CN111849028A - Graft polymerization type light stabilizer and preparation method thereof - Google Patents
Graft polymerization type light stabilizer and preparation method thereof Download PDFInfo
- Publication number
- CN111849028A CN111849028A CN202010576079.8A CN202010576079A CN111849028A CN 111849028 A CN111849028 A CN 111849028A CN 202010576079 A CN202010576079 A CN 202010576079A CN 111849028 A CN111849028 A CN 111849028A
- Authority
- CN
- China
- Prior art keywords
- light stabilizer
- type light
- graft polymerization
- polymerization type
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07D211/56—Nitrogen atoms
- C07D211/58—Nitrogen atoms attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of plastic additives, and particularly relates to a graft polymerization type light stabilizer and a preparation method thereof, wherein 4-amino-2, 2,6, 6-tetramethylpiperidine and p-bromostyrene are used as raw materials, under the action of an acid binding agent, an intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine is synthesized firstly, the intermediate is subjected to polymerization reaction under the conditions of a catalyst, high temperature and high pressure and the like, after the reaction is finished, cooling and washing are carried out, activated carbon is added for dehydration and decoloration, filtering is carried out, and filtrate is distilled to obtain the graft polymerization type light stabilizer; the graft polymerization type light stabilizer is an auxiliary agent which can inhibit or slow down the degradation of a high polymer material due to photo-oxidation, has excellent thermal stability and low volatility, and has better compatibility with the high polymer material; the synthesis process is simple, the preparation cost is low and the yield is high.
Description
Technical Field
The invention belongs to the technical field of plastic additives, and particularly relates to a graft polymerization type light stabilizer and a preparation method thereof.
Background
The light stabilizer is an additive of high molecular products, which can shield or absorb the energy of ultraviolet rays, quench singlet oxygen and decompose hydroperoxide into inactive substances, etc., so that the possibility of photochemical reaction can be eliminated or slowed down, and the process of photoaging can be prevented or delayed under the radiation of light, thereby achieving the purpose of prolonging the service life of the high molecular products.
The hindered amine is an organic amine compound with steric hindrance, has a good inhibition effect on the photo-oxidative degradation reaction of high polymers and organic compounds, and is a light stabilizer with excellent performance. However, the molecular weight of the existing hindered amine light stabilizer is generally small, the compatibility with high molecular materials is not good, and the existing hindered amine light stabilizer is not resistant to extraction, so that the research on the high molecular weight hindered amine light stabilizer is the leading trend of the market of the existing light stabilizer.
The high molecular weight polymeric light stabilizer has the characteristics of excellent processing thermal stability, very low volatility, migration resistance, extraction resistance, gas fading resistance and the like. The light stabilizer has good resin intermiscibility and good water extraction resistance, and has excellent long-acting light aging resistance compared with a common low-molecular-weight hindered amine light stabilizer. The product is widely used for products such as polypropylene (pp), polyethylene (pe), polystyrene (ps), abs resin, polyurethane (pu), polyester elastomer and the like. Has good synergistic effect with the antioxidant and the ultraviolet absorbent, and can further improve the heat resistance and the light aging resistance of the product.
Disclosure of Invention
The invention solves the technical problems in the prior art and provides a graft polymerization type light stabilizer and a preparation method thereof.
In order to solve the problems, the technical scheme of the invention is as follows:
a graft polymerization type light stabilizer has the following structural formula:
wherein n is 8-10.
The synthesis process route of the graft polymerization type light stabilizer is as follows:
wherein n is 8-10.
Preferably, the preparation method of the graft polymerization type light stabilizer comprises the following steps:
step 1, adding a certain mass of an intermediate 2,2,6, 6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine, a polymerization catalyst and an auxiliary catalyst into a polymerization reaction kettle, then adding a proper amount of an organic solvent, and starting stirring;
and 2, replacing air with nitrogen, introducing nitrogen to increase the pressure in the reaction kettle, starting a heating system, raising the temperature to perform polymerization reaction, cooling and washing after a period of reaction, adding activated carbon into an organic layer after water separation for dehydration and decoloration, filtering to remove the activated carbon, and distilling the filtrate to obtain the graft polymerization type light stabilizer.
