CN101691328A - Method for preparing fluorine-containing acrylate monomer - Google Patents
Method for preparing fluorine-containing acrylate monomer Download PDFInfo
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- CN101691328A CN101691328A CN200910153219A CN200910153219A CN101691328A CN 101691328 A CN101691328 A CN 101691328A CN 200910153219 A CN200910153219 A CN 200910153219A CN 200910153219 A CN200910153219 A CN 200910153219A CN 101691328 A CN101691328 A CN 101691328A
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Abstract
The invention provides a method for preparing fluorine-containing acrylate monomer. Azeotrope mixture is formed by acrylic acid alkyl ester and fluorine-containing alcohol through excess acrylic acid alkyl ester and generated alkyl alcohol in the presence of catalyst and polymerization inhibitor. The mixture of the acrylic acid alkyl ester and the fluorine-containing acrylate is distilled from a balance system, and is separated through a high-efficiency rectification tower in the presence of polymerization inhibitor to prepare the fluorine-containing acrylate monomer with purity more than over 99.9 percent.
Description
Technical field
The present invention relates to a kind of preparation method of acrylate monomer, relate in particular to a kind of preparation method of fluorinated acrylate monomer.
Background technology
Fluorine is the element of the electronegativity maximum known to up to now, its atom covalence radius (0.064nm) is only big slightly than hydrogen atom, so after the hydrogen on the hydrocarbon key (C-H) was replaced by fluorine, the bond energy of the carbon-fluorine bond (C-F) that fluorine atom and carbon atom form had increased 63kJ/mol.Simultaneously since fluorine atom to check the constraint effect of extranuclear electron and bonding electrons cloud stronger, C-F key polarity is little, it is lower to contain between the polymer molecule of C-F key reactive force.The perfluorinated acrylate polymkeric substance is to introduce full-fluorine group on the side chain of original copolymer; because perfluor side chain orientation outwardly; main chain and interior molecules are formed " shielding protection "; the electronic cloud of fluorine atom shields carbon carbon major key well; guaranteed the stability of carbon-carbon bond, and then made that stable physical property, weather resistance and the chemical proof of perfluorinated acrylate base polymer are all better.Thereby the perfluorinated acrylate polymer materials has the use properties of many excellences.Study the synthetic significance that just has more of fluorine-containing (methyl) acrylate monomer.
At present, the method for the preparation of having reported fluorine-containing (methyl) acrylate according to the difference of starting raw material, can be divided into the preparation method and has two kinds.A kind of is starting raw material with the fluorine-containing alcohol, as: the flat 2-295348 communique of Japanese kokai publication sho 59-181239 communique and Te Kai is a catalyzer with the vitriol oil or phosphoric anhydride respectively, is feedstock production fluorine-containing (methyl) acrylate with (methyl) vinylformic acid and fluorine-containing alcohol.United States Patent (USP) 3,719,698 have reported that with (methyl) vinylformic acid and fluorine-containing alcohol be raw material, trifluoroacetic anhydride is Preparation of Catalyst fluorine-containing (methyl) vinylformic acid fluorinated ester.Japanese kokai publication sho 59-117503 communique, spy open clear 59-117504 communique and the flat 3-163004 communique of Te Kai and then disclose to react under alkaline condition with (methyl) acryloyl halide and fluorine-containing alcohol and generate fluorine-containing (methyl) acrylate.
Another kind of is that starting raw material also can prepare fluorine-containing (methyl) acrylate with fluorine-containing haloalkane, as: Japanese Patent Publication 39-18112 communique, Japanese Patent Publication 48-30611 communique, the special fair 4-16451 communique of Japan, the special fair 4-16452 communique of Japan, the special fair 9-59215 communique of Japanese Patent Publication 61-57813 communique and Japan etc.
In the presence of catalyzer and stopper, by transesterify, the method that is prepared senior (methyl) alkyl acrylate by rudimentary (methyl) alkyl acrylate is known.Because the special chemical property of fluorine-containing alcohol, at present also not about being the report of raw material mass preparation fluorine-containing (methyl) acrylate by (methyl) acrylate and fluorine-containing alcohol.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of fluorinated acrylate monomer in the presence of catalyzer and stopper, makes high purity fluorinated acrylate monomer by transesterification reaction by alkyl acrylate and fluorine-containing alcohol.
