CN107129432A - A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone - Google Patents
A kind of synthetic method of ultra-violet absorber 4,4`- bis- epoxide benzophenone Download PDFInfo
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- CN107129432A CN107129432A CN201710416860.7A CN201710416860A CN107129432A CN 107129432 A CN107129432 A CN 107129432A CN 201710416860 A CN201710416860 A CN 201710416860A CN 107129432 A CN107129432 A CN 107129432A
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/54—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition of compounds containing doubly bound oxygen atoms, e.g. esters
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention discloses a kind of ultra-violet absorber 4, the synthetic method of the epoxide benzophenone of 4'- bis-, this method is：Using P-hydroxybenzoic acid as initiation material, hydroxyl is protected through acetylation；Under zinc chloride, POCl3 catalysis, synthetically prepared intermediate P-hydroxybenzoic acid phenyl ester is reacted with phenol Fredel Crafts；Again intermediate 4,4- dihydroxy benaophenonels are prepared through deacetylated protection group and Fries rearrangements；Finally with potassium carbonate into salt, TBAB catalysis is reacted with 1- bromo-n-hexanes by Williamson to be synthesized, and obtains the epoxide benzophenone products of 4,4'- bis-；The present invention has advantages below：Reaction condition is gentle, low temperature in normal pressure, and quality control is stable；Feed stock conversion is high, and side reaction is effectively suppressed；The three wastes are few, and pollution is light, favourable to environment and producer's labour protection.
Description
Technical field
The present invention relates to the synthetic method of UV absorbers, and in particular to a kind of ultra-violet absorber 4, the oxygen of 4'- bis-
The synthetic method of base benzophenone.
Background technology
Ultra-violet absorber (benzophenone analog derivative) is a kind of widely used high polymer material function additive, its energy
It is strong to absorb ultraviolet, while being also widely used in the fields such as daily-use chemical industry, medicine, agricultural chemicals, plastics, coating.Because the earth is smelly
The destruction of oxygen layer is increasingly severe, and radiation of the solar ultraviolet to the earth is more and more stronger, therefore ultra-violet absorber is various
One of essential functional additives such as high polymer material, skin sparing articles for use.In recent years, both at home and abroad to the ultraviolet of high-quality
The demand of light absorbers constantly increases.Have developed once in the world as：Containing sulfonic acid acid, the miscellaneous azo hexichol of benzene azoles two of amido class
Class ultra-violet absorber, benzotriazole ultraviolet absorbent etc..It is rarely seen to there is the related of synthesising title compound to report.
The content of the invention
The purpose of the present invention, is to overcome above-mentioned limitation, so as to provide a kind of ultra-violet absorber 4, the epoxides of 4'- bis-
The synthetic method of benzophenone, this method raw and auxiliary material is easy to get, and reaction condition is gentle, simple and safe operation, high conversion rate, product
Steady quality, the three wastes are easily disposed less.
The purpose of the present invention is achieved through the following technical solutions：A kind of ultra-violet absorber 4,4'- bis- epoxide hexichol
The synthetic method of ketone, step includes：
Step A：Hydroxyl is protected in P-hydroxybenzoic acid acetylation；
Step B：Under zinc chloride, POCl3 catalysis, synthetically prepared intermediate pair is reacted with phenol Fredel-Crafts
MPHB；
Step C：Deacetylated protection group and Fries rearrangements prepare intermediate 4,4- dihydroxy benaophenonels；
Step D：Finally with potassium carbonate into salt, TBAB catalysis is reacted with 1- bromo-n-hexanes by Williamson
Synthesis, obtains the epoxide benzophenone products of 4,4'- bis-.