Preferably, the intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, the solvent, the catalyst and the auxiliary catalyst, and the activated carbon are fed according to the mass ratio: 1: 3-6: 0.005-0.015: 0.001-0.005: 0.008-0.012.
Preferably, the organic solvent in step 1 and 2 is any one of xylene, toluene, DMF and tetrahydrofuran.
Preferably, the polymerization catalyst in step 1 is any one of titanocene dichloride, zirconocene dichloride and titanium chloride/aluminum alkyl, and any one of auxiliary catalysts MAO, EAO and modified MMAO.
Preferably, the polymerization temperature in the step 2 is 120-180 ℃, the polymerization pressure is 1.0-4.0MPa, and the reaction time is 4-10 hours.
Preferably, the preparation method of the intermediate 2,2,6, 6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine in the step 1 comprises the following steps:
adding a certain amount of p-bromostyrene into a reaction kettle, adding a proper amount of organic solvent and polymerization inhibitor, starting stirring to mix uniformly, controlling the temperature to be 50-80 ℃, dropwise adding 4-amino-2, 2,6, 6-tetramethylpiperidine, controlling the temperature to be 50-80 ℃, starting dropwise adding alkali liquor, keeping the temperature to be 80-110 ℃ after dropwise adding, reacting for 3-8 hours at the temperature of 80-110 ℃, washing with water after the reaction is finished, taking an organic layer after water is separated, and evaporating the solvent to dryness to obtain an intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine;
preferably, the p-bromostyrene, the 4-amino-2, 2,6, 6-tetramethylpiperidine, the organic solvent, the polymerization inhibitor and the alkali are fed according to the mass ratio: 1: 0.868-1.02: 2-5: 0.005-0.01: 0.22-0.44.
Compared with the prior art, the invention has the advantages that,
The graft polymerization type light stabilizer obtained by the invention is an auxiliary agent which can inhibit or slow down the degradation of the high polymer material due to the photooxidation, and compared with the prior HALS product, the graft polymerization type light stabilizer has more excellent ultraviolet and thermal stability, low volatility and better compatibility with the high polymer material; has good compatibility with most industrial solvents and excellent polymer compatibility, and is suitable for polypropylene, polyethylene plastics, fiber products and the like.
The graft polymerization type light stabilizer has the advantages of simple synthesis process, low preparation cost and high yield, and is an ideal process for realizing industrial production.
The specific implementation mode is as follows:
in order to enhance the understanding of the present invention, the following detailed description of the present invention is given with reference to the examples.
Example 1:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
75.2g of an intermediate 2,2,6, 6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine, 225g of dimethylbenzene, 0.38g of titanocene dichloride and 0.076g of a cocatalyst MAO are added into a polymerization reaction kettle, after air is replaced by nitrogen, stirring is started to fully mix the materials, then nitrogen is introduced to ensure that the pressure in the kettle reaches 1.2Mpa, a heating system is started to heat to 120 ℃ for reaction for 5 hours, then the temperature is reduced and washing is carried out, after water separation, 0.75g of activated carbon is added into an organic layer for dehydration and decoloration, filtering is carried out, filtrate is directly distilled to prepare 69.8g of the graft polymerization type light stabilizer, and the yield of the step is 92.8%.
Example 2:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
152.6g of intermediate 2,2,6, 6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine, 535g of dimethylbenzene, 0.91g of titanocene dichloride and 0.16g of cocatalyst MAO are added into a polymerization reaction kettle, nitrogen replaces air, stirring is started to fully mix the materials, nitrogen is introduced to ensure that the pressure in the kettle reaches 2.0Mpa, a heating system is started to heat to 140 ℃ for reaction for 6 hours, then the temperature is reduced for washing, 1.55g of active carbon is added into an organic layer after water separation for dehydration and decoloration, filtering is carried out, filtrate is distilled to prepare 140.3g of the graft polymerization type light stabilizer, and the yield in the step is 91.9%.
