CN113264869A - Hindered phenol antioxidant and preparation method thereof - Google Patents
Hindered phenol antioxidant and preparation method thereof Download PDFInfo
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- CN113264869A CN113264869A CN202110551964.5A CN202110551964A CN113264869A CN 113264869 A CN113264869 A CN 113264869A CN 202110551964 A CN202110551964 A CN 202110551964A CN 113264869 A CN113264869 A CN 113264869A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/06—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D211/36—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D211/58—Nitrogen atoms attached in position 4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
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- C08L7/00—Compositions of natural rubber
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Abstract
The invention relates to a hindered phenol antioxidant and a preparation method thereof, and the hindered phenol antioxidant disclosed by the invention is prepared by 1, 4-addition reaction and ester exchange reaction in the presence of a catalyst; compared with the application of the existing antioxidant containing hindered phenol in rubber, the hindered phenol antioxidant disclosed by the invention shows the superiority of the antioxidant and the gain of the antioxidant on the cohesive force of the rubber; the rubber has a good synergistic effect on the aspect of heat and oxygen resistance of rubber due to the fact that the rubber has hindered phenol and low-alkalinity hindered amine structures; in addition, the antioxidant prepared by the invention has the advantages of good compatibility with natural rubber, low volatility, migration resistance and the like, so that the antioxidant can be uniformly dispersed in the natural rubber, and the antioxidant is prevented from being volatilized or extracted under the action of a solvent due to heating.
Description
Technical Field
The invention relates to a hindered phenol antioxidant and a preparation method thereof, belonging to the field of light stabilizers.
Background
In the process of storage, processing and use of polymer materials such as rubber, plastic, fiber, film and the like, under the condition of light and oxygen, oxidation easily occurs to cause degradation or crosslinking of molecular chains, so that surface defects of the materials and poor performance of the materials are caused, wherein the rubber has the most fatal defect of thermal-oxidative aging resistance due to the fact that a large amount of unsaturated carbon-carbon double bonds (-C-), and the service life of the rubber is greatly shortened.
In order to retard or inhibit the aging of the polymer material, the most common and effective method is to add an antioxidant, which acts as an antioxidant by interrupting the chain growth reaction of free radicals in the aging process of the polymer material, capturing the free radicals, and forming a substance with a relatively stable structure.
The common phenol antioxidants are mostly small molecular substances, are easily heated and are easily volatilized in the processing and using processes, so that the actual effective components of the antioxidants in the high polymer materials are greatly reduced. In addition, in the use process of the high polymer material, the micromolecular phenolic antioxidant is easy to migrate out or extract from the matrix under the action of heat or solvent, so that the use performance of the high polymer material is reduced, and the environment is also adversely affected.
Disclosure of Invention
In order to solve the defects of the small molecular antioxidant, the invention selects the intermediate of the hindered phenol antioxidant as a molecular chain, introduces a group which is beneficial to improving the oxidation resistance through molecular design, and prepares the macromolecular antioxidant containing one hindered phenol and two hindered amine functional groups. Due to the synergistic antioxidation effect of the hindered phenol and the hindered phenol, the antioxidant shows very outstanding thermal-oxidative-aging-resistant performance in a high polymer material, and the antioxidant also has good compatibility with a nonpolar polymer, so that the antioxidant is prevented from being volatilized due to heating or being extracted under the action of a solvent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first purpose of the invention is to provide a hindered phenol antioxidant containing a hindered amine structure.
The second purpose of the invention is to provide a preparation method of the hindered phenol antioxidant.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a hindered phenol antioxidant having a structure represented by formula (1):
the molecular formula of the antioxidant is C41H73N3O3。
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of hindered phenol antioxidant containing hindered amine structure comprises the following reaction synthesis process route:
the preparation method comprises the following steps:
1) carrying out 1, 4-addition reaction on the compound shown in the formula (2) and 2, 6-di-tert-butylphenol in the presence of a catalyst 1 to obtain an intermediate compound shown in the formula (3);
2) in the presence of a catalyst 2, carrying out ester exchange reaction on an intermediate compound shown as a formula (3) and 1, 2, 2, 6, 6-pentamethyl-4-piperidinol to obtain a hindered phenol antioxidant shown as a formula (1).
