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Publication numberCN1727338 A
Publication typeApplication
Application numberCN 200410065921
Publication date1 Feb 2006
Filing date27 Dec 2004
Priority date27 Dec 2004
Publication number200410065921.2, CN 1727338 A, CN 1727338A, CN 200410065921, CN-A-1727338, CN1727338 A, CN1727338A, CN200410065921, CN200410065921.2
Inventors徐俊伟, 黄建, 邓爱斌
Applicant常州华钛化学有限公司
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Compound in benzotriazole category possessing alkenyl ester type structure, and preparation method
CN 1727338 A
Abstract
A benzotriazole compound with enylester structure, its preparing process and its application as optical stabilizer used for preventing ageing of polymer are disclosed.
Claims(7)  translated from Chinese
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 ester structure having the benzotriazole compounds, characterized in that it is of the general formula (I) compounds: 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 an alkylene group.
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 for producing said 1-enyl ester structure having benzotriazole-based compound as claimed in claim characterized in that it is the result of the following process scheme: by reacting 3-hydroxy alkyl-substituted formula (II) Compound 和通式(IV)烯基甲酸 And formula (IV) alkenyl carboxylic acid 进行醇酸酯化反应来制备通式(I)化合物。 Be prepared by reacting an alkyd esterification compounds of general formula (I). 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 in, X, R, R1, R2, R3, M is as defined in formula I defined.
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 for producing said 1-enyl ester structure having benzotriazole-based compound as claimed in claim characterized in that it is the result of the following process scheme: Formula (II) compound and formula (V) alkylene lower alkyl esters of formic acid base 进行酯交换化反应来制备通式(I)化合物。 Transesterification reaction to general formula (I) compound. 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 in, X, R, R1, R2, R3, M is as defined for formula I as defined; R4 is C1 ~ C4 alkyl group.
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 for producing said 1-enyl ester having the structure of formula benzotriazole compounds as claimed in claim characterized in that it is the result of the following process scheme: by reacting 3-halo-substituted alkyl group 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 formula (IV) alkenyl carboxylic acid or alkali metal salt thereof prepared by reacting the formula (I) compound. 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。 The above-mentioned formula III, IV in, X, R, R1, R2, R3, M is as defined for formula I as defined; Y is a halogen and sulfonyloxy.
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。 Compound of formula I according to claim 1, R1, R2, R3 one or more of the group may be an unsaturated alkenyl, multiple alkenyl group having the general formula I characterized by an ester structure.
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。 1 and 5 of said application with a vinyl ester structural formula benzotriazole compound as claimed in claim, characterized in that the polymer used in anti-aging light stabilizers.
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 an ester compound of formula 5 benzotriazole with an alkenyl group as a light stabilizer 7. A method of use of said claim, characterized in that it is administered in an amount of 0.05 to 10%.
Description  translated from Chinese
具有烯基酯式结构的苯并三唑类化合物及其制备方法 Benzotriazole compounds having vinyl ester structure and preparation method

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 ultraviolet radiation can effectively absorb structural modification of 2- and preparation methods (2-hydroxyphenyl) alkenyl esters of formula benzotriazole compounds of structure units introduced. 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 this invention relates to 2- (2-hydroxyphenyl) benzotriazole compounds alkenyl ester introducing new structure and its use as an ultraviolet absorber.

背景技术 BACKGROUND

: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 demanding polymer processing and conditions of use, benzotriazole compounds will be modified to achieve the improvement of the chemical structure of 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。 To achieve the above characteristics of the application requirements, as described in European Patent Publication EP0738718A a phenyl ring 3-substituted α- cumyl modification method; U.S. Patent No. 6,166,218 discloses 5-benzo ring modifications introduced -CF3; and U.S. Patent No. 6,268,505 6,407,254 discloses the introduction of 2,4-imidazoline dione in the phenyl ring 3-5,5-disubstituted structures. 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-described technique involves more than a simple extension of the structure and the group replacement, not related to the structure of the alkenyl group.

