CN101029032A - Preparation of benzotrizole light stabilizer - Google Patents
Preparation of benzotrizole light stabilizer Download PDFInfo
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- CN101029032A CN101029032A CN 200710057112 CN200710057112A CN101029032A CN 101029032 A CN101029032 A CN 101029032A CN 200710057112 CN200710057112 CN 200710057112 CN 200710057112 A CN200710057112 A CN 200710057112A CN 101029032 A CN101029032 A CN 101029032A
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Abstract
A process for preparing the benzotriazole as photostabilizer includes such steps as dissolving 2-nitro-2'-hydroxy-5'-methyl azobenzene and 2-nitro-2'-hydroxy-3'- tert-butyl-5'-methyl propionate azobenzene in the mixture of alcohol and alkali solution, adding hydrazine hydrate, heating, reflux reaction, using hydrochloric acid to neutralize the reaction liquid, depositing, filtering, water washing, drying to obtain an intermediate, dissolving it in the mixture of alcohol and alkali, adding sodium dithionate, stirring while reacting, adding ice water, neutralizing, filtering, drying, and recrystallizing in alcohol or isopropanol.
Description
Technical field
The present invention relates to a kind of preparation method of benzotriazole light stabilizer, belong to the photostabilizer technology.
Background technology
The benzotriazole light stabilizer structural formula is suc as formula shown in (I):
In the formula (I) R be-H ,-Cl or-Br; R
1For-H, C
1-C
12Alkyl, C
1-C
4Alkoxyl phenyl ,-Cl, (C
1-C
8Alkyl) phenyl, C
5-C
6Cycloalkyl, C
2-C
9Alkoxyl group acyl group, carboxy ethyl or C
7-C
9Phenylalkyl; R
2For-H, C
1-C
12Alkyl ,-Cl, C
5-C
6Alkoxyl group, C
7-C
9Phenylalkyl or-C
nH
2n-COOCH
3(n is 0,1,2,3,4).
Benzotriazole light stabilizer is a kind of high molecular synthetic material auxiliary agent, is widely used in the organic polymers such as plastics, synthetic rubber, synthon, dyestuff, coating and pigment, prevents that it is aging under uviolizing, prolongs its work-ing life.In addition, also can make an addition in the makeup, prevent the radiation of sunlight middle-ultraviolet lamp to human body skin, the protection HUMAN HEALTH has very high economic worth.
One of synthetic method of benzotriazole by hydrazine hydrate reduction, obtains intermediate oxynitride (III) by the azobenzene compound shown in the formula (II) earlier, obtains benzotriazole light stabilizer through reduction again.
Formula (II) and (III) in R be-H ,-Cl or-Br; R
1For-H, C
1-C
12Alkyl, C
1-C
4Alkoxyl group, phenyl ,-Cl, (C
1-C
8Alkyl) phenyl, C
5-C
6Cycloalkyl, C
2-C
9Alkoxyl group acyl group, carboxy ethyl or C
7-C
9Phenylalkyl; R
2For-H, C
1-C
12Alkyl ,-Cl, C
5-C
6Alkoxyl group, C
7-C
9Phenylalkyl or-C
nH
2n-COOCH
3(n is 0,1,2,3,4).
One of existing synthetic method is to be that raw material is that the reductive agent single stage method makes benzotriazole light stabilizer with the hydrazine hydrate with the compound shown in the formula (II).The patent of report has US4001266, DE2454889, Fr2292708.This method used solvent be diethylene glycol diethyl ether, it costs an arm and a leg.And the temperature of reaction is at least 100 ℃, and the side reaction of azo bond fracture takes place easily, forms a large amount of amine byproducts.In addition,, need to prolong the reaction times, in the still-process of reacting by heating thing,, have the danger of blasting because ether solvent has the characteristic of easy generation poly oxide in order to distill out the water in the reagent.
Another method is under the solvent of second alcohol and water, with the compound shown in the formula (II) is that raw material is by preparing intermediate (III) with hydrazine hydrate earlier, use the intermediate shown in the zinc powder reduction formula (III) to make benzotriazole light stabilizer then, synthetic method has Japanese Patent JP53063379.This method need be handled reacting a large amount of zn cpds and the alkali lye in back owing to used excessive zinc powder and alkali lye, and this process steps is loaded down with trivial details, and the cycle of reaction is long, contaminate environment.
Summary of the invention
The object of the invention has provided a kind of method for preparing benzotriazole light stabilizer, and the solvent that this procedure is used is cheap, environmentally safe, and preparation cost is low.