Further, in step 1), the mass ratio of the compound represented by the formula (2), 2, 6-di-tert-butylphenol and the catalyst 1 is 1: 0.8-2: 0.01 to 0.5.
Further, in the step 1), the catalyst 1 is any one of L-proline, potassium carbonate and cesium carbonate.
Further, in the step 1), the reaction solvent is any one of toluene, xylene and cyclohexane.
Further, in the step 1), the reaction temperature of the 1, 4-addition reaction is 50-170 ℃. Exemplary reaction temperatures for the 1, 4-addition reaction include, but are not limited to, 60-65 ℃, 80-85 ℃, 130-135 ℃, and the like.
Further, in the step 1), the reaction time of the 1, 4-addition reaction is 2-12 hours.
Further, in step 2), the mass ratio of the intermediate compound represented by the formula (3), 1, 2, 2, 6, 6-pentamethyl-4-piperidinol, and catalyst 2 is 1: 0.8-1.4: 0.001 to 0.01.
Further, in the step 2), the catalyst 2 is any one of tetraethyl titanate, tetrabutyl titanate and dibutyltin oxide.
Further, in the step 2), the reaction solvent is any one of toluene, xylene and cyclohexane.
Further, in the step 2), the reaction temperature of the ester exchange reaction is 90-170 ℃. Exemplary reaction temperatures for the transesterification reaction include, but are not limited to, 95-100 deg.C, 110-115 deg.C, 160-165 deg.C, and the like.
Further, in the step 2), the reaction time of the ester exchange reaction is 4-16 hours.
Compared with the prior art, the invention has the following beneficial effects because the technology is adopted:
the application of the hindered phenol antioxidant prepared by the invention in rubber shows the superiority of the hindered phenol antioxidant in oxidation resistance and the gain of the hindered phenol antioxidant to the cohesive force of the rubber; the rubber has a good synergistic effect on the aspect of heat and oxygen resistance of rubber due to the fact that the rubber has hindered phenol and low-alkalinity hindered amine structures; the antioxidant prepared by the invention has the advantages of good compatibility with natural rubber, low volatility, migration resistance and the like, so that the antioxidant can be uniformly dispersed in the natural rubber, and the antioxidant is prevented from being volatilized or extracted under the action of a solvent due to heating.
Drawings
FIG. 1 is an infrared spectrum of a target product prepared in example 6.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1:
the preparation of the compound represented by the formula (2) comprises the following steps:
400g of N-butyl-2, 2, 6, 6-tetramethyl-4-piperidylamine, 190g of methyl propiolate, 4g of triethylamine and 800g of toluene are added into a 2L four-neck round-bottom flask, the temperature is raised to 80 ℃ under the protection of nitrogen, the mixture is kept and stirred for 6 hours, sampling is carried out to be qualified, and 576g of the compound shown as the formula (2) is obtained through reduced pressure distillation and is light yellow oily liquid.
Example 2:
the preparation of the compound represented by the formula (3) comprises the following steps:
a100 mL four-necked round-bottomed flask was charged with 10g of the compound represented by the formula (2) prepared in example 1, 7g of 2, 6-di-tert-butylphenol, 0.05g of L-proline and 20g of toluene, nitrogen was replaced, the mixture was stirred, the temperature was raised to 105 ℃ and the reaction was maintained for 12 hours, HPLC (high performance liquid chromatography) detected that the content of the compound represented by the formula (2) was less than 3%, the mixture was cooled to room temperature, and the mixture was washed with water and distilled to be desolventized to obtain 15.4g of the compound represented by the formula (3) as a white solid.