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。 A fragment alkenyl U.S. Patent 6,489,486 discloses a process for the alkylation of benzene ring 3, and then by O- alkylation rearrangement way possible to obtain due to the steric hindrance 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 limited temperature resistance, weather resistance, holding effect, volatility and compatibility properties such aspects, the present invention discloses a formula (I) with an ester of formula alkenyl benzotriazole structure to serve as a new type of an ultraviolet absorber, and provide information on the formula (I) of the production method, having a mild reaction conditions, high selectivity, low cost 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。 Since this 2- (2-hydroxyphenyl) benzotriazole having a benzene ring 3-enyl ester structure, when the process is applied to it as an ultraviolet absorber and a polymer material used in the processing, it is possible that the light Grafting polymerization effect exists between the stable and active fragments of the polymeric substrate; the same reaction characteristics because of polymerizable, such that its 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 the reaction characteristics of the general formula (I) has the structure such that aging characteristics of the polymer having better weather resistance and holding effect. 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。 Another modification is based on the structure of formula alkenyl ester groups, of the general formula (I) compounds may be various polymeric substrates have better compatibility, including coatings and plastics.

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 an alkylene 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 three alternative cost-effective technology solutions to the synthesis of compounds of formula (I), the 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: by reacting 3-hydroxyalkyl-substituted formula (II) compound 和通式(IV)烯基甲酸 And formula (IV) alkenyl carboxylic acid 进行醇酸酯化反应来制备通式(I)化合物。 Be prepared by reacting an alkyd esterification compounds of general formula (I).

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 in, X, R, R1, R2, R3, M is as defined in formula I defined.

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 Option Two: by formula (II) compounds of the general formula (V) alkenyl, lower alkyl esters of formic acid 进行酯交换化反应来制备通式(I)化合物。 Transesterification reaction to general formula (I) compound.

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 in, X, R, R1, R2, R3, M is as defined for formula I as defined; 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 scheme III: (III) compound by reaction of 3-alkyl-substituted or halo-substituted alkyl 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 formula (IV) alkenyl carboxylic acid or alkali metal salt thereof prepared by reacting the formula (I) compound.

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。 The above-mentioned formula III, IV in, X, R, R1, R2, R3, M is as defined for formula I as defined; Y is a halogen and sulfonyloxy.