The present invention is realized that by the following technical programs a kind of preparation method of benzotriazole light stabilizer is characterized in that comprising following process:
1. be raw material with the compound shown in the formula (II), this compound comprises 2-nitro-2 '-hydroxyl-5 '-methyl-benzene, 2-nitro-2 '-hydroxyl-the 3 '-tertiary butyl-5 '-methyl propionate base nitrogen benzide.By raw material and alkali mol ratio is 1: (5-6), with material dissolution in the mixed solvent of ethanol and sodium hydroxide, or with material dissolution in the mixed solvent of ethanol and potassium hydroxide, the mol ratio of ethanol and alkali is (6-7): 1, the mass concentration of alkali lye is 10-18%.The mass concentration that adds the 0.4-0.7 mole by every mole of material in mixed solution is 80% hydrazine hydrate then, is heated to backflow, 80～90 ℃ of back flow reaction 2-2.5 of temperature control hours.After reacting completely, the solution colour flavescence is that 37% hydrochloric acid neutralization reaction liquid pH is 5～7 with mass concentration.Generate precipitation, after filtration, washing, drying obtains intermediate 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride or obtain intermediate 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride.
2. 1 prepared intermediate and alkali mol ratio are 1 set by step: (5-6), intermediate is dissolved in the mixed solvent of ethanol and sodium hydroxide, or intermediate is dissolved in the mixed solvent of ethanol and potassium hydroxide, the mol ratio of ethanol and alkali is (6-7): 1, and the mass concentration of alkali lye is 10-18%.In temperature of reaction is under 80-90 ℃, the sodium hyposulfate that in mixed solution, slowly adds the 1.3-1.6 mole by every mole of intermediate, stirring reaction 1-2 hour, when solution colour becomes yellow-green colour, dropping in 0 ℃ of frozen water, is that 10% hydrochloric acid is neutralized to neutrality with massfraction, filters, drying obtains thick product, obtains pure product with 95% ethanol or Virahol recrystallization again.
Advantage of the present invention is that (1) uses cheap alcoholic solvent to replace ether solvent, and preparation cost is cheap.(2) hydrazine hydrate of Shi Yonging and sodium hyposulfate reductive agent clean and effective, environmental friendliness.
Embodiment
Below the present invention is elaborated with reference to following example.
Embodiment 1
The preparation of 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole
With 28g 2-nitro-2-hydroxy-5-methyl base nitrogen benzide (91.8%), 20g sodium hydroxide, 200ml ethanol and 122g water join in the 500ml there-necked flask, adding 6g mass concentration is 80% hydrazine hydrate, control reaction temperature is at 81 ℃, stirring reaction is 2 hours under the rotating speed of 300r/min, solution became light yellow after reaction was finished, slowly drip the hydrochloric acid of 60ml 37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 23g 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride product, yield is 95.4%.
Get the above-mentioned product 2-nitro that makes-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride 13g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, be heated to backflow, slowly add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is at 81 ℃, and reaction was carried out 1 hour, and color became oyster after reaction was finished, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole 21g with ethyl alcohol recrystallization, productive rate is 93.3%.
Embodiment 2
The preparation of 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole
With 28g 2-nitro-2-hydroxy-5-methyl base nitrogen benzide (91.8%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, adding 6g mass concentration is 80% hydrazine hydrate, control reaction temperature is at 81 ℃, stirring reaction is 2 hours under the rotating speed of 300r/min, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml 37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 21g 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride product, yield is 87.1%.
Get the above-mentioned product 2-nitro that makes-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride 13g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, be heated to backflow, slowly add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is at 81 ℃, and reaction was carried out 1 hour, and color became oyster after reaction was finished, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole 11g with ethyl alcohol recrystallization, productive rate is 97.8%.
Embodiment 3
The preparation of 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole
With 28g 2-nitro-2-hydroxy-5-methyl base nitrogen benzide (91.8%), 22g sodium hydroxide, 200ml ethanol and 136g water join in the 500ml there-necked flask, adding 6g mass concentration is 80% hydrazine hydrate, control reaction temperature is at 81 ℃, stirring reaction is 2 hours under the rotating speed of 300r/min, solution became light yellow after reaction was finished, slowly drip the hydrochloric acid of 60ml 37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 22g 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride product, yield is 91.2%.
Get the above-mentioned product 2-nitro that makes-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride 13g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, be heated to backflow, slowly add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is at 81 ℃, and reaction was carried out 1 hour, and color became oyster after reaction was finished, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole 10g with ethyl alcohol recrystallization, productive rate is 88.9%.
Embodiment 4
The preparation of 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole
With 28g 2-nitro-2-hydroxy-5-methyl base nitrogen benzide (91.8%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, adding 4.5g mass concentration is 80% hydrazine hydrate, control reaction temperature is at 81 ℃, stirring reaction is 2 hours under the rotating speed of 300r/min, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml 37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 21g 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride product, yield is 87.1%.