Among the present invention, term acrylate is meant acrylate and methacrylic ester.
The preparation method of fluorinated acrylate monomer of the present invention, alkyl acrylate and fluorine-containing alcohol are in the presence of catalyzer and stopper, by the alkyl alcohol formation azeotropic mixture of excessive alkyl acrylate and generation.Distillate the mixture of alkyl acrylate and fluorinated acrylate from equilibrium system, this mixture obtains the high purity fluorinated acrylate monomer after separating by high-efficient spiral-screen column.
Alkyl acrylate of the present invention is shown in structural formula I:
Wherein, R
1Be independently selected from hydrogen or methyl; R
2Be independently selected from the C of hydroxyl or amido replacement
1-C
22The straight or branched alkyl, preferred C
1-C
5Alkyl, more preferably methyl.These alkyl acrylates are as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid dimethylin ethyl ester, (methyl) Hydroxyethyl acrylate and (methyl) Propylene glycol monoacrylate etc.
Described fluorine-containing alcohol is the C that is replaced by a fluorine atom at least
1-C
22Saturation unit alcohol, as: 2,2,2 tfifluoroethyl alcohol, 2,2-difluoro propyl alcohol, 3,3, the 3-trifluoropropanol, 2,2,3, the 3-C3-Fluoroalcohol, 1,1-dihydro five fluorine propyl alcohol, hexafluoroisopropanol, 4,4,4-three fluoro butanols, 2,2,3,4,4,4-hexafluoro butanols, 1,1-dihydro perfluor butanols, 4,4,5,5, the 5-Pentafluorobenzyl pentanol, 1,1,5-three hydrogen octafluoropentanols, 1,1-dihydro perfluor hexanol, 1,1,2,2-perfluor hexanol, 1,1,7-three hydrogen perfluor enanthol, 1,1,2,2-tetrahydrochysene perfluor octanol, 1,1-dihydro perfluor octanol, 1,1,9-three hydrogen perfluor nonyl alcohols, 1,1,2,2-tetrahydrochysene perfluor decyl alcohol, 1,1,11-three hydrogen perfluor undecyl alcohols, 1,1,2,2-tetrahydrochysene perfluor lauryl alcohol, 1,1,2,2-tetrahydrochysene perfluor tetradecyl alcohol, 1,1-dihydro perfluor tetradecyl alcohol, 1,1,2,2-tetrahydrochysene perfluor hexadecanol, 1,1-dihydro perfluor stearyl alcohol and 1,1,2,2-tetrahydrochysene perfluor eicosanol etc.In preparation process, after fluorine-containing alcohol added, making in the reaction system alkyl methacrylate or alkyl acrylate and fluorine-containing alcohol mol ratio was 1.05: 1-10: 1, and preferred 1: 1-5: 1.
Stopper of the present invention is selected from phenols or aromatic amine compounds, as: diphenyl sulfide, thiodiphenylamine, quinhydrones monomethyl ether, Resorcinol, phenol, 4-methyl-2,6-tert.-butyl phenol, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base or 4-oxygen-2,2,6, one of 6-tetramethyl piperidine-N-oxygen base and composition thereof.The consumption of described stopper under each situation is 10-5,000ppm.
Catalyzer of the present invention comprises organic and mineral acid catalyst, organic and those skilled in the art such as inorganic alkaline catalyst, salt, metal oxide-type catalyzer and organo-metallic catalyst catalyzer commonly used in carrying out transesterification reaction.Wherein, an acidic catalyst include but not limited to sulfuric acid, tosic acid, methylsulfonic acid, trifluoromethayl sulfonic acid, Phenylsulfonic acid, xylene monosulfonic acid, naphthene sulfonic acid, Witco 1298 Soft Acid, phosphoric acid and (or) phosphoric anhydride, trifluoroacetic anhydride etc., also can be their mixture; Basic catalyst includes but not limited to sodium ethylate, potassium ethylate, salt of wormwood, yellow soda ash, lime carbonate, sodium hydroxide, potassium hydroxide and calcium hydroxide etc., also can be their mixture; The catalyzer of other suggestion also comprises C
1-C
4The titanium alcoholate of-alkyl, as: metatitanic acid tetramethyl--, tetraethyl--, tetra isopropyl-, four n-propyls-, four isobutyl-s-and tetra-n-butyl-ester (referring to EP-B1298867, EP-A2960877) and titanium phenates (German Patent DOS2008618); Metallo-chelate, as: the inner complex of hafnium, titanium, zirconium or calcium; The organic tin catalyzer, as: dibutyl tin oxide and butyl stannic oxide etc.In the reaction of synthetic fluorine-containing (methyl) acrylate of transesterification reaction of the present invention, can use the catalyzer of 30% weight at the most.