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 compound of formula I above, wherein X, R, R1, R2, R3, M and its definition of those compounds defined in claim 1 of the same is a novel compound, its properties lies in the 3-position of the phenyl ring with alkenyl 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 of the group may be an alkenyl group, the alkenyl ester structure characteristic can be understood as an ester structure polyene group characteristics. 因而其也是本发明的目的。 Thus it is the 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 General formula (I), specific examples of novel compounds are: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) benzotriazole 2- (2'-hydroxy - 3 '- (α- -methacryloyloxy meth) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (acryloyloxyethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxyethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (2 - butenoyl oxymethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butene-acyl oxymethyl) 5'- ) benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadiene acyl oxymethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy -3' - (α- -methacryloyloxy meth) 5'-tert-butyl ) benzotriazole 2- (2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy-3' - ( α- methyl-2-butene-acyl oxymethyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-Tek Singh ) 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'-(丙烯酰基氧乙基)-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))-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 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'Texin Ji) benzotriazole 2- (2'-hydroxy-3' - (2-butene acyl oxymethyl) 5'Texin Ji) benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butene-acyl oxymethyl) 5'Texin Ji ) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) benzotriazole 2- (2 ' - hydroxy -3 '- (α--methacryloyloxy-methyl) -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' - (acryloyloxypropyl) -5 '- (1-methyl- 1-phenylethyl)) benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl-oxopropyl) -5' - (1-methyl-1-phenyl-ethyl 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' - (α - methacryloyloxy-methyl) 5'-methyl) -5-chloro-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxyethyl) 5'-methyl) -5- chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxyethyl) 5'-methyl) -5-chloro-benzotriazole 2- ( 2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy -3' - (α- methyl-2-butene acyl oxymethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'-tert-butyl) -5-chloro- benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butene-acyl oxymethyl) 5'-tert-butyl) -5-chloro-benzotriazole 2- ( 2'-hydroxy-3 '- (acryloyloxy-methyl) 5'Texin Ji) -5-chloro-benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyl oxymethyl) 5'Texin Ji) -5-chloro-benzotriazole 2- (2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'Texin Ji) -5- chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- methyl-2-butene-acyl oxymethyl) 5'Texin Ji) -5-chloro-benzo triazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) --5- chloro-benzotriazole 2- ( 2'-hydroxy -3 '- (α--methacryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) --5- chloro-benzotriazole 2- (2 '- hydroxy-3' - (acryloyloxyethyl) -5 '- (1-methyl-1-phenylethyl)) --5- chloro-benzotriazole 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'-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'-(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。 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy -3' - (α- -methacryloyloxy meth) 5'-methyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxypropyl) 5'-methyl ) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl-oxopropyl) 5'-methyl) -5-trifluoromethyl-benzo triazole 2- (2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'-methyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy-3 '- (α- methyl-2-butene-acyl oxymethyl) 5'-methylphenyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy-3' - (1,3 - pentadienoyl oxymethyl) 5'-methylphenyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-t butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'-tert-butyl) -5-trifluoromethyl benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxyethyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy - 3 '- (α- methacryloyl oxyethyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3' - (acryloyloxy-methyl ) 5'Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'Texin Ji) 5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (2-butene-acyl oxymethyl) 5'Texin Ji) -5-trifluoromethyl-benzo three oxazole 2- (2'-hydroxy -3 '- (α- methyl-2-butenoyl yloxymethyl) 5'Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2 '- hydroxy-3' - (1,3-pentadiene acyl oxymethyl) 5'Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3'- (acryloyloxy-methyl) -5 '- (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyloxy-methyl) -5 '- (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy-3' - (2 - butenoyl oxymethyl) -5 '- (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy -3' - (α - methyl-2-butenoyl yloxymethyl) -5 '- (1-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 '- (acryloyloxyethyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy - 3 '- (α- methacryloyl oxyethyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy- -3 '- (2-butenoyl-oxoethyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy- -3 '- (α- methyl-2-butene-acyl-oxyethyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole 2- (2'-hydroxy-3 '- (1,3-pentadienoyl-oxoethyl) -5' - (1-methyl-1-phenylethyl)) --5--trifluoromethyl-benzo three oxazole another aspect, the present invention relates to a 2-hydroxyphenyl benzotriazole-based compound containing the above-mentioned formula (I), alone or with at least one other UV-A and / or UV-B Yanzhe agent New UV absorber, 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 the above defined formula (I) of the new 2-hydroxyphenyl benzotriazole-based compound used as a light stabilizing agent.

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'-(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 Particularly preferred compounds are used as an ultraviolet absorber: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) benzotriazole 2- (2'-hydroxy-3 '- (α- -methacryloyloxy meth) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (acryloyloxyethyl) 5'-methyl) benzene benzotriazole 2- (2'-hydroxy -3 '- (α- methacryloyl oxyethyl) 5'-methyl) benzotriazole 2- (2'-hydroxy-3' - (acryloyl oxymethyl) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'-tert-butyl) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'Texin Ji) benzotriazole 2- (2'-hydroxy -3' - (α- -methacryloyloxy A yl) 5'Texin Ji) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxyethyl) 5'Texin Ji) benzotriazole 2- (2'- hydroxy -3 '- (α- methacryloyl oxyethyl) 5'Texin Ji) benzotriazole 2- (2'-hydroxy-3' - (acryloyloxy-methyl) -5' (1-methyl-1-phenylethyl)) benzotriazole 2- (2'-hydroxy -3 '- (α--methacryloyloxy-methyl) -5' - (1-methyl - 1-phenylethyl)) benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) -5-chloro-benzotriazole 2- (2 '- hydroxy -3' - (α- -methacryloyloxy meth) 5'-methylphenyl) -5-chloro-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy A yl) 5'-tert-butyl) -5-chloro-benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'-tert-butyl) - 5-chloro-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'Texin Ji) -5-chloro-benzotriazole 2- (2'-hydroxy- -3 '- (α- -methacryloyloxy meth) 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--methacryloyloxy-methyl) - 5 '- (1-methyl-1-phenylethyl)) --5- chloro-benzotriazole 2- (2'-hydroxy-3' - (acryloyloxy-methyl) 5'-methyl ) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'-methylphenyl) -5-trifluoromethyl-benzo triazole

