CN104926966A - Fluorine-containing polymer for low-energy surface coating and preparation method thereof - Google Patents
Fluorine-containing polymer for low-energy surface coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a fluorine-containing polymer for low-energy surface coating and a preparation method thereof. The molecular formula of the polymer is [CH2(CH3)C(COOCH(CF2CF3)(C(CF3)2))]n. The preparation method comprises the following steps: (1) reducing pentafluoro ethyl isopropyl ketone into alcohol; (2) reacting obtained alcohol with methacryloyl chloride to generate fluorine-containing unsaturated ester monomers; (3) polymerizing the fluorine-containing unsaturated ester monomers to obtain fluorine-containing polymer. The fluorine-containing polymer has the characteristics of easily-available raw material, simple synthesis, low cost, high performance/price ratio, and excellent surface performance.
Description
Technical field
The invention belongs to fluoropolymer and technology of preparing thereof, particularly a kind of fluoropolymer technology of preparing of low-energy surface coating.
Background technology
Fluorine atom is that in all elements, electronegativity is maximum, and Van der Waals atomic radius is minimum in addition to hydrogen, and atomic pola-rizability is again minimum.Therefore, in fluorocarbon chain, C-F key is highly stable, and when being subject to chemical reagent or being subject to thermal effect at high temperature, first what in molecule, fracture occurs is C-C key instead of C-F key, and due to the effect of C-F key, makes the Distance Shortened of C-C key, and bond energy increases, also more firm.Because the van der Waals radius of fluorine atom is slightly larger than hydrogen atom, but less than the atomic radius of other all elements, just carbon skeleton is tightly encased, play good " shielding effect ", not easily have an effect with other chemical reagent, the gravitation between fluorocarbon is also very little.These constitutional featuress of all fluorocarbon chains, make fluorochemicals have high surface, high heat-resistant stability and high chemical stability; Its fluorine-containing alkyl not only hydrophobic but also hate oil, i.e. so-called " three is high ", " two hate ".
The above-mentioned special property of fluorochemicals makes it become excellent low energy coatings material, is widely used in the surface modification of body material, improve matrix corrosion-resistant, friction, wearing and tearing and fatigability.
Fiber base material fluorochemicals is carried out process to improve it to refuse water, refuse the existing report of technology that is oily and resistance to soil corrosion.The fluorochemicals reported comprises fluorinated acrylate polymer, fluorine-containing carbodiimide compound, fluorinated ester and fluorine-containing urethane and carbamide compound.
In addition, fluorochemicals is also for the surface modification of hard substrate (as brick, stone and glass).Hard substrate after being modified both can delay the variable color of its brick caused because being exposed to rainwater and greasy dirt and stone, also can delay its by ectocine the speed of catamorphism.
The coating that performance is excellent is especially generally (as C containing long perfluoroalkyl chain
6f
12~ C
12f
25) fluorochemicals because the structure of this long perfluor carbochain gives fluorochemicals low-down surface energy, the base material after such fluorochemicals process has excellent water and oil-resistant.Comprehensive cost and performance are considered, best coating is preferably containing straight chain perfluoro capryl (C
8f
17) compound.
But research shows: PFOS/PFOA compounds is one of material of the most difficult degradation found at present, and they not only have persistence, biological accumulation, even also have the possibility of long distance environment migration.Organism is once take in PFOS/PFOA class fluorochemicals, it can be distributed in blood of human body and liver, due to the stability that it is intrinsic, therefore be difficult to be decomposed by the metabolism of human body, such as " half efflux time " of perfluoro octyl sulfonic acid in human body reaches 8.7 years, namely PFOS/PFOA class fluorochemicals has very high bioconcentration and multiple toxicity in human body, not only can cause the injury to human respiratory, and ewborn infant even can be caused dead.Accordingly, Environmental Protection Agency (EPA) has issued voluntary 2010 ~ 2015 years Perfluorocaprylic Acids and its esters environmental planning, i.e. 2010/15PFOA Stewardship Program; This plan regulation PFOS/PFOA class fluorochemicals can progressively be forbidden producing and selling and using.Therefore, develop brand-new degradable fluorocarbon to replace existing PFOS/PFOA class fluorocarbon surfactant comprehensively, and evaluate its biological degradability and the impact on environment simultaneously, become one of urgent theoretical investigation problem, and cause the great attention of various countries researchist.
From structure, the general optimum carbon fluorine chain length of low energy coatings fluorochemicals is 6 ~ 10.There is research to claim: the fluorocarbon surfactant of straight chain shows minimum surface tension under relatively high working concentration, and side chain fluorocarbon surfactant uses at relatively low concentration, reduce surface tension but more effective.
To sum up, we select with perfluorethyl isopropyl ketone is initial feed, has synthesized fluorine-containing methacrylate polymkeric substance, has raw material and is easy to get, synthesizes the features such as simple, cost is low, cost performance is high, product surface excellent performance.