Example 3:
the preparation of the compound represented by the formula (1) comprises the following steps:
15.4g of the compound represented by the formula (3) prepared in example 2, 5.6g of 1, 2, 2, 6, 6-pentamethyl-4-piperidinol, which was added to a 100mL four-necked round-bottomed flask, were heated to 105 ℃ for 0.5 hour, 0.04g of dibutyltin oxide was added thereto, the reaction was carried out while evaporating methanol, the reaction mixture was kept warm for 12 hours and then sampled to be qualified, the reaction mixture was adjusted to be weakly alkaline, washed with water and dried, and distilled under reduced pressure to obtain 18g of a white product with a yield of 90%.
Example 4:
100g of the compound represented by the formula (2) prepared in example 1, 73g of 2, 6-di-tert-butylphenol, 0.6g of L-proline and 300g of toluene were charged into a 1L four-necked round-bottomed flask, nitrogen gas was replaced, stirring was started, the temperature was raised to 105 ℃ and the reaction was maintained for 10 hours, HPLC detection showed that the content of the compound represented by the formula (2) was less than 3%, the reaction was cooled to room temperature, and the solvent was distilled off by washing with water to obtain 164g of an intermediate compound represented by the formula (3). Dissolving the compound shown in the formula (3) in 250g of toluene, adding 73g of 1, 2, 2, 6, 6-pentamethyl-4-piperidinol into a reaction bottle, heating to 105 ℃, adding 1g of dibutyltin oxide after 0.5h, distilling out methanol accompanied by reaction, keeping the temperature for 12h, sampling and detecting to be qualified, adjusting the reaction solution to be alkalescent, washing with water, drying, and distilling under reduced pressure to obtain 197g of white product with the yield of 93%.
Example 5:
100g of the compound represented by the formula (2) prepared in example 1, 70g of 2, 6-di-tert-butylphenol, 10g of cesium carbonate and 300g of toluene were charged into a 1L four-necked round-bottomed flask, nitrogen gas was replaced, stirring was started, the temperature was raised to 110 ℃, the reaction was maintained for 12 hours, the content of the compound represented by the formula (2) was less than 3% by HPLC, the reaction mixture was cooled to room temperature, washed with water and distilled, and the solvent was removed, whereby 158g of the intermediate compound represented by the formula (3) was obtained. Dissolving the compound shown in the formula (3) in 250g of toluene, adding 66g of 1, 2, 2, 6, 6-pentamethyl-4-piperidinol into a reaction bottle, heating to 110 ℃, adding 0.8g of dibutyltin oxide after 0.5h, distilling out methanol along with the reaction, keeping the temperature for reaction for 12h, sampling and detecting to be qualified, adjusting the reaction solution to be alkalescent, washing with water, carrying out suction filtration and drying, and carrying out reduced pressure distillation to obtain 188g of a white product with the yield of 89%.
Example 6:
500g of the compound represented by the formula (2) prepared in example 1, 346g of 2, 6-di-tert-butylphenol, 9g of L-proline and 1000g of xylene are charged into a 3L reaction kettle, nitrogen is replaced, stirring is started, the temperature is raised to 130 ℃, the temperature is kept for reaction for 10 hours, the content of the compound represented by the formula (2) is detected to be lower than 3% by HPLC, the temperature is reduced to room temperature, water washing and distillation are carried out, and after a solvent is removed, 825g of the intermediate compound represented by the formula (3) is obtained. Dissolving a compound shown as a formula (3) in 1000g of dimethylbenzene, adding 330g of 1, 2, 2, 6, 6-pentamethyl-4-piperidinol into a reaction kettle, heating to 130 ℃, adding 2.2g of dibutyltin oxide after 0.5h, distilling out methanol along with the reaction, keeping the temperature for reaction for 12h, sampling and detecting to be qualified, adjusting the reaction solution to be alkalescent, washing with water, drying, and distilling under reduced pressure to obtain 1025g of white product with the yield of 97%.
The target product prepared in this example was detected by an infrared spectrometer, the infrared spectrum is shown in figure 1,
the infrared spectrum shown in figure 1 can be seen at 1460cm-1、1363cm-1Absorption peaks indicate the presence of the stretching and bending vibration vC-H of vCH3 and vCH 2.
