, vacuum drying. 淋洗液选择50%乙醇水溶液,脱色处理选择利用活性炭吸附。 Select eluent 50% aqueous ethanol, decolorized using activated carbon adsorption selected. 处理后的纯品产物经HPLC分析,其含量≥98.0%。 Pure product was processed by HPLC analysis, the content thereof is ≥98.0%. 干燥处理后可以得到408.2g纯品浆状物,产率为91%。 After the drying process can be obtained pure product slurry was 408.2g, 91% yield. 通过1HNMR、13CNMR及MS测试,说明目标产物符合2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-甲基)苯并三唑的结构特性。 By 1HNMR, 13CNMR and MS Test, described in line with the desired product 2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5'-methyl) benzotriazole structural characteristics. 具体的元素分析情况如下:实测值(计算值)C66.78%(66.87%);H5.09%(5.26%);N12.94(13.00%)。 Specific Elemental analysis is as follows: Found (calcd) C66.78% (66.87%); H5.09% (5.26%); N12.94 (13.00%).

制备实施例七:(工艺方案三)[2-(2'-羟基-3'-(α-甲基丙烯酰基氧甲基)-5'-特辛基)苯并三唑的制备]采用与实施例六相同的方法,用497g2-(2'-羟基-3'-氯甲基-5'-特辛基)苯并三唑为原料,其余的保持不变,此时反应时间需要5小时,产率为90%。 Example Preparation process scheme seven :( c) [2- (2'-hydroxy -3 '- (α- methacryloyl oxymethyl) -5' Texin Ji) preparing benzotriazoles] and using a method according to a sixth embodiment of the same, with 497g2- (2'- hydroxy-3'-methyl-5'-chloro Texin Ji) benzotriazole as a starting material, the rest remains unchanged, when the desired reaction time 5 hours yield 90%. 1HNMR、13CNMR及MS确证了目标化合物的结构。 1HNMR, 13CNMR and MS confirmed the structure of the target compound. 具体的元素分析情况如下:实测值(计算值)C70.84%(70.76%);H7.05%(7.13%);N10.21(10.32%)。 Specific Elemental analysis is as follows: Found (calcd) C70.84% ​​(70.76%); H7.05% (7.13%); N10.21 (10.32%).

按照如上的工艺方案可以制备得到如下的目标化合物(见表1):表1:目标化合物的原料以及化合物结构式 The process according to the above scheme can be prepared as the target compound (see Table 1): Table 1: a compound of starting material and the target compound of formula

应用实施例部分:应用实施例1:在聚丙烯PP扁丝中的光稳定作用a)将表2中所涉及的各目标化合物1g、1g三(壬基代苯基)亚磷酸酯、0.5g乙二醇[β-(3,5-二叔丁基4-羟基苯基)丙酸酯]和1g硬脂酸钙在涡轮混合器中与1Kg熔体指数为3.5的聚丙烯粉相混合。 Part Application Example: Application Example 1: Light stabilization in polypropylene PP flat yarn, a) in Table 2 each of the target compound involved 1g, 1g tris (nonyl substituted phenyl) phosphite, 0.5g glycol [β- (3,5- di-t-butyl-4-hydroxyphenyl) propionate] and calcium stearate 1g turbine mixer polypropylene powder is mixed with 3.5 melt index 1Kg. 将该混合物在230℃下挤压得到PP颗粒,拉伸比1∶6,PP扁丝:50μm。 The obtained mixture was extruded PP particles at 230 ℃, stretching ratio 1:6, PP flat yarns: 50μm.

将上述扁丝束在白板上并暴露于65WR天候老化仪(按照ASTMD2565-85标准)中,黑板温度64℃。 The above-described flat tow on the board and exposed to a 65WR weather meter (according to ASTMD2565-85 Standard), the black panel temperature 64 ℃. 借助恒速张力仪对各种曝光时间后的样品进行剩余韧度测量,由此测得达到原始韧度半数(T50)所需要的曝光时间。 By means of constant-speed tension meter samples after various exposure time remaining tenacity measured, whereby the measured exposure time to reach half of the original tenacity (T50) needed.

表2:光稳定剂的添加情况 T50(小时)没有光稳定剂 400目标化合物1 2400 Table 2: adding the light stabilizer T50 (hours) without stabilizer 400 light title compound 12,400

目标化合物3 2490目标化合物5 2700目标化合物10 2900b)按照a)的方法,只将乙二醇[β-(3,5-二叔丁基4-羟基苯基)丙酸酯]的添加量加大到1.0g/1000gPP粉。 Title compound 32 490 52 700 the title compound the title compound 10 2900b) according to a) of the method, only the ethylene glycol [β- (3,5- di-t-butyl-4-hydroxyphenyl) propionate] was added in an amount added great to 1.0g / 1000gPP powder. 其结果如表3。 The results are shown in Table 3.

表3:光稳定剂的添加情况 T50(小时)没有光稳定剂 400目标化合物1 3000目标化合物3 3100目标化合物5 3300目标化合物10 3600c)按照b)的方法,再将光稳定剂的添加量增加到1.5g/1000gPP粉。 Table 3: Add the light stabilizer T50 400 target compound (h) is not the target light stabilizer compound 33,100 13,000 53,300 title compound the title compound 10 3600c) according to b) was added and then the amount of the light stabilizer increases to 1.5g / 1000gPP powder. 其结果如表4。 The results are shown in Table 4.