Example 3:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
233.7g of intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, 930g of dimethylbenzene, 2.33g of zirconocene dichloride and 0.62g of cocatalyst EAO are added into a polymerization reaction kettle, nitrogen replaces air, stirring is started to fully mix the materials, nitrogen is introduced to ensure that the pressure in the kettle reaches 2.5Mpa, a heating system is started to heat to 150 ℃ for reaction for 6 hours, then the temperature is reduced for washing, 2.5g of activated carbon is added into an organic layer after water separation for dehydration and decoloration, filtering is carried out, filtrate is distilled to prepare 209.8g of the graft polymerization type light stabilizer, and the yield in the step is 89.7%.
Example 4:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
adding 301.6g of intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, 1400g of dimethylbenzene, 2.8g of zirconocene dichloride and 1.1g of cocatalyst MAO into a polymerization reaction kettle, after replacing air with nitrogen, starting stirring to fully mix the materials, introducing nitrogen to ensure that the pressure in the kettle reaches 3.5Mpa, starting a heating system to heat to 165 ℃ for reaction for 6 hours, then cooling and washing, adding activated carbon into an organic layer after water separation for dehydration and decoloration, filtering, distilling filtrate to prepare 279.8g of the graft polymerization type light stabilizer, wherein the yield of the step is 92.7%.
Example 5:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
adding 450g of an intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, 2475g of dimethylbenzene, 5.4g of zirconocene dichloride and 1.8g of a cocatalyst MAO into a polymerization reaction kettle, after air is replaced by nitrogen, starting stirring to fully mix materials, introducing nitrogen to enable the pressure in the kettle to reach 3.5Mpa, starting a heating system to heat to 175 ℃ for reaction for 8 hours, then cooling and washing, adding 4.5g of activated carbon into an organic layer after water separation for dehydration and decoloration, filtering, distilling a filtrate to obtain 406g of the graft polymerization type light stabilizer, wherein the yield of the step is 90.2%.
Example 6:
a preparation method of a graft polymerization type light stabilizer comprises the following steps:
602.6g of intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, 3600g of dimethylbenzene, 9.0g of zirconocene dichloride and 3.0g of cocatalyst MAO are added into a polymerization reaction kettle for nitrogen replacement, the pressure in the kettle reaches 4.0MPa by introducing nitrogen, a heating system is started to heat up to 180 ℃ for reaction for 10 hours, then the temperature is reduced and the water is washed, 7.2g of activated carbon is added into an organic layer after water is separated for dehydration and decoloration, the filtration is carried out, the filtrate is distilled to prepare 545.4g of the graft polymerization type light stabilizer, and the yield in the step is 90.5%.
Example 7:
the samples obtained in examples 1 to 6 were subjected to thermogravimetric data respectively, and the results of comparison with the thermogravimetric data of some existing stabilizers in the market after the average value thereof was taken are shown in the following table:
| sample name | Temperature at 1% weight loss/. degree.C | Temperature at 5% weight loss/. degree.C | Temperature at 10% weight loss/. degree.C |
| Average values of samples in examples | 317 | 387 | 421 |
| Light stabilizer 770 | 208 | 258 | 287 |
| Light stabilizer 622 | 314 | 337 | 351 |
| Light stabilizer 944 | 296 | 382 | 409 |
By comparison, the higher temperature required for the light stabilizer at the same 5% and 10% loss indicates that the loss of the light stabilizer is less likely and the higher temperature resistance is more beneficial at the same processing temperature.
Example 8:
the stabilizer is added into a TPR product according to the weight ratio of 0.1 percent and 0.5 percent respectively, and then the performances before and after the addition are respectively detected, specifically as follows:
the hardness in the table is directly measured by a type A Shore durometer; the impact strength is measured by adopting a Zwick5113 intelligent digital pendulum bob impact tester, the specifications of the sample pieces are that the length of the sample is 80 +/-2 mm, the width is 10 +/-0.2 mm, the thickness is 4 +/-0.2 mm, the notch depth of the sample is 1/3 of the thickness of the sample, the notch width is 2 +/-0.2 mm, the number of each sample piece is 10, and the average value is measured to obtain the final impact strength of each sample piece; the aging equipment is a fluorescent ultraviolet lamp aging test box, and the experimental conditions are as follows: the lamp light type is UV-A, and the irradiance is 0.89W/m2The illumination is carried out for 8 hours at 60 ℃, the condensation is carried out for 4 hours at 50 ℃, and the aging is carried out circularly and alternately; compression set is measured as the percentage of the original height to which the sample failed to recover, as measured by the 37% compression set of the unadditized TPE, which means that the sample recovered only 63% of the compressed thickness.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and all equivalent substitutions or substitutions made on the above-mentioned embodiments are included in the scope of the present invention.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and also comprise the technical scheme formed by equivalent replacement of the technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (9)
1. A graft polymerization type light stabilizer is characterized in that the structural formula is as follows:
wherein n is 8-10.