Preferably, step A is specially：0.375mol P-hydroxybenzoic acid is added into thiacyclohexane, in 30~35 DEG C of drops
Plus 0.44~0.46mol chloroacetic chlorides, drip off in 35~40 DEG C of insulation reaction 2h, excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains 0.36mol to acetoxy-benzoic acid, yield 97%；
Step B is specially：Put into successively into dichloro-benzenes 0.36mol to acetoxy-benzoic acid, 0.38~0.40mol
Phenol, 0.42~0.44mol POCl3s, 0.72~0.75mol zinc chloride, in 65~70 DEG C of insulation reaction 2h, are cooled to 30
DEG C, thread is poured into frozen water, is stood to divide and is removed water, then is washed to neutrality；Instill 90~120ml's into organic phase in 10~15 DEG C
28% ammoniacal liquor, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, and filtering, filter cake is used
Ethyl alcohol recrystallization, obtains 0.34mol P-hydroxybenzoic acid phenyl esters, yield 94.4%；
Step C is specially：Into anhydrous carbon disulfide add 0.34mol P-hydroxybenzoic acid phenyl ester, 0.38~
0.45mol alchlors, stirring temperature rising reflux reaction 6h, are cooled to 30 DEG C, thread is poured into frozen water, stand to divide and remove water, then water
It is washed till neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain about 0.33mol white crystalline bodies
4,4- dihydroxy benaophenonels, yield 97%；
Step D is specially：0.33mol 4,4- dihydroxy benaophenonels, 0.25~0.28mol carbon is put into acetone
Sour potassium, 0.70~0.75mol1- bromo-n-hexanes, 0.014~0.019mol TBABs, stir temperature rising reflux 48h, reaction
Feed liquid is changed into white from yellow green, and solvent acetone is sloughed in air-distillation, and washing is desalted, ethyl alcohol recrystallization, obtains 0.31mol whites
Flaky crystal product 4,4- bis- epoxide benzophenone, yield >=92%, content (HPLC methods)：>=99.5%；Fusing point 104.5
~105.0 DEG C.
Each step reaction equation is as follows：
In summary, the present invention has advantages below：Reaction condition is gentle, low temperature in normal pressure, and quality control is stable；Raw material
High conversion rate, side reaction is effectively suppressed；The three wastes are few, and pollution is light, favourable to environment and producer's labour protection.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment
It is only used for explaining the present invention, is not intended to limit the scope of the present invention..
Embodiment 1：
(1) 51.8g (0.375mol) P-hydroxybenzoic acid is added into 100ml thiacyclohexanes, in 30~35 DEG C of dropwise additions
35.30g (0.45mol) chloroacetic chloride, is dripped off in 35~40 DEG C of insulation reaction 2h.Excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains to acetoxy-benzoic acid 65.5g, yield 97%；
(2) put into successively into 180ml dichloro-benzenes to acetoxy-benzoic acid 65.5g (0.36mol), phenol 35.8g
(0.38mol), POCl3 66 (0.43mol), zinc chloride 98g (0.72mol), in 65~70 DEG C of insulation reaction 2h, are cooled to
30 DEG C, thread is poured into 300ml frozen water, is stood to divide and is removed water, then is washed to neutrality；28% is instilled into organic phase in 10~15 DEG C
Ammoniacal liquor 90ml, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, and filtering, filter cake is used
Ethyl alcohol recrystallization, obtains P-hydroxybenzoic acid phenyl ester 85g (0.34mol) yield 94.4%；
(3) P-hydroxybenzoic acid phenyl ester 85g (0.34mol), alchlor 53g are added into the anhydrous carbon disulfide of 200ml
(0.4mol) stirring temperature rising reflux reaction 6h, is cooled to 30 DEG C, thread is poured into 300ml frozen water, stands to divide and removes water, then is washed to
It is neutral；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain white crystalline body 4,4- dihydroxy two
Benzophenone 71g (0.33mol), yield 97%；
(4) 4,4- dihydroxy benaophenonels 71g (0.33mol), potassium carbonate 35g are put into 250ml acetone
(0.25mol), 1- bromo-n-hexanes 116g (0.7mol), TBAB 4.5g (0.014mol), stir temperature rising reflux 48h, instead
Feed liquid is answered to be changed into white from yellow green.Solvent acetone is sloughed in air-distillation, and washing is desalted, and ethyl alcohol recrystallization obtains white plates
Crystalline product 4, the epoxide benzophenone of 4- bis-.118.4g (0.31mol), yield 92%；Content (HPLC methods)：99.5%；It is molten
104.2~104.8 DEG C of point.