1450cm-1、1425cm-1Absorption peak, indicating the presence of vC ═ C of the phenyl ring.
At 1739cm-1Has a strong absorption peak of vC ═ O, and the molecule has 3 oxygen atoms and is 1047cm-1There is a strong absorption peak for vC-O indicating the presence of ester groups in the molecule.
At 2800 and 3000cm-1The position is the characteristic absorption peak of saturated CH and benzene ring CH.
At 3600cm-1Has a absorption peak of vOH.
The product molecule can thus be demonstrated to have the following structural formula:
comparative example 1:
example 4 was repeated, except that the reaction solution prepared from the 1, 4-addition reaction step with the temperature of the elevated temperature changed to room temperature and the remaining conditions were unchanged had a product content of 9% (HPLC).
Comparative example 2:
example 4 was repeated, except that the reaction solution prepared from the 1, 4-addition reaction step with the temperature of 135 ℃ was changed, and the remaining conditions were not changed, and the product content was 94% (HPLC).
Test example:
rubber is widely applied in daily life and national industry and is one of important materials used by human beings, but the rubber contains a large amount of unsaturated C ═ C double bonds, so that the thermal-oxidative aging resistance of the rubber is poor, and in order to delay or inhibit the aging of the rubber, the most common and effective method is to add an antioxidant to play a role in antioxidation. In this application, antioxidant 1010 commonly used in the market and the antioxidant prepared in example 6 of the present invention were respectively selected for a comparative test of thermal oxidative aging resistance.
Sample preparation: sample 1 was prepared by first passing 1kg of natural rubber through an open mill 10 times (roll gap 0.4-0.6mm), then adding 0.3kg of nano calcium carbonate, 50g of zinc oxide, 20g of stearic acid, 5g of rubber accelerator CZ, 5g of rubber accelerator DM and 10g of antioxidant 1010 by conventional mixing method, and finally adding 15g of sulfur. And standing the rubber compound for 30 hours, vulcanizing the rubber compound on a hydraulic flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time is the positive vulcanization time and is measured by a rotor-free vulcanizing instrument.
Sample 2 1kg of natural rubber was first passed through an open mill 10 times (roll gap 0.4-0.6mm), then 0.3kg of nano calcium carbonate, 50g of zinc oxide, 20g of stearic acid, 5g of rubber accelerator CZ, 5g of rubber accelerator DM and 10g of the antioxidant prepared in example 6 of the present invention were added according to a conventional mixing method, and finally 15g of sulfur was added. And standing the rubber compound for 30 hours, vulcanizing the rubber compound on a hydraulic flat vulcanizing machine, wherein the vulcanization temperature is 150 ℃, and the vulcanization time is the positive vulcanization time and is measured by a rotor-free vulcanizing instrument.
Test 1: test for vulcanization Properties
The vulcanization characteristics of the natural rubber compound are determined on a rotor-free vulcanizer according to GB/T9869-1997, the test temperature is 150 +/-1 ℃, and the test results are as follows:
it can be seen from the table that the vulcanization rate of the natural rubber compound with the antioxidant 1010 added and the natural rubber compound with the antioxidant prepared in the embodiment 6 of the present invention is lower than that of the natural rubber compound without the antioxidant at the test temperature of 150 ± 1 ℃, which indicates that the hindered phenol antioxidant has the function of delaying rubber vulcanization, and the reason may be that the antioxidant captures free radicals generated in the vulcanization process of rubber, thereby inhibiting rubber vulcanization, and in addition, the natural rubber compound with the antioxidant prepared in the embodiment 6 of the present invention has a lower vulcanization rate than that of the natural rubber compound with the antioxidant 1010 added, so that the antioxidant provided by the present invention has a better antioxidant effect than that of the antioxidant 1010 commonly used in the market, thereby more effectively inhibiting rubber vulcanization and improving the sulfur oxidation resistance of the natural rubber.