2. The preparation method of the graft polymerization type light stabilizer according to claim 1, wherein the synthesis process route of the preparation method is as follows:
wherein n is 8-10.
3. The method for producing a graft polymerization type light stabilizer according to claim 2, characterized by comprising the steps of:
step 1, adding an intermediate 2,2,6, 6-tetramethyl-N- (4-vinyl phenyl) piperidine-4-amine, a polymerization catalyst and an auxiliary catalyst into a polymerization reaction kettle, then adding a proper amount of an organic solvent, and starting stirring;
and 2, replacing air with nitrogen, introducing nitrogen to increase the pressure in the reaction kettle, starting a heating system, raising the temperature to perform polymerization reaction, cooling and washing after a period of reaction, adding activated carbon into an organic layer after water separation for dehydration and decoloration, filtering to remove the activated carbon, and distilling the filtrate to obtain the graft polymerization type light stabilizer.
4. The method for preparing the graft polymerization type light stabilizer according to claim 3, wherein the intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine, the solvent, the catalyst and the auxiliary catalyst, and the activated carbon are fed in the mass ratio of: 1: 3-6: 0.005-0.015: 0.001-0.005: 0.008-0.012.
5. The method for preparing a graft polymerization type light stabilizer according to claim 3, wherein the organic solvent used in the steps 1 and 2 is any one of xylene, toluene, DMF, and tetrahydrofuran.
6. The method for preparing a graft polymerization type light stabilizer according to claim 3, wherein the polymerization catalyst in step 1 is any one of titanocene dichloride, zirconocene dichloride and titanium chloride/aluminum alkyl, and the auxiliary catalyst is any one of MAO, EAO and modified MMAO.
7. The method for preparing a graft polymerization type light stabilizer as claimed in claim 3, wherein the polymerization temperature in step 2 is 120-180 ℃, the polymerization pressure is 1.0-4.0MPa, and the reaction time is 4-10 hours.
8. The process for producing a graft polymerization type light stabilizer according to claim 3, wherein the intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidin-4-amine of step 1 is produced by:
Adding p-bromostyrene into a reaction kettle, adding a proper amount of organic solvent and polymerization inhibitor, starting stirring to uniformly mix the p-bromostyrene and the polymerization inhibitor, controlling the temperature to be 50-80 ℃, dropwise adding 4-amino-2, 2,6, 6-tetramethylpiperidine, controlling the temperature to be 50-80 ℃, starting dropwise adding alkali liquor, keeping the temperature to be 80-110 ℃ after dropwise adding, reacting for 3-8 hours, washing with water after the reaction is finished, taking an organic layer after water is separated, and evaporating the solvent to dryness to obtain an intermediate 2,2,6, 6-tetramethyl-N- (4-vinylphenyl) piperidine-4-amine.