Embodiment 2：
(1) 51.8g (0.375mol) P-hydroxybenzoic acid is added into 100ml thiacyclohexanes, in 30~35 DEG C of dropwise additions
36.10g (0.46mol) chloroacetic chloride, is dripped off in 35~40 DEG C of insulation reaction 2h.Excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains to acetoxy-benzoic acid 65.4g, yield 97%；
(2) put into successively into 180ml dichloro-benzenes to acetoxy-benzoic acid 65.4g (0.36mol), phenol 37.7g
(0.4mol), POCl3 67.5 (0.44mol), zinc chloride 98g (0.72mol), in 65~70 DEG C of insulation reaction 2h, are cooled to
30 DEG C, thread is poured into 300ml frozen water, is stood to divide and is removed water, then is washed to neutrality；28% is instilled into organic phase in 10~15 DEG C
Ammoniacal liquor 90ml, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, and filtering, filter cake is used
Ethyl alcohol recrystallization, obtains P-hydroxybenzoic acid phenyl ester 84.8g (0.34mol) yield 94.3%；
(3) P-hydroxybenzoic acid phenyl ester 84.8g (0.34mol), alchlor are added into the anhydrous carbon disulfide of 200ml
60g (0.45mol) stirring temperature rising reflux reaction 6h, are cooled to 30 DEG C, thread is poured into 300ml frozen water, stand to divide and remove water, then water
It is washed till neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain white crystalline body 4,4- dihydroxies
Base benzophenone 71.2g (0.33mol), yield 97.1%；
(4) 4,4- dihydroxy benaophenonels 71.2g (0.33mol), potassium carbonate 40g are put into 250ml acetone
(0.28mol), 1- bromo-n-hexanes 116g (0.7mol), TBAB 5g (0.016mol), stir temperature rising reflux 48h, reaction
Feed liquid is changed into white from yellow green.Solvent acetone is sloughed in air-distillation, and washing is desalted, ethyl alcohol recrystallization, obtains white plates knot
Brilliant product 4, the epoxide benzophenone of 4- bis-.118.3g (0.31mol), yield 92.1%；Content (HPLC methods) 99.6%；It is molten
104.1~104.5 DEG C of point.
Embodiment 3：
(1) 51.8g (0.375mol) P-hydroxybenzoic acid is added into 100ml thiacyclohexanes, in 30~35 DEG C of dropwise additions
34.50g (0.44mol) chloroacetic chloride, is dripped off in 35~40 DEG C of insulation reaction 2h.Excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains to acetoxy-benzoic acid 65.5g, yield 97%；
(2) put into successively into 180ml dichloro-benzenes to acetoxy-benzoic acid 65.5g (0.36mol), phenol 35.8g
(0.39mol), POCl3 66 (0.43mol), zinc chloride 104g (0.73mol), in 65~70 DEG C of insulation reaction 2h, are cooled to
30 DEG C, thread is poured into 300ml frozen water, is stood to divide and is removed water, then is washed to neutrality；28% is instilled into organic phase in 10~15 DEG C
Ammoniacal liquor 120ml, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, filtering, filter cake
With ethyl alcohol recrystallization, P-hydroxybenzoic acid phenyl ester 85g (0.34mol) yield 94.4% is obtained；
(3) P-hydroxybenzoic acid phenyl ester 85g (0.34mol), alchlor 50g are added into the anhydrous carbon disulfide of 200ml
(0.38mol) stirring temperature rising reflux reaction 6h, is cooled to 30 DEG C, thread is poured into 300ml frozen water, stands to divide and removes water, then washes
To neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain white crystalline body 4,4- dihydroxy
Benzophenone 71g (0.33mol), yield 97%；
(4) 4,4- dihydroxy benaophenonels 71g (0.33mol), potassium carbonate 35g are put into 250ml acetone
(0.25mol), 1- bromo-n-hexanes 124g (0.75mol), TBAB 6g (0.019mol), stir temperature rising reflux 48h, instead
Feed liquid is answered to be changed into white from yellow green.Solvent acetone is sloughed in air-distillation, and washing is desalted, and ethyl alcohol recrystallization obtains white plates
Crystalline product 4, the epoxide benzophenone of 4- bis-.118.5g (0.31mol), yield 92.1%；Content (HPLC methods)：99.5%；
104.5~105.0 DEG C of fusing point.