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)-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。 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3' - (α - methacryloyloxy-methyl) 5'-tert-butyl) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' Texin Ji) -5-trifluoromethyl-benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'Texin Ji) -5-trifluoromethyl methyl benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethylbenzene benzotriazole 2- (2'-hydroxy -3 '- (α--methacryloyloxy-methyl) -5' - (1-methyl-1-phenylethyl)) --5- trifluoromethyl benzotriazole most preferred formula (I) compound as follows: 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) benzotriazole 2- (2'- hydroxy -3 '- (α- -methacryloyloxy meth) 5'-methyl) benzotriazole 2- (2'-hydroxy -3' - (α--methacryloyloxy-methyl) - 5'-t-butyl) benzotriazole 2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) 5'Texin Ji) benzotriazole 2- (2' - hydroxy -3 '- (α- -methacryloyloxy meth) 5'-methylphenyl) -5-chloro-benzotriazole 2- (2'-hydroxy -3' - (α- methacryloyl acyl oxymethyl) 5'-tert-butyl) -5-chloro-benzotriazole 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'Texin Ji) -5 - the term alkyl chloro-benzotriazole in the present invention represents containing 1-21 carbon atoms, preferably a saturated straight-chain or branched alkyl group having 1 to 8 carbon atoms, e.g., methyl, ethyl, propyl group, isopropyl, butyl, sec-butyl, tert-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 represents an alkoxy group bonded through an oxygen atom contain 1 to 21 carbon atoms, preferably a saturated straight-chain or branched alkyl group having 1 to 8 carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, neo-pentyloxy, hexyloxy, 2-ethyl - hexyloxy, 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 represents a cycloalkyl group and 2-21 carbon atoms C5 ~ C7 substituted 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 represents C2-21 carbon atoms, carboxylic acid and C1 ~ C18 alkyl esters, such as formyloxy, acetoxy, propionyloxy, butyryloxy, 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。 Represents the above-described alkyl group substituted aryl group, an alkoxy group as defined substituted aryl, alkyl and alkoxy groups 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 represents containing at least one double bond and 2-21 carbon atoms, preferably a straight-chain or branched hydrocarbon group having 2 to 8 atoms, and 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 represents toluenesulfonyloxy group, a 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 represents C1 ~ C18 alkylene group, preferably a saturated straight-chain and branched-chain alkylene group having 1 to 8 carbon atoms, e.g., methylene, ethylene, trimethylene, isopropyl support, butylene, sec-butylene , t-butylene, pentamethylene, new pentamethylene, hexamethylene, 2-ethyl - hexamethylene, 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 is hydrogen, 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 5-substituted benzo ring of hydrogen, chloro, trifluoromethyl, difluoromethyl a chloro group, a fluoro dichloromethyl, more choice for hydrogen, chlorine. 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 a C1-C8 straight chain and branched alkyl groups and C1-C8 substituted cumyl, more choice is methyl, t-butyl, Texin Ji, α- cumyl. 优选M为C1-C4烷撑,更优选为甲撑和乙撑,最优选是甲撑。 Preferably M is 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 according to the invention, of the general formula (I) compounds can be selected as shown in the following chemical reaction formula 1-3 to be prepared, which are mapped to the above-described process scheme 1-3.