It is to finish in the reactor heating that can use steam, infrared, oil bath, electricity etc. or a plurality of previous reaction device that transesterify of the present invention prepares fluorinated acrylate technology, preferably carry out in a reactor or two placed in-line reactors, reactor has the rectifying tower of at least one attaching and the condenser of conventional design is housed if necessary.Described reactor heating needs be equipped with mechanical stirring device with (or) also need to be connected vacuum unit in the internal circulation pump.
Rectifying tower has known design and has the internals (for example: bubble cap plate, Suo Man tower tray, valve tray, screen tray or double-pass tray) that possesses isolating active or contain stopping composition in bulk or that pile up.The tower that is connected on the reactor has a common 10-100 theoretical tray.Reflux ratio generally is 1-15: 1, and preferred 1-5: 1.Condenser has known design equally, for example: tubulose or plate heat exchanger.
A kind of preparation method of fluorinated acrylate monomer of the present invention, it comprises the steps:
1. with alkyl acrylate and 10-5, the 000ppm stopper adds in the reaction vessel, add the fluorine-containing alcohol thorough mixing then after, add catalyzer again.
2. stir down at shielding gas (as: nitrogen), different according to alkyl acrylate that adds and fluorine-containing alcohol boiling point, adopt normal pressure or pressure reducing mode to mixture heating up to boiling.Distillation is except that alkyl alcohol that produces in the dereaction and excessive alkyl acrylate.When detecting less than the alkyl alcohol in the reaction mixture, chromatogram stops heating.
3. the mixture with step 2 distillation back gained carries out just steaming under normal pressure or decompression, to remove catalyzer.Use high-efficient spiral-screen column in the presence of stopper, mixture to be separated afterwards and obtain fluorinated acrylate.
The beneficial effect that the present invention realizes:
The preparation method of fluorinated acrylate monomer of the present invention adopts alkyl acrylate and fluorine-containing alcohol in the presence of catalyzer and stopper, makes fluorinated acrylate monomer purity greater than more than 99.9% by transesterification reaction.
Embodiment
Below describe technical scheme of the present invention in detail.Only for the explanation concrete grammar, the scale of this method is not subjected to the restriction of embodiment to the embodiment of the invention.
Embodiment 1
Use is equipped with the rectifying tower of known structure and churned mechanically 1L4 mouth flask as reactor.
At first, in reactor, drop into 400.5g (4 moles) methyl methacrylate, the 4-acetamido-2 of (182.1g 1 mole) hexafluoro butanols, 0.04g, 2,6,6-tetramethyl piperidine-N-oxyradical adds 0.74g (0.003 mole) metatitanic acid tetramethyl ester (purity 70%), the setting stirring velocity is 130r/min, with the speed of 20ml/min nitrogen is imported in the reactor.Begin heating, under normal pressure, carry out transesterification reaction.When the temperature in the reactor was increased to 101 ℃, mixture came to life, and began to collect the azeotropic mixture of distilled methyl alcohol/methyl methacrylate outside system.Between the reaction period, momentarily take a sample the reaction solution in reactor, analyze, measure transformation efficiency with gas-chromatography.
After 4 hours, transformation efficiency reaches 90% in the reaction beginning, finishes reaction.Reaction times is 4 hours.Amount with gas chromatographic analysis distilled methyl alcohol/methyl methacrylate azeotropic mixture is 68.6g, and methanol content is 42.1% (28.8g), and methyl methacrylate content is 57.9% (39.8g).