Get the above-mentioned product 2-nitro that makes-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride 13g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, be heated to backflow, slowly add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is at 81 ℃, and reaction was carried out 1 hour, and color became oyster after reaction was finished, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole 10.8g with ethyl alcohol recrystallization, productive rate is 95.6%.
Embodiment 5
The preparation of 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole
With 28g 2-nitro-2-hydroxy-5-methyl base nitrogen benzide (91.8%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, adding 7g mass concentration is 80% hydrazine hydrate, control reaction temperature is at 81 ℃, stirring reaction is 2 hours under the rotating speed of 300r/min, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml 37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 20.5g 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride product, yield is 91.1%.
Get the above-mentioned product 2-nitro that makes-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride 13g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, slowly add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is at 81 ℃, reaction was carried out 1 hour, reaction is finished the back color and is become oyster, and in 0 ℃ of frozen water of reaction solution impouring, the adding mass concentration is that to be neutralized to pH be 7 for 10% hydrochloric acid, separate out precipitation, filtration drying obtains thick product, obtains 2-(2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole 10.5g with ethyl alcohol recrystallization, and productive rate is 93.3%.
Embodiment 6
2-[2-hydroxyl-3-the tertiary butyl-5-(3-methyl propionate base) phenyl]-preparation of 2H-benzotriazole
With 43g 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl] nitrogen benzide (89.5%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, control reaction temperature is at 82 ℃, the hydrazine hydrate that slowly adds 5g 80%, behind the stirring reaction 2 hours, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 27.8, and productive rate is 75.1%.
Get the above-mentioned product 2-nitro that makes-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 19g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, divide many batches to add the 16g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is about 90 ℃, reacted about 1 hour, reaction is finished, the material color becomes oyster, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain the 2-[2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl with the Virahol recrystallization]-2H-benzotriazole 14.5g, productive rate is 81.9%.
Embodiment 7
2-[2-hydroxyl-3-the tertiary butyl-5-(3-methyl propionate base) phenyl]-preparation of 2H-benzotriazole
With 43g 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl] nitrogen benzide (89.5%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, control reaction temperature is at 82 ℃, the hydrazine hydrate that slowly adds 6g 80%, behind the stirring reaction 2 hours, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 30, and productive rate is 81%.
Get the above-mentioned product 2-nitro that makes-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 19g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, divide many batches to add the 16g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is about 90 ℃, reacted about 1 hour, reaction is finished, the material color becomes oyster, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain the 2-[2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl with the Virahol recrystallization]-2H-benzotriazole 15.5g, productive rate is 87.5%.
Embodiment 8
2-[2-hydroxyl-3-the tertiary butyl-5-(3-methyl propionate base) phenyl]-preparation of 2H-benzotriazole
With 43g 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl] nitrogen benzide (89.5%), 18g sodium hydroxide, 200ml ethanol and 110g water join in the 500ml there-necked flask, control reaction temperature is at 82 ℃, the hydrazine hydrate that slowly adds 7g 80%, behind the stirring reaction 2 hours, solution became light yellow after reaction was finished, the hydrochloric acid of slow Dropwise 5 0ml37%, the pH that neutralizes is 6, produces a large amount of yellow mercury oxides, filter, use 100ml water washing twice respectively, drying obtains 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 27, and productive rate is 72.9%.
Get the above-mentioned product 2-nitro that makes-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride 19g, 10g sodium hydroxide, 100ml ethanol and 92g water join in the 500ml there-necked flask, divide many batches to add the 15g sodium hyposulfate, rotating speed with 500r/min stirs, control reaction temperature is about 90 ℃, reacted about 1 hour, reaction is finished, the material color becomes oyster, in 0 ℃ of frozen water of reaction solution impouring, adding mass concentration and be 10% hydrochloric acid, to be neutralized to pH be 7, separates out precipitation, and filtration drying obtains thick product, obtain the 2-[2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl with the Virahol recrystallization]-2H-benzotriazole 15.3g, productive rate is 86.1%.