化学反应式一: A chemical reaction: 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。 A process scheme in the present, the use of alcoholic hydroxyl and alkenyl acids benzene ring 3 on to the esterification reaction. 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。 Benzotriazole compounds of formula II and formula IV alkenyl acid molar ratio selection 1:0.1 to 10, preferably from 0.8 to 1.2, 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 catalyst can be selected sulfuric acid, phosphoric acid, alkane sulfonic acids, aryl sulfonic acids and polycarboxylic inorganic acid, 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, select (e.g.) phenothiazine, hydroquinone, hydroquinone monomethyl ether or a compound thereof and may be air, 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 as 100 to 5000ppm, more preferably 2000ppm to 3000ppm (by 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 the entrainer, optionally used in the present invention, saturated hydrocarbons (e.g. cyclohexane) or an aromatic hydrocarbon (e.g. toluene); the present invention, more preferred entrainer is benzene and toluene.

反应器中的反应温度优选70至160℃,更优选为90至130℃。 The reaction temperature in the reactor preferably 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 can be atmospheric, subatmospheric or at atmospheric pressure carried out continuously or intermittently, wherein more selection is carried out under normal pressure conditions the gap.

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, the use of an alcoholic hydroxyl group and alkenyl acid lower alkyl ester on the benzene ring 3 to carry out an ester exchange reaction. 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。 The molar ratio of benzotriazole compounds of formula II and an acid of formula V lower alkyl ester alkenyl selection 1/1 to 20, preferably from 1/1 to 15, and most preferably 1:1.2 ~ 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-methoxy phenol, hydroquinone, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine piperidinyl free radical (4-hydroxyphenyl -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 compounds, the amount of the polymerization inhibitor is selected as 10 to 10000ppm, preferably 100 to 5000ppm, 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。 The present invention is suitable transesterification catalysts include C1-C3 lower alkyl sodium alkoxide, dibutyltin oxide, dibutyltin methoxide, C4-C8 alkyl zinc, lithium, alkenyl acid C1-C4 alkyl quaternary ammonium salts, 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 usually 0.1 to 10 mol%, preferably 0.5 to 7 mol%, most preferably 1 to 5 mol% of the catalyst concentration.

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 present invention utilizing two Oldershaw distillation column, the appropriate plate number Oldershaw distillation column 5 to 40, more preferably from 10 to 20. 回流比选择10~30。 Select reflux ratio of 10 to 30.

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 used in the present invention, saturated hydrocarbons (e.g. cyclohexane, n-hexane) or aromatic hydrocarbons (such as toluene), the present invention is preferably added to 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 in the reactor preferably 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 to 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 can be atmospheric, subatmospheric or at atmospheric pressure carried out continuously or intermittently, wherein more selected to be slightly under reduced pressure gap situation.

化学反应式三: Three chemical reaction: 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 use of 3-substituted benzene ring of formula III leaving group Y and a carboxylic acid group or a carboxylate structure of formula IV under basic conditions the condensation of groups on the formula I compounds. 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。 As the compound of alkaline substances Alternatively 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 process step is preferably two steps, the first step is to get dry formula IV corresponding carboxylic acid salt compound was prepared by the acid-base neutralization; the second step and continue to prepare the target compound of formula III Contract 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 an alkali hydroxide choice 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 solid, or may be more than 10% of an aqueous system. 中和反应的温度选择0~100℃,选择为25~60℃。 The reaction temperature and choice of 0 ~ 100 ℃, 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 dehydration treatment, conventional dehydration method 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%。 Need to select the phase transfer catalyst in the second step to increase the reaction rate, a suitable catalyst may be quaternary ammonium salts, most preferably tetramethylammonium chloride, in an amount relative to the carboxylic acid salts of 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-methoxy phenol, hydroquinone, phenothiazine, 4-hydroxy-2,2,6,6-tetramethylpiperidine piperidinyl free radical (4-hydroxyphenyl -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 to the carboxylic acid salts of formula IV is selected as 0.05 to 1 in terms of 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。 The 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℃。 Step two condensation reaction temperature 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 to 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 can be a solvent or solvent-free conditions, the solvent can be selected 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 will illustrate the invention, 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-substituted benzotriazole compounds via the corresponding diazonium salts and 2,6-5 bis (hydroxyalkyl) - coupling of alkylphenol , when the coupling due to a hydroxyalkyl group detachment, such as a compound 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 the 2- (2-hydroxyphenyl) benzotriazole benzene ring 3 is H, in the phenyl ring at position 3 C atoms may be electrophilic substitution reaction, 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] : A) Example of a process scheme :( Preparation [2- (2'-hydroxy-3 '- (acryloyloxy) methyl) benzo-triazole-5'] (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 1000ml 2000ml of benzene was added to the 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。 In the above mixture was added 0.8g of phenothiazine, 75g acrylic acid and heated to slow 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 stirring for 4 hours, to observe water separator water collected.