Summary of the invention
The object of the present invention is to provide fluoropolymer of a kind of low-energy surface coating and preparation method thereof.
Method of the present invention comprises: (1) perfluorethyl isopropyl ketone is reduced into alcohol; (2) alcohol and methacrylic chloride react and generate fluorine-containing unsaturated ester monomer; (3) fluorine-containing unsaturated ester monomer polymerization obtains fluoropolymer.The method has following advantage: raw material is easy to get, technique is simple, cheap, reproducible.And polymkeric substance water and oil repellant performance is studied, find that product has excellent water and oil repellant.
The present invention is a kind of fluoropolymer of low-energy surface coating, and its structural formula is as follows:
Wherein, n>3.
The preparation method of above-mentioned fluoropolymer, comprises the steps:
(1) in-30 DEG C ~ room temperature and organic solvent, sodium borohydride and perfluorethyl isopropyl ketone reaction obtain fluoro-containing intermediate compound 1 in 5 ~ 10 hours; Described sodium borohydride and the mol ratio of perfluorethyl isopropyl ketone are 1 ~ 2:1.
Described organic solvent can be glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran (THF), methylene dichloride, DMF, benzene or 1,2-ethylene dichloride; Temperature of reaction is recommended as-10 DEG C ~ room temperature.
Step (1) product suggestion be followed successively by through aftertreatment purifying: cancellation react, successively with deionized water and saturated ammonium chloride solution washing, organic phase again through anhydrous sodium sulfate drying, filtration, underpressure distillation.Described quenching method: with dilute sulphuric acid or dilute hydrochloric acid solution cancellation reaction under ice-water bath.
(2) in-30 DEG C ~ room temperature and organic solvent, fluoro-containing intermediate 1, methacrylic chloride, alkali and solvent reaction obtain fluorine-containing methacrylate compound 2 in 1 ~ 10 hour; The mol ratio of described fluoro-containing intermediate 1, methacrylic chloride, alkali is 1:1 ~ 1.5:1 ~ 1; Described alkali is organic bases.
Described organic bases can be triethylamine, pyridine, N, N-diisopropyl ethyl amine, diethylamine, piperidines or N-methyl piperidine etc.
Described organic solvent is glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran (THF), methylene dichloride, DMF, benzene or 1,2-ethylene dichloride.
The product of step (2) is through processing purifying as follows: with the dilute sulphuric acid cancellation reaction of 5% under ice-water bath, use deionized water and saturated common salt water washing successively, organic phase, through anhydrous sodium sulfate drying, is filtered, underpressure distillation.
(3), in organic solvent with 30 DEG C ~ 200 DEG C, compound 2 and radical initiator heat polymerization reaction take place and obtain polymkeric substance 3 in 10 ~ 50 hours; The usage quantity of described radical initiator is 0.1% ~ 5% of compound 2 molar weight; Described radical initiator is azo compound, acyl peroxide, alkyl peroxide, hydroperoxide.
Described organic solvent is one of following or both mixtures: aliphatic hydrocrbon, clicyclic hydrocarbon, ether, ester, alcohol, ketone, DMSO; DMF.As normal hexane, normal heptane, hexanaphthene, benzene,toluene,xylene, ether, glycol dimethyl ether, diethylene glycol dimethyl ether, ethyl acetate, butylacetate, ethanol, Virahol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), DMSO, DMF, trichloroethane, phenylfluoroform or C
4f
90CH
3.Described organic solvent preferentially selects the solvent of low water solubility: ethyl acetate, butylacetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).The usage quantity of described solvent is recommended as 5% ~ 90% of reaction system total mass.
Through following aftertreatment and purifying in the product of step (3): filter, solid priority methyl alcohol and washing with acetone, after drying, obtain polymkeric substance.
Above-mentioned reaction is carried out under being recommended in protection of inert gas.Described gas is nitrogen, argon gas etc.
The reaction equation of described reaction is:
Method of the present invention has that raw material is easy to get, technique is simple, cheap, reproducible, and polymkeric substance of the present invention has excellent water and oil repellant.
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but these examples of implementation are only as illustrating, instead of limits the invention.
Embodiment
Below in conjunction with example, the present invention is described in further detail.
Embodiment 1: the synthesis of fluoro-containing intermediate compound 1
Add 2.28g sodium borohydride in 100mL jacketed reaction tubes, under argon shield, add 40mLTHF, ice-water bath is lowered the temperature, and slowly drips 19g perfluorethyl isopropyl ketone.Be added dropwise to complete rear system and move to room temperature reaction 12h.Careful reacting with the cancellation of 30mL5% aqueous sulfuric acid under ice-water bath, organic phase through deionized water and saturated ammonium chloride solution washing, then uses anhydrous sodium sulfate drying, filters.Air distillation removing methylene chloride, then underpressure distillation, final 18g colourless liquid 1.