Test 2: mechanical Property test
The tensile strength of rubber is the ultimate ability of a rubber article to resist tensile failure, and is one of the important indicators for a rubber article, and the life of a natural rubber article is directly related to the tensile strength. The test results of the effects of the antioxidant prepared in example 6 of the invention and the antioxidant 1010 on the mechanical properties of the vulcanized natural rubber are as follows: (tensile Property measured in accordance with GB/T528-2009, tensile Rate of 500mm min-1(ii) a The tearing strength is measured according to GB/T529-; shore A hardness was measured according to GB/T531.1-2008).
As can be seen from the table, the tensile strength of the vulcanized natural rubber is 28.65MPa when no antioxidant is added, the tensile strength of the vulcanized natural rubber is highest and is 29.62MPa when the antioxidant prepared in inventive example 6 is added, and the tensile strength of the vulcanized natural rubber is 28.78MPa when the antioxidant 1010 is added, which indicates that the antioxidant prepared in inventive example 6 has better tensile properties than the antioxidant 1010 for the vulcanized natural rubber. In addition, with the addition of the antioxidant, the elongation at break, the tear strength, the hardness and the like of the natural rubber are changed differently, and it can be known from the table that the antioxidant prepared in the embodiment 6 of the invention has better mechanical properties on vulcanized rubber of the natural rubber than the antioxidant 1010, so that the antioxidant prepared in the embodiment 6 of the invention can effectively improve the cohesive force of the rubber material and prolong the service life of the rubber material.
Test 3: thermo-oxidative aging resistance test
The natural rubber is inevitably subjected to heat and oxygen in different degrees in the processes of processing, storing and using, the heat and oxygen aging can reduce the excellent performance of the natural rubber, and finally, the use value of the natural rubber is completely lost. The antioxidant is added into the natural rubber to prevent the thermal oxidative decomposition of the natural rubber during processing and the thermal oxidative aging during storage and use, and the artificial accelerated thermal oxidative aging test can be used for evaluating the thermal oxidative aging resistance of the natural rubber and identifying the antioxidant effect of the antioxidant. In order to evaluate the thermal-oxidative aging resistance of the antioxidant prepared in the embodiment 6 and the antioxidant 1010 on natural rubber, the accelerated thermal-oxidative aging test of the test is carried out according to GB/T3512-2014, the aging temperature is 120 +/-1 ℃, and the aging time is 180 hours. After aging for 180 hours, the tensile strength retention rate and the elongation at break retention rate of the blank sample, the natural rubber vulcanized rubber of the antioxidant prepared in the embodiment 6 of the invention and the natural rubber vulcanized rubber prepared by the antioxidant 1010 are respectively tested, the tensile property is determined according to GB/T528--1The test results are as follows:
as can be seen from the table, compared with the natural rubber vulcanized rubber without the antioxidant, the vulcanized rubber added with the antioxidant or the antioxidant 1010 prepared in the embodiment 6 of the invention has much higher tensile strength retention rate and elongation at break retention rate, and the antioxidant 1010 both prepared in the embodiment 6 of the invention can effectively inhibit the thermal oxidative aging of the natural rubber. After aging for 180 hours, the tensile strength retention rate and the elongation at break retention rate of the natural rubber vulcanized rubber added with the antioxidant prepared in the embodiment 6 of the invention are higher than those of the vulcanized rubber added with the antioxidant 1010, which shows that the thermal oxidation aging resistance of the antioxidant prepared in the embodiment 6 of the invention to natural rubber is better than that of the antioxidant 1010. The antioxidant prepared in example 6 of the present invention has much fewer hindered phenol groups than the antioxidant 1010 at the same addition level, however, the antioxidant prepared in example 6 of the present invention has thermal-oxidative aging resistance up to the level of the antioxidant 1010, even better than the latter. The reason for this may be as follows: in the molecular structure of the antioxidant prepared in the embodiment 6 of the invention, hindered amine and hindered phenol groups exist, wherein the hindered amine has the function of an auxiliary antioxidant and can generate a synergistic antioxidation effect with hindered phenol. In addition, the antioxidant prepared in the embodiment 6 of the invention has better compatibility with the natural rubber, so that the antioxidant can be uniformly dispersed in the natural rubber, and the antioxidant is prevented from being volatilized due to heating or being extracted under the action of a solvent.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (10)
1. A hindered phenol antioxidant characterized by having a structure represented by the formula (1):
2. a method for preparing the hindered phenol antioxidant of claim 1, wherein the synthetic process route is as follows:
3. the method of preparing a hindered phenol antioxidant of claim 2, comprising the steps of:
1) carrying out 1, 4-addition reaction on the compound shown in the formula (2) and 2, 6-di-tert-butylphenol in the presence of a catalyst 1 to obtain an intermediate compound shown in the formula (3);
2) in the presence of a catalyst 2, carrying out ester exchange reaction on an intermediate compound shown as a formula (3) and 1, 2, 2, 6, 6-pentamethyl-4-piperidinol to obtain a hindered phenol antioxidant shown as a formula (1).
4. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in step 1), the mass ratio of the compound represented by the formula (2), 2, 6-di-tert-butylphenol and the catalyst 1 is 1: 0.8-2: 0.01 to 0.5.
5. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the catalyst 1 is any one of L-proline, potassium carbonate and cesium carbonate.
6. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the reaction temperature of the 1, 4-addition reaction is 50-170 ℃; the reaction time is 2-12 hours.
7. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in step 2), the mass ratio of the intermediate compound represented by formula (3), 1, 2, 2, 6, 6-pentamethyl-4-piperidinol, and the catalyst 2 is 1: 0.8-1.4: 0.001 to 0.01.
8. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 2), the catalyst 2 is any one of tetraethyl titanate, tetrabutyl titanate and dibutyltin oxide.
9. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 2), the reaction temperature of the ester exchange reaction is 90-170 ℃; the reaction time is 4-16 hours.
10. The method for preparing a hindered phenol antioxidant according to claim 3, wherein: in the step 1), the reaction solvent is any one of toluene, xylene and cyclohexane; in the step 2), the reaction solvent is one of toluene, xylene and cyclohexane.
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| CN101885701A (en) * | 2010-06-28 | 2010-11-17 | 北京天罡助剂有限责任公司 | Hindered amine compound having double-hindered phenol structure for light stabilizer and preparation method thereof |
| CN102337001A (en) * | 2011-10-13 | 2012-02-01 | 珠海市远康企业有限公司 | Polyformaldehyde with thermal stability and weather resistance and preparation method thereof |
| CN105294543A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Method for preparing weather-proof anti-aging auxiliary agent simultaneously containing hindered phenol and hindered amine structures |
| CN106588663A (en) * | 2016-10-28 | 2017-04-26 | 南雄志精细化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN112010800A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered phenol-containing hindered amine light stabilizer and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101885701A (en) * | 2010-06-28 | 2010-11-17 | 北京天罡助剂有限责任公司 | Hindered amine compound having double-hindered phenol structure for light stabilizer and preparation method thereof |
| CN102337001A (en) * | 2011-10-13 | 2012-02-01 | 珠海市远康企业有限公司 | Polyformaldehyde with thermal stability and weather resistance and preparation method thereof |
| CN105294543A (en) * | 2015-11-11 | 2016-02-03 | 华南理工大学 | Method for preparing weather-proof anti-aging auxiliary agent simultaneously containing hindered phenol and hindered amine structures |
| CN106588663A (en) * | 2016-10-28 | 2017-04-26 | 南雄志精细化工有限公司 | Hindered phenol antioxidant and preparation method thereof |
| CN112010800A (en) * | 2020-09-08 | 2020-12-01 | 宿迁联盛科技股份有限公司 | Hindered phenol-containing hindered amine light stabilizer and preparation method and application thereof |
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