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 device, when the separated water close to 18ml of time, you can 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。 While towards the end of the reaction phase can be analyzed by high performance liquid chromatography (HPLC). 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 starting material was 2- (2'-hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole, and the disappearance of 2- (2'-hydroxy-3 '- (acryloyloxy-methyl) 5'-methyl) benzotriazole generation was confirmed.

反应完成后将反应混合物进行水洗,萃取处理。 Completion of the reaction, the reaction mixture was washed with water, extraction treatment. 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 organic layer solvent was removed under reduced pressure benzene residue was rinsed, 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, bleaching treatment option of using activated carbon adsorption. 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 of ≥98.0%. 干燥处理后可以得到281.5g纯品浆状物,产率为91%。 Pure product can be obtained slurry was 281.5g, 91% yield after drying.

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 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-methyl 2'-hydroxy-3 ')] a) Preparation Example II :( process scheme (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) using the same method as in Example one embodiment, methacrylic acid substitution with 90g acrylic acid, with 10g of concentrated sulfuric acid in place of p-toluenesulfonic acid, in this case, the reaction time was extended to 8 hours, 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 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。 B) Preparation Example III :( process scheme [2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) Preparation of 5'-methyl-benzotriazole)] in 2000ml equipment with a thermometer, a stirrer, a gas inlet tube and a reaction vessel equipped with a reflux distillation column control device was added 255.3g 2- (2'- hydroxy-3'-hydroxymethyl-5'-methyl) benzotriazole , 600ml of n-hexane, 0.5g 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℃。 In the above mixture was added 1.0g of dibutyltin oxide, 500g of methyl methacrylate, at 300mmHg pressure was raised to reflux, at this time the kettle temperature at the bottom 70 ℃. 控制回流比10~30,塔顶温度为38~55℃。 Control reflux ratio of 10 to 30, the top temperature of 38 ~ 55 ℃. 甲醇将被作为共沸物的形式被移出。 Methanol will be used as an azeotrope is removed. 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, the bottoms temperature was raised to 74 ℃, and the overhead temperature was maintained at 55 ℃ longer possible or lower temperature level. 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%。 Was sampled and analyzed by HPLC, can learn 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。 Was added p-toluene sulfonate such that immediately after the end of the reaction the catalyst deactivation, the control means change at reflux for 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。 Completion of the reaction, the reaction mixture was washed with water, extraction treatment. 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。 Trace benzotriazole unreacted reactants and other by-products can be eluted leaching way. 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, bleaching treatment option of using activated carbon adsorption. 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 of ≥98.0%. 干燥处理后可以得到297.2g纯品浆状物,产率为92%。 Pure product can be obtained slurry was 297.2g, a yield of 92% after the drying process. 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- -methacryloyloxy meth) 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 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 IV Preparation process scheme [2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) benzo-triazole-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%。 (Target Compound 3) using the same method as in Example three, with 339.3g2- (2'- hydroxy-3'-hydroxymethyl-5'Texin Ji) benzotriazole as the raw material, the rest remains unchanged In this case the 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)C70.80%(70.76%);H7.10%(7.13%);N10.26(10.32%)。 Specific elemental analysis 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- ((acryloyloxy-methyl-2'-hydroxy-3 ')] b) Preparation Example V :( process scheme (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。 (The title compound 4) using the same method as in Example IV, catalyst was changed to 0.5g of lithium hydroxide, the amount is adjusted to 900g methyl acrylate without using the 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 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。 