The mixture that obtains after reaction finished under the 18000 handkerchief conditions, by underpressure distillation, is removed catalyzer and stablizer at 115 ℃, is not contained the mixture of catalyzer and stablizer.With the 613.4g mixture that gas chromatographic analysis obtains, methyl methacrylate is 44.2%, and the hexafluoro butanols is 4.5%, and methacrylic acid hexafluoro butyl ester is 51.2%, and transformation efficiency is 91.9%.
And then use high-efficient spiral-screen column to separate each raw material and resultant, obtain the methacrylic acid hexafluoro butyl ester of purity more than 99.9%.
By the methacrylic acid hexafluoro butyl ester that obtains by rectifying tower as can be known, be 91.9% for the transformation efficiency of hexafluoro butanols, yield is 89.6%.
Embodiment 2
Reaction unit is identical with embodiment 1.
In reactor, drop into 300.4g (3 moles) methyl methacrylate, the Resorcinol of (182.1g 1 mole) hexafluoro butanols, 0.84g, add 1.0g (0.004 mole) Dibutyltin oxide, the setting stirring velocity is 130r/min, speed with 20ml/min imports air in the reaction solution, begins heating.When the temperature in the reactor was increased to 101 ℃, mixture came to life, and began to collect the azeotropic mixture of distilled methyl alcohol/methyl methacrylate outside system.Between the reaction period, momentarily take a sample the reaction solution in reactor, analyze, measure transformation efficiency with gas-chromatography.
After 4 hours, transformation efficiency reaches 90% in the reaction beginning, finishes reaction.Reaction times is 4 hours.The amount that records distilled methyl alcohol/methyl methacrylate azeotropic mixture is 66.3g, and methanol content is 42.5% (28.2g), and methyl methacrylate content is 57.5% (38.1g).
The mixture that obtains after reaction finished under the 18000 handkerchief conditions, by underpressure distillation, is removed catalyzer and stablizer at 115 ℃, is not contained the mixture of catalyzer and stablizer.With the 416.2g mixture that gas chromatographic analysis obtains, methyl methacrylate is 39.7%, and the hexafluoro butanols is 4.8%, and methacrylic acid hexafluoro butyl ester is 55.4%, and transformation efficiency is 91.8%.
And then use high-efficient spiral-screen column to separate each raw material and resultant, obtain the methacrylic acid hexafluoro butyl ester of purity more than 99.9%.
By the methacrylic acid hexafluoro butyl ester that obtains by rectifying tower as can be known, be 91.8% for the transformation efficiency of hexafluoro butanols, yield is 89.4%.
Embodiment 3
Reaction unit is identical with embodiment 1.
In reactor, drop into 300.4g (3 moles) methyl methacrylate, 232.1g (1 mole) octafluoropentanol, the thiodiphenylamine of 0.16g.Then, add 2.77g (0.02 mole) salt of wormwood, settings stirring velocity is 130r/min, with the speed of 20ml/min air is imported in the reaction solution, begins to heat.When the temperature in the reactor was increased to 107 ℃, mixture came to life, and began to collect the azeotropic mixture of distilled methyl alcohol/methyl methacrylate outside system.Between the reaction period, momentarily take a sample the reaction solution in reactor, analyze, measure transformation efficiency with gas-chromatography.
After 4 hours, finish reaction in the reaction beginning, the amount of collecting distilled methyl alcohol/methyl methacrylate azeotropic mixture altogether is 65.9g, and methanol content is 35.6% (27.8g), and methyl methacrylate content is 64.4% (38.1g).
The mixture that obtains after reaction finished under the 18000 handkerchief conditions, by underpressure distillation, is removed catalyzer and stablizer at 118 ℃, is not contained the mixture of catalyzer and stablizer.With the 466.2g mixture that gas chromatographic analysis obtains, methyl methacrylate is 38.2%, and the hexafluoro butanols is 7.0%, and methacrylic acid hexafluoro butyl ester is 54.8%, and transformation efficiency is 88.7%.
And then use high-efficient spiral-screen column to separate each raw material and resultant, obtain the methacrylic acid hexafluoro butyl ester of purity more than 99.9%.