Embodiment 4：
(1) 51.8g (0.375mol) P-hydroxybenzoic acid is added into 100ml thiacyclohexanes, in 30~35 DEG C of dropwise additions
34.50g (0.45mol) chloroacetic chloride, is dripped off in 35~40 DEG C of insulation reaction 2h.Excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains to acetoxy-benzoic acid 65.5g, yield 97%；
(2) put into successively into 180ml dichloro-benzenes to acetoxy-benzoic acid 65.5g (0.36mol), phenol 35.8g
(0.38mol), POCl3 66 (0.43mol), zinc chloride 104g (0.75mol), in 65~70 DEG C of insulation reaction 2h, are cooled to
30 DEG C, thread is poured into 300ml frozen water, is stood to divide and is removed water, then is washed to neutrality；28% is instilled into organic phase in 10~15 DEG C
Ammoniacal liquor 120ml, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, filtering, filter cake
With ethyl alcohol recrystallization, P-hydroxybenzoic acid phenyl ester 85g (0.34mol) yield 94.4% is obtained；
(3) P-hydroxybenzoic acid phenyl ester 85g (0.34mol), alchlor 50g are added into the anhydrous carbon disulfide of 200ml
(0.42mol) stirring temperature rising reflux reaction 6h, is cooled to 30 DEG C, thread is poured into 300ml frozen water, stands to divide and removes water, then washes
To neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain white crystalline body 4,4- dihydroxy
Benzophenone 71g (0.33mol), yield 97%；
(4) 4,4- dihydroxy benaophenonels 71g (0.33mol), potassium carbonate 35g are put into 250ml acetone
(0.26mol), 1- bromo-n-hexanes 124g (0.72mol), TBAB 6g (0.016mol), stir temperature rising reflux 48h, instead
Feed liquid is answered to be changed into white from yellow green.Solvent acetone is sloughed in air-distillation, and washing is desalted, and ethyl alcohol recrystallization obtains white plates
Crystalline product 4, the epoxide benzophenone of 4- bis-.118.5g (0.31mol), yield 92.1%；Content (HPLC methods)：99.5%；
104.5~105.0 DEG C of fusing point.
Embodiment 5：
(1) 51.8g (0.375mol) P-hydroxybenzoic acid is added into 100ml thiacyclohexanes, in 30~35 DEG C of dropwise additions
34.50g (0.44mol) chloroacetic chloride, is dripped off in 35~40 DEG C of insulation reaction 2h.Excessive chloroacetic chloride and solvent is reclaimed in air-distillation
Thiacyclohexane, adds ethyl alcohol recrystallization and obtains to acetoxy-benzoic acid 65.5g, yield 97%；
(2) put into successively into 180ml dichloro-benzenes to acetoxy-benzoic acid 65.5g (0.36mol), phenol 35.8g
(0.39mol), POCl3 66 (0.43mol), zinc chloride 104g (0.74mol), in 65~70 DEG C of insulation reaction 2h, are cooled to
30 DEG C, thread is poured into 300ml frozen water, is stood to divide and is removed water, then is washed to neutrality；28% is instilled into organic phase in 10~15 DEG C
Ammoniacal liquor 120ml, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, filtering, filter cake
With ethyl alcohol recrystallization, P-hydroxybenzoic acid phenyl ester 85g (0.34mol) yield 94.4% is obtained；
(3) P-hydroxybenzoic acid phenyl ester 85g (0.34mol), alchlor 50g are added into the anhydrous carbon disulfide of 200ml
(0.38mol) stirring temperature rising reflux reaction 6h, is cooled to 30 DEG C, thread is poured into 300ml frozen water, stands to divide and removes water, then washes
To neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain white crystalline body 4,4- dihydroxy
Benzophenone 71g (0.33mol), yield 97%；
(4) 4,4- dihydroxy benaophenonels 71g (0.33mol), potassium carbonate 35g are put into 250ml acetone
(0.27mol), 1- bromo-n-hexanes 124g (0.74mol), TBAB 6g (0.018mol), stir temperature rising reflux 48h, instead
Feed liquid is answered to be changed into white from yellow green.Solvent acetone is sloughed in air-distillation, and washing is desalted, and ethyl alcohol recrystallization obtains white plates
Crystalline product 4, the epoxide benzophenone of 4- bis-.118.5g (0.31mol), yield 92.1%；Content (HPLC methods)：99.5%；
104.5~105.0 DEG C of fusing point.