C) :( Example VI Preparation process scheme [2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) Preparation of 5'-methyl-benzotriazole)] will 119.5g of methyl methacrylate and 55.5g of sodium hydroxide for neutralization, methacrylic acid can be obtained 150.0g anhydrous sodium manner 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。 Added to the anhydrous sodium salt equipped with a thermometer, a stirrer and a condenser reaction vessel, 380g2- (2'- hydroxy-3'-methyl-5'-chloro-methyl) benzotriazole, 1000mlDMF, 0.9 g tetramethylammonium chloride and 0.6g of phenothiazine was stirred at 110 ℃ for 4 hours. 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%。 Was sampled and analyzed by HPLC, can learn 2- (2'-hydroxy-3'-methyl-5'-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 resulting sodium chloride was filtered off by filtration manner may be after completion of the reaction. 在10mmHg减压条件下移除DMF后。 DMF is removed under reduced pressure after 10mmHg. 反应完成后将反应混合物进行水洗,萃取处理。 Completion of the reaction, the reaction mixture was washed with water, extraction treatment. 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 unreacted reactants and other by-products can be eluted leaching way. 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, bleaching treatment option of using activated carbon adsorption. 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 of ≥98.0%. 干燥处理后可以得到408.2g纯品浆状物,产率为91%。 Pure product can be obtained slurry was 408.2g, 91% yield after drying. 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- -methacryloyloxy meth) 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 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 VII Preparation process scheme :( c) [2- (2'-hydroxy -3 '- (α- -methacryloyloxy meth) benzo-triazole-5'Texin Ji)] using the the same manner as in Example VI was conducted using 497g2- (2'- hydroxy-3'-methyl-5'-chloro Texin Ji) benzotriazole as raw material, the rest remains unchanged, then the reaction time 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)C70.84%(70.76%);H7.05%(7.13%);N10.21(10.32%)。 Specific elemental analysis 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 According to the above process scheme can be prepared as the target compound (see Table 1): Table 1: Raw material compound 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。 Application Example: Application Example 1: Light stabilizing action in polypropylene PP flat yarn in a) to form the respective target compound 1g 2 involved, 1g tris (nonyl-substituted phenyl) phosphite, 0.5g glycol [β- (3,5- di-t-butyl-4-hydroxyphenyl) propionate] and 1g of calcium stearate in a turbine mixer and a melt index of 3.5 1Kg a polypropylene powder is mixed. 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 mixture was extruded at 230 ℃ obtained PP granules, stretching ratio 1:6, PP Biansi: 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 flat tow on the whiteboard and exposed to weathering 65WR instrument (in accordance with ASTMD2565-85 standard), the blackboard 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。 Constant speed tension meter by means of the samples after various exposure time remaining toughness measurements performed, thereby measured reaches half the original tenacity (T50) required exposure time.

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: Add a case where the light stabilizer T50 (hours) without light stabilizers target compound 12 400 400

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。 The title compound the title compound 52 700 32 490 target compound 10 2900b) according to a) a 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 a case where the light stabilizer T50 (hours) without light stabilizer 400 of the title compound the title compound 33 100 13 000 53 300 the title compound the title compound 10 3600c) according to b) of the method, and then the addition 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: 2 with addition of a light stabilizer of T50 (hours) without light stabilizer 400 of the title compound the title compound 33 700 13 600 53 800 the title compound the title compound 104 000 Application Example: Light stabilizing action in polypropylene PP fiber 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: 130 / 37dtex, draw ratio: 1:3.2,100% elongation of the accelerated aging test: xenon lamp aging test [Xenotest 1200], black panel temperature: 55 ℃ Determination Its tensile strength decreased to 50% of the time required, 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 in the light stabilizer type of PP fiber light stability

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Classifications
International ClassificationC08K5/3475, C07D249/20
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