Claims (1)
1. the preparation method of a benzotriazole light stabilizer is characterized in that comprising following process:
1). to comprise that 2-nitro-2 '-hydroxyl-5 '-methyl-benzene and 2-nitro-2 '-hydroxyl-3 '-tertiary butyl-5 '-methyl propionate base nitrogen benzide is a raw material, by raw material and alkali mol ratio is 1: (5-6), with material dissolution in the mixed solvent of ethanol and sodium hydroxide, or with material dissolution in the mixed solvent of ethanol and potassium hydroxide, the mol ratio of ethanol and alkali is (6-7): 1, the mass concentration of alkali lye is 10-18%, the mass concentration that adds the 0.4-0.7 mole by every mole of material in mixed solution is 80% hydrazine hydrate then, be heated to backflow, 80～90 ℃ of back flow reaction 2-2.5 of temperature control hours, after reacting completely, the solution colour flavescence, with mass concentration is that 37% hydrochloric acid neutralization reaction liquid pH is 5～7, generate precipitation, after filtration, washing, drying obtains intermediate 2-nitro-2-hydroxy-5-methyl base phenyl)-2 hydrogen-benzotriazole oxynitride or obtain intermediate 2-nitro-[the 2-hydroxyl-3-tertiary butyl-5-(3-methyl propionate base) phenyl]-2 hydrogen-benzotriazole oxynitride;
2). set by step 1) prepared intermediate and alkali mol ratio be 1: (5-6), intermediate is dissolved in the mixed solvent of ethanol and sodium hydroxide, or intermediate is dissolved in the mixed solvent of ethanol and potassium hydroxide, the mol ratio of ethanol and alkali is (6-7): 1, the mass concentration of alkali lye is 10-18%, in temperature of reaction is under 80-90 ℃, the sodium hyposulfate that in mixed solution, slowly adds the 1.3-1.6 mole by every mole of intermediate, stirring reaction 1-2 hour, when solution colour becomes yellow-green colour, drop in 0 ℃ of frozen water, with massfraction is that 10% hydrochloric acid is neutralized to neutrality, filter, drying obtains thick product, obtains pure product with 95% ethanol or Virahol recrystallization again.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102285926A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for synthesizing benzotriazole compounds |
| CN103351349A (en) * | 2013-07-01 | 2013-10-16 | 天长市天佳化工科技有限公司 | Synthetic method for benzotriazole ultraviolet absorbent UV-P |
| CN103450105A (en) * | 2013-07-26 | 2013-12-18 | 浙江常山科润化学有限公司 | Preparation method of benzotriazole ultraviolet absorbent |
| CN103508967A (en) * | 2013-10-11 | 2014-01-15 | 浙江常山科润化学有限公司 | Preparation method of benzotriazole ultraviolet absorbent UV-P |
| CN105153058A (en) * | 2015-08-06 | 2015-12-16 | 天津大学 | Synthetic method of benzotriazoles compound |
| CN105884703A (en) * | 2016-05-31 | 2016-08-24 | 启东金美化学有限公司 | Preparation method of ultraviolet light absorber UV-PS |
| CN106008378A (en) * | 2016-05-31 | 2016-10-12 | 启东金美化学有限公司 | Preparation method of benzotriazole ultraviolet light absorber |
| WO2017152685A1 (en) * | 2016-03-09 | 2017-09-14 | 黄秀茹 | Additive for polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102285926A (en) * | 2011-06-30 | 2011-12-21 | 浙江工业大学 | Method for synthesizing benzotriazole compounds |
| CN102285926B (en) * | 2011-06-30 | 2013-06-19 | 浙江工业大学 | Method for synthesizing benzotriazole compounds |
| CN103351349A (en) * | 2013-07-01 | 2013-10-16 | 天长市天佳化工科技有限公司 | Synthetic method for benzotriazole ultraviolet absorbent UV-P |
| CN103450105A (en) * | 2013-07-26 | 2013-12-18 | 浙江常山科润化学有限公司 | Preparation method of benzotriazole ultraviolet absorbent |
| CN103450105B (en) * | 2013-07-26 | 2015-06-17 | 浙江常山科润化学有限公司 | Preparation method of benzotriazole ultraviolet absorbent |
| CN103508967A (en) * | 2013-10-11 | 2014-01-15 | 浙江常山科润化学有限公司 | Preparation method of benzotriazole ultraviolet absorbent UV-P |
| CN103508967B (en) * | 2013-10-11 | 2015-08-26 | 浙江常山科润化学有限公司 | The preparation method of a kind of benzotriazole ultraviolet absorbent UV-P |
| CN105153058A (en) * | 2015-08-06 | 2015-12-16 | 天津大学 | Synthetic method of benzotriazoles compound |
| CN105153058B (en) * | 2015-08-06 | 2018-02-09 | 天津大学 | A kind of synthetic method of benzotriazole compound |
| WO2017152685A1 (en) * | 2016-03-09 | 2017-09-14 | 黄秀茹 | Additive for polymer |
| CN105884703A (en) * | 2016-05-31 | 2016-08-24 | 启东金美化学有限公司 | Preparation method of ultraviolet light absorber UV-PS |
| CN106008378A (en) * | 2016-05-31 | 2016-10-12 | 启东金美化学有限公司 | Preparation method of benzotriazole ultraviolet light absorber |
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