表4:光稳定剂的添加情况 T50(小时)没有光稳定剂 400目标化合物1 3600目标化合物3 3700目标化合物5 3800目标化合物10 4000应用实施例2:在聚丙烯PP纤维中的光稳定作用PP纤维级I:0.1%硬脂酸钙+0.05%β-(4-羟基-3,5-二叔丁基苯基)丙酸正十八碳醇酯+0.05%三(2,4-二叔丁基苯基)亚磷酸酯+0.25%TiO2复丝:130/37dtex,拉伸比:1∶3.2,100%拉伸率加速老化试验:氙灯老化试验[Xenotest 1200],黑板温度:55℃测定其拉伸强度下降到50%时所需时间,具体结果如表5所示。 Table 4: Example 2 was added the light stabilizer T50 400 target compound (h) 13 600 no light stabilizer of the title compound the title compound 53 800 33 700 104 000 Application title compound: Light stabilizing action in polypropylene fibers PP PP fiber grade I: 0.1% calcium stearate + 0.05% β- (4- hydroxy-3,5-di-t-butylphenyl) propionate, n-octadecanol ester + 0.05% tris (2,4-di-t butylphenyl) phosphite + 0.25% TiO2 multifilament yarn: 130 / 37dtex, draw ratio:% stretch 1:3.2,100 accelerated aging tests: xenon lamp aging test [Xenotest 1200], black panel temperature: 55 deg.] C measured the tensile strength decreased to 50% of the required time, the specific results are shown in table 5.

表5 光稳定剂类型对PP纤维光稳定性的影响 Table 5 Effect of light stabilizers of the type of fiber optic stability PP

Claims (7)

  1. 1.一种带有烯基酯式结构的苯并三唑类化合物,其特征在于它是通式为(I)的化合物: An alkenyl compound having a benzotriazole ester of the structure, characterized in that it is a compound of formula (I) are: 其中,X=3,4,5,6位取代的氢、卤素、烷基或烷氧基;R=烷基、环烷基、羧酸基、芳基或取代芳基;R1、R2和R3独立地是氢、烷基或链烯基;M为亚烃基。 Wherein, X = 3,4,5,6-substituted hydrogen, halogen, alkyl or alkoxy; R = alkyl group, a cycloalkyl group, a carboxylic acid group, an aryl group or a substituted aryl group; R1, R2 and R3 is independently hydrogen, alkyl or alkenyl group; M is a hydrocarbylene group.
  2. 2.如权利要求1所说的带有烯基酯式结构的苯并三唑类化合物的制备方法,其特征在于它是经过如下工艺方案:通过3-羟烷基取代的通式(II)化合物 2. The method as benzotriazole compounds having alkenyl esters of said structure as claimed in claim 1, characterized in that it is the result of the following process scheme: by reacting 3-hydroxyalkyl-substituted formula (II) compound 和通式(IV)烯基甲酸 And formula (IV) alkenyl acid 进行醇酸酯化反应来制备通式(I)化合物。 For alkyd esterification of general formula (I) compound. 上述式II、IV中,X,R,R1,R2,R3,M的定义同通式I中的定义。 The above-described formula II, IV, the definition of X, R, R1, R2, R3, M is the same as defined in formula I.
  3. 3.如权利要求1所说的带有烯基酯式结构的苯并三唑类化合物的制备方法,其特征在于它是经过如下工艺方案:通式(II)化合物和通式(V)烯基甲酸低烷基酯 3. The method as benzotriazole compounds having alkenyl esters of said structure as claimed in claim 1, characterized in that it is the result of the following process scheme: Formula (II) and a compound of formula (V) alkenyl lower alkyl carbamic acid ester 进行酯交换化反应来制备通式(I)化合物。 A transesterification reaction of the compound of general formula (I). 上述式II、V中,X,R,R1,R2,R3,M的定义同通式I中的定义;R4是C1~C4烷基。 The above formula II, V, the definition of X, R, R1, R2, R3, M is the same as defined in formula I; R4 is C1 ~ C4 alkyl group.
  4. 4.如权利要求1所说的带有烯基酯式结构的苯并三唑类化合物的制备方法,其特征在于它是经过如下工艺方案:通过3-卤烷基取代或磺酰氧烷基取代的通式(III)化合物 4. The method as benzotriazole compounds having alkenyl esters of said structure as claimed in claim 1, characterized in that it is the result of the following process scheme: The 3-halo-substituted alkyl or alkyl sulfonyloxy substituted formula (III) compound 和通式(IV)烯基甲酸或者其碱金属盐反应来制备通式(I)化合物。 And alkenyl carboxylic acid or an alkali metal salt of the general formula (IV) to prepare a compound of formula (I). 上述式III、IV中,X,R,R1,R2,R3,M的定义同通式I中的定义;Y是卤素和磺酰氧基。 Formula III, IV, the definition of X, R, R1, R2, R3, M is the same as defined in formula I; Y is halogen and sulfonyloxy group.
  5. 5.权利要求1中的通式I化合物,R1、R2、R3中的一个或多个基团可以是为不饱和链烯基,通式I具有多烯基特征的酯式结构。 A compound of formula I according to claim 1, R1, R2, R3 one or more groups may be an unsaturated alkenyl group, an alkenyl group having a plurality of general formula I wherein the ester structure.
  6. 6.如权利要求1和5所说的带有烯基酯式结构的苯并三唑类化合物的应用,其特征在于用于聚合物防老化的光稳定剂。 5 and application of said benzotriazole-based compound with a vinyl ester of Formula 6. The structure as claimed in claim 1, characterized in that the polymer for anti-aging agent, a light stabilizer.
  7. 7.一种使用权利要求1和5所说的带有烯基酯式的苯并三唑类化合物作为光稳定剂的方法,其特征在于它的施用量为0.05~10%。 1 and 5 with the alkenyl ester of compound of formula benzotriazole as a light stabilizer of said A use as claimed in claim, characterized in that it is administered in an amount of 0.05 to 10%.
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