By the methacrylic acid hexafluoro butyl ester that obtains by rectifying tower as can be known, be 88.7% for the transformation efficiency of hexafluoro butanols, yield is 86.5%.
Embodiment 4
Use is equipped with the rectifying tower of known structure and churned mechanically 3L4 mouth flask as reactor.
In reactor, drop into 1051.3g (10.5 moles) methyl methacrylate, the 4-acetamido-2,2,6 of 637.4g (3.5 moles) hexafluoro butanols, 0.14g, 6-tetramethyl piperidine-N-oxyradical.Then, add 17.2g (0.1 mole) tosic acid, settings stirring velocity is 130r/min, with the speed of 20ml/min air is imported in the reaction solution, begins to heat.When the temperature in the reactor was increased to 101 ℃, mixture came to life, and began to collect the azeotropic mixture of distilled methyl alcohol/methyl methacrylate outside system.Between the reaction period, momentarily take a sample the reaction solution in reactor, analyze, measure transformation efficiency with gas-chromatography.
After 4 hours, finish reaction in the reaction beginning, the amount of collecting distilled methyl alcohol/methyl methacrylate azeotropic mixture altogether is 208.4g, and methanol content is 47.8% (99.7g), and methyl methacrylate content is 52.2% (108.7g).
The mixture that obtains after reaction finished under the 18000 handkerchief conditions, by underpressure distillation, is removed catalyzer and stablizer at 115 ℃, is not contained the mixture of catalyzer and stablizer.With the 1480.3g mixture that gas chromatographic analysis obtains, methyl methacrylate is 41.3%, and the hexafluoro butanols is 5.3%, and methacrylic acid hexafluoro butyl ester is 53.5%, and transformation efficiency is 91.1%.
And then use high-efficient spiral-screen column to separate each raw material and resultant, obtain the methacrylic acid hexafluoro butyl ester of purity more than 99.9%.
By the methacrylic acid hexafluoro butyl ester that obtains by rectifying tower as can be known, be 91.1% for the transformation efficiency of hexafluoro butanols, yield is 89.0%.
Embodiment 5
Use is equipped with the rectifying tower of known structure and churned mechanically 3L4 mouth flask as reactor.
At first, in reactor, drop into 1051.3g (10.5 moles) methyl methacrylate, the thiodiphenylamine of 637.4g (3.5 moles) hexafluoro butanols, 0.8g.Then, add 15.7g (0.15 mole) vitriol oil, settings stirring velocity is 130r/min, with the speed of 20ml/min air is imported in the reaction solution, begins to heat.When the temperature in the reactor was increased to 101 ℃, mixture came to life, and began to collect the azeotropic mixture of distilled methyl alcohol/methyl methacrylate outside system.Between the reaction period, momentarily take a sample the reaction solution in reactor, analyze, measure transformation efficiency with gas-chromatography.
After 5 hours, finish reaction in the reaction beginning.Collect distilled methyl alcohol/methyl methacrylate azeotropic mixture 208.4g altogether, wherein methanol content is 47.8% (99.7g), and methyl methacrylate content is 52.2% (108.7g).
The mixture that obtains after reaction finished under the 18000 handkerchief conditions, by underpressure distillation, is removed catalyzer and stablizer at 115 ℃, is not contained the mixture of catalyzer and stablizer.With the 1480.3g mixture that gas chromatographic analysis obtains, methyl methacrylate is 41.3%, and the hexafluoro butanols is 5.3%, and methacrylic acid hexafluoro butyl ester is 53.2%, and transformation efficiency is 90.9%.
And then use high-efficient spiral-screen column to separate each raw material and resultant, obtain the methacrylic acid hexafluoro butyl ester of purity more than 99.9%.
By the methacrylic acid hexafluoro butyl ester that obtains by rectifying tower as can be known, be 90.9% for the transformation efficiency of hexafluoro butanols, yield is 88.3%.
Claims (10)
1. the preparation method of a fluorinated acrylate monomer comprises the following steps: alkyl acrylate and fluorine-containing alcohol in the presence of catalyzer and stopper, by the alkyl alcohol formation azeotropic mixture of excessive alkyl acrylate and generation; Isolate the mixture of alkyl acrylate and fluorinated acrylate again from system, in the presence of stopper, this mixture obtains fluorinated acrylate monomer after separating by rectifying tower.
2. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that comprising the steps:
A. with alkyl acrylate and 10-5, the 000ppm stopper adds in the reaction vessel, add the fluorine-containing alcohol thorough mixing then after, add catalyzer again;
B. under shielding gas, stir, different according to alkyl acrylate that adds and fluorine-containing alcohol boiling point, adopt normal pressure or pressure reducing mode to mixture heating up to boiling; Distillation is except that alkyl alcohol that produces in the dereaction and excessive alkyl acrylate; When detecting less than the alkyl alcohol in the reaction mixture, chromatogram stops heating;
C. the mixture with step b distillation back gained carries out just steaming under normal pressure or decompression, to remove catalyzer; Use high-efficient spiral-screen column in the presence of stopper, mixture to be separated afterwards and obtain fluorinated acrylate.
3. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that described alkyl acrylate is shown in structural formula I:
Wherein, R
1Be independently selected from hydrogen or methyl; R
2Be independently selected from the C of hydroxyl or amido replacement
1-C
22The straight or branched alkyl.
4. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that the C of described fluorine-containing alcohol for being replaced by a fluorine atom at least
1-C
22Saturation unit alcohol.
5. the preparation method of fluorinated acrylate monomer according to claim 1 and 2, it is characterized in that (methyl) alkyl acrylate and fluorine-containing alcohol are according to 1.05: 1-10: 1 ratio is mixed.
6. the preparation method of fluorinated acrylate monomer according to claim 1, it is characterized in that described stopper is selected from diphenyl sulfide, thiodiphenylamine, quinhydrones monomethyl ether, Resorcinol, phenol, 4-methyl-2,6-tert.-butyl phenol, 4-hydroxyl-2,2,6,6-tetramethyl piperidine-N-oxygen base or 4-oxygen-2,2,6, one of 6-tetramethyl piperidine-N-oxygen base and composition thereof.
7. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that described catalyzer comprises organic and mineral acid catalyst, organic and inorganic alkaline catalyst, salt, metal oxide-type catalyzer and organo-metallic catalyst.
8. according to the preparation method of claim 1,2 or 7 described fluorinated acrylate monomers, the usage quantity of catalyzer is the 0.1-30% of pure weight.
9. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that described theoretical number of plates of rectifying tower is 10-100.
10. the preparation method of fluorinated acrylate monomer according to claim 1 is characterized in that described rectifying tower reflux ratio is 1-15: 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217703A (en) * | 2020-02-21 | 2020-06-02 | 上海仰世实业有限公司 | Preparation method of hexafluorobutyl acrylate |
| CN111393289A (en) * | 2020-05-09 | 2020-07-10 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
| CN111440475A (en) * | 2020-05-24 | 2020-07-24 | 华月圆 | UV orange-peel agent and orange-peel paint |
| CN112585113A (en) * | 2018-08-14 | 2021-03-30 | 中央硝子株式会社 | Method for purifying fluorine-containing polymerizable monomer by distillation |
-
2009
- 2009-10-29 CN CN200910153219A patent/CN101691328A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112585113A (en) * | 2018-08-14 | 2021-03-30 | 中央硝子株式会社 | Method for purifying fluorine-containing polymerizable monomer by distillation |
| CN112585113B (en) * | 2018-08-14 | 2023-08-22 | 中央硝子株式会社 | Process for distillative purification of fluorine-containing polymerizable monomers |
| CN111217703A (en) * | 2020-02-21 | 2020-06-02 | 上海仰世实业有限公司 | Preparation method of hexafluorobutyl acrylate |
| CN111393289A (en) * | 2020-05-09 | 2020-07-10 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
| CN111393289B (en) * | 2020-05-09 | 2022-09-13 | 安徽灵达高新材料有限公司 | Method for preparing fluorinated acrylate from fluorinated alcohol |
| CN111440475A (en) * | 2020-05-24 | 2020-07-24 | 华月圆 | UV orange-peel agent and orange-peel paint |
| CN111440475B (en) * | 2020-05-24 | 2022-09-30 | 华月圆 | UV orange-peel agent and orange-peel paint |
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Application publication date: 20100407 |