9. The method for preparing a graft polymerization type light stabilizer according to claim 3, wherein the materials of p-bromostyrene, 4-amino-2, 2,6, 6-tetramethylpiperidine, organic solvent, polymerization inhibitor and alkali are calculated according to the mass ratio: 1: 0.868-1.02: 2-5: 0.005-0.01: 0.22-0.44.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576079.8A CN111849028A (en) | 2020-06-22 | 2020-06-22 | Graft polymerization type light stabilizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010576079.8A CN111849028A (en) | 2020-06-22 | 2020-06-22 | Graft polymerization type light stabilizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111849028A true CN111849028A (en) | 2020-10-30 |
Family
ID=72988014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010576079.8A Pending CN111849028A (en) | 2020-06-22 | 2020-06-22 | Graft polymerization type light stabilizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111849028A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101033A (en) * | 1987-08-12 | 1992-03-31 | Atochem North America, Inc. | Process for preparing reactive hindered amine light stabilizers |
| CN1084183A (en) * | 1992-09-09 | 1994-03-23 | 中国科学院化学研究所 | A kind of preparation method with high-molecular optical stablizer of auto-synergistic effect |
| CN101973927A (en) * | 2010-10-26 | 2011-02-16 | 南通惠康国际企业有限公司 | Preparation method of light stabilizer 4-allyloxy-2,2,6,6-tetramethylpiperidine |
| US20190048114A1 (en) * | 2017-08-10 | 2019-02-14 | International Business Machines Corporation | Non-halogenated flame retardant hindered amine light stabilizer impact modifiers |
-
2020
- 2020-06-22 CN CN202010576079.8A patent/CN111849028A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5101033A (en) * | 1987-08-12 | 1992-03-31 | Atochem North America, Inc. | Process for preparing reactive hindered amine light stabilizers |
| CN1084183A (en) * | 1992-09-09 | 1994-03-23 | 中国科学院化学研究所 | A kind of preparation method with high-molecular optical stablizer of auto-synergistic effect |
| CN101973927A (en) * | 2010-10-26 | 2011-02-16 | 南通惠康国际企业有限公司 | Preparation method of light stabilizer 4-allyloxy-2,2,6,6-tetramethylpiperidine |
| US20190048114A1 (en) * | 2017-08-10 | 2019-02-14 | International Business Machines Corporation | Non-halogenated flame retardant hindered amine light stabilizer impact modifiers |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4442250A (en) | Piperidyl derivatives of macrocyclic triazine compounds, possessing a stabilizing activity for polymers, and processes for their preparation | |
| CN1486346A (en) | Resorcinolic derivative for rubber compounds | |
| US4722806A (en) | Alkylated polyalkylenepolyamines, substituted oxo-piperazinyl-triazines and UV light stabilized compositions | |
| CN108586320B (en) | Polymeric rubber stabilizer and preparation method thereof | |
| EP0299925A1 (en) | Piperidine-triazine compounds for use as stabilizers for organic materials | |
| CN111849028A (en) | Graft polymerization type light stabilizer and preparation method thereof | |
| EP0377324A2 (en) | Substituted polyaminotriazines and the method of their preparation | |
| CN108863908B (en) | Polymerization type rubber stabilizer intermediate and preparation method thereof | |
| CN111808225B (en) | High molecular weight polymeric light stabilizer and preparation method thereof | |
| CN116368181A (en) | Monomer composition for synthesizing recycled plastic, method for preparing the same, and recycled plastic and molded article using the same | |
| CN111747885B (en) | Light stabilizer intermediate and preparation method thereof | |
| CN111423579B (en) | Flame-retardant nylon resin and preparation method thereof | |
| CN110606984A (en) | Light stabilizer and preparation method thereof | |
| CN113149963B (en) | Benzotriazole-hindered amine composite light stabilizer and preparation process thereof | |
| US4633016A (en) | Diphenylamine age resisters for rubber | |
| CN116284706A (en) | A polymeric hindered amine light stabilizer and its preparation method | |
| JP6905101B2 (en) | Hydrolysis resistant composition containing polyethylene terephthalate (PET) | |
| CN111040247B (en) | A kind of vulcanizing agent and its application | |
| CN114195921A (en) | Polymeric steric hindrance amine and preparation method and application thereof | |
| CN113861168B (en) | Polymeric hindered amine light stabilizer and preparation method thereof | |
| CN111303481A (en) | Oligomeric hindered amine light stabilizer and preparation method thereof | |
| CN111100083B (en) | Method for reducing solid waste in production of antioxidant 3114 | |
| CN114854213B (en) | Plate flame-retardant additive and application thereof | |
| CN116854593B (en) | Esterified acetylenic hydrosilylation inhibitor, preparation method and liquid silicone rubber | |
| CN109020798B (en) | Colored flame retardant tetra (bromophenoxy) p-benzoquinone compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201030 |
|
| RJ01 | Rejection of invention patent application after publication |