Claims (2)
1. a kind of ultra-violet absorber 4, the synthetic method of the epoxide benzophenone of 4'- bis-, it is characterised in that：Step includes：
Step A：P-hydroxybenzoic acid acetylation protection hydroxyl obtains chemical formula and is：
Step B：Under zinc chloride, POCl3 catalysis, synthetically prepared intermediate is reacted to hydroxyl with phenol Fredel-Crafts
Phenol benzoate, the P-hydroxybenzoic acid phenyl ester chemical formula is：
Step C：Obtaining chemical formula after deacetylated protection group is：Intermediate 4,4- bis- are prepared with Fries rearrangements
Dihydroxy benaophenonel, 4, the 4- dihydroxy benaophenonels chemical formula is：
Step D：Finally with potassium carbonate into salt, TBAB catalysis is reacted with 1- bromo-n-hexanes by Williamson to be synthesized,
The epoxide benzophenone products of 4,4'- bis- are obtained, epoxide benzophenone chemical formula is 4, the 4'- bis-：
2. a kind of ultra-violet absorber 4 according to claim 1, the synthetic method of the epoxide benzophenone of 4'- bis-, its
It is characterised by：The step A is specially：0.375mol P-hydroxybenzoic acid is added into thiacyclohexane, in 30~35 DEG C of dropwise additions
0.44~0.46mol chloroacetic chlorides, are dripped off in 35~40 DEG C of insulation reaction 2h, excessive chloroacetic chloride and solvent ring is reclaimed in air-distillation
Hexane, adds ethyl alcohol recrystallization and obtains 0.36mol to acetoxy-benzoic acid, yield 97%；
The step B is specially：Put into successively into dichloro-benzenes 0.36mol to acetoxy-benzoic acid, 0.38~0.40mol
Phenol, 0.42~0.44mol POCl3s, 0.72~0.75mol zinc chloride, in 65~70 DEG C of insulation reaction 2h, are cooled to 30
DEG C, thread is poured into frozen water, is stood to divide and is removed water, then is washed to neutrality；Instill 90~120ml's into organic phase in 10~15 DEG C
28% ammoniacal liquor, drop finishes room temperature reaction 3h, stands to divide and removes water, the normal pressure azeotropic that adds water again boils off solvent dichloro-benzenes, and filtering, filter cake is used
Ethyl alcohol recrystallization, obtains 0.34mol P-hydroxybenzoic acid phenyl esters, yield 94.4%；
The step C is specially：Into anhydrous carbon disulfide add 0.34mol P-hydroxybenzoic acid phenyl ester, 0.38~
0.45mol alchlors, stirring temperature rising reflux reaction 6h, are cooled to 30 DEG C, thread is poured into frozen water, stand to divide and remove water, then water
It is washed till neutrality；Solvent carbon disulfide is sloughed in air-distillation, with alcohol-water (1：3) recrystallize, obtain about 0.33mol white crystalline bodies
4,4- dihydroxy benaophenonels, yield 97%；
The step D is specially：0.33mol 4,4- dihydroxy benaophenonels, 0.25~0.28mol carbon is put into acetone
Sour potassium, 0.70~0.75mol1- bromo-n-hexanes, 0.014~0.019mol TBABs, stir temperature rising reflux 48h, reaction
Feed liquid is changed into white from yellow green, and solvent acetone is sloughed in air-distillation, and washing is desalted, ethyl alcohol recrystallization, obtains 0.31mol whites
Flaky crystal product 4,4- bis- epoxide benzophenone, yield >=92%, content (HPLC methods)：>=99.5%；Fusing point 104.5
~105.0 DEG C.
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| CN112321963A (en) * | 2020-09-25 | 2021-02-05 | 李世兵 | Anti-yellowing plastic alloy material and preparation method thereof |
| CN113582829A (en) * | 2021-08-04 | 2021-11-02 | 武汉大学 | Benzophenone-based flexible room-temperature phosphorescent crystal, and preparation method and application thereof |
| CN114341227A (en) * | 2019-08-27 | 2022-04-12 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN116622218A (en) * | 2023-05-10 | 2023-08-22 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
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| CN1696094A (en) * | 2005-04-28 | 2005-11-16 | 武汉大学 | Method for preparing 4,4'-dihydroxy benzophenone |
| CN106588611A (en) * | 2016-11-17 | 2017-04-26 | 江苏富比亚化学品有限公司 | Process for producing benzophenone ultraviolet ray absorbent |
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| CN109957996A (en) * | 2019-04-10 | 2019-07-02 | 王又清 | A kind of anti-ultraviolet anti-aging corrugated paper |
| CN114341227A (en) * | 2019-08-27 | 2022-04-12 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN114341227B (en) * | 2019-08-27 | 2024-04-30 | Dic株式会社 | Phenolic resin, curable resin composition, and cured product thereof |
| CN112321963A (en) * | 2020-09-25 | 2021-02-05 | 李世兵 | Anti-yellowing plastic alloy material and preparation method thereof |
| CN113582829A (en) * | 2021-08-04 | 2021-11-02 | 武汉大学 | Benzophenone-based flexible room-temperature phosphorescent crystal, and preparation method and application thereof |
| CN116622218A (en) * | 2023-05-10 | 2023-08-22 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
| CN116622218B (en) * | 2023-05-10 | 2023-12-12 | 苏州美福瑞新材料科技有限公司 | Ageing-resistant polyurethane material, preparation method and application thereof on sealing ring |
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