Productive rate: 100%; Colourless liquid;
1h NMR (DMSO-d
6, 300MHz): δ (ppm) 5.17 (d, J=22.5Hz, (CF
3)
2cFCH (OH) CF
2cF
3, 1H), 8.42 (d, J=8.4Hz, (CF
3)
2cFCH (OH) CF
2cF
3, 1H);
19f NMR (CD
3oD; 282MHz;): δ (ppm)-73.40 ~-73.65 (3F);-77.46 ~-77.62 (3F);-84.30 (3F);-121.25 ~-122.50 (1F) ,-130.70 ~-132.10 (1F) ,-183.75 ~-184.05 (1F); GC-MS (EI): m/z149,199.
Embodiment 2: the synthesis of fluoro-containing intermediate compound 2
100mL jacketed reaction tubes, under argon shield, add 40mL diethylene glycol dimethyl ether, 14g compound 1 and 14mLN, N-diisopropyl ethyl amine, mixed system is cooled to-10 DEG C, slowly adds 5g methacrylic chloride under vigorous stirring, room temperature reaction 8h.Careful reacting with the cancellation of 30mL5% aqueous sulfuric acid under ice-water bath, organic phase through deionized water and saturated ammonium chloride solution washing, then uses anhydrous sodium sulfate drying, filters.Underpressure distillation, final 12g colourless liquid 2.
Productive rate: 70%; Colourless liquid;
1h NMR (CDCl
3, 300MHz): δ (ppm) 1.98 (s, 3H), 5.82 (s, 1H), 6.35 ~ 6.20 (m, 2H);
19f NMR (CDCl
3282MHz;): δ (ppm)-72.75 ~-73.00 (3F);-76.13 ~-76.30 (3F);-83.61 (3F);-119.54 ~-120.81 (1F) ,-124.90 ~-125.15 (1F) ,-183.10 ~-183.40 (1F);
13c NMR (100MHz, CDCl
3): δ (ppm) 17.804,129.964,133.714,163.066; IR (cm
-1): 2969.3,1764.3,1639.2,1459.6; HRMS (EI): m/z calcdfor (CF
3)
2cFCH (CF
2cF
3) OCO (CH
3) C=CH
2: 386.0176, found386.0172.
Embodiment 3: the synthesis of fluoropolymer
Wherein, n>3.
Add the ethyl acetate of 6.3mg Diisopropyl azodicarboxylate, 3g compound 2 and 2mL in 10mL tube sealing, argon gas seals after driving away the oxygen in system, and react 2 days at tube sealing is placed in 100 DEG C, system separates out a large amount of white solid.Filter, after solids with methanol and washing with acetone twice, dry 1.3g white powder fluoropolymer.
IR (cm
-1): 2974.7,1777.5,1483.4; Calculated value (Anal.Calcd for) C
10h
6f
12o
2: C, 31.10; H, 1.57; F, 59.04. measured value (Found): C, 31.52; H, 1.52; F, 58.19.
Embodiment 4: polymkeric substance water and oil repellant is tested
Coating solution is the mass concentration that polymkeric substance and 1,1,2-Refrigerant R 113 are made into is the solution of 3%.The preparation method of cover glass is as follows: cover glass cuts into the square piece of 15mm × 15mm, and square piece is immersed in ethanol and takes out with clean tweezers after cleaning, and oven drying, dries in the air to room temperature.Cover glass coating method is as follows: with careful one jiao that clamps square piece of clean tweezers, square piece is inserted a moment in coating solution, afterwards, slowly takes out from solution stably, dries under room temperature.The square piece of 6 plated films is prepared according to above-mentioned preparation method.
The contact angle of test membrane and water and normal hexane respectively, often kind of solution surveys three times, averages for three times.Test condition: liquid volume 3 microlitre, height 0.5 centimetre, magnification 7 times.Result is as following table 1.
The contact angle of cover glass and water and normal hexane when table 1 film and non-film
Claims (14)
1. the degradability low-energy surface coating fluoropolymer as shown in structural formula 3:
Wherein, n>3.
2. degradability fluoropolymer as shown in Equation 3 according to claim 1, is characterized in that described preparation method comprises the steps:
(1) in-30 DEG C ~ room temperature and organic solvent, sodium borohydride and perfluorethyl isopropyl ketone reaction obtain fluoro-containing intermediate compound 1 in 5 ~ 10 hours; Described sodium borohydride and the mol ratio of perfluorethyl isopropyl ketone are 1 ~ 2:1;
(2) in-30 DEG C ~ room temperature and organic solvent, fluoro-containing intermediate 1, methacrylic chloride, alkali and solvent reaction obtain fluorine-containing methacrylate compound 2 in 1 ~ 10 hour; The mol ratio of described fluoro-containing intermediate 1, methacrylic chloride, alkali is 1:1 ~ 1.5:1 ~ 1.; Described alkali is organic bases;
(3), in organic solvent with 30 DEG C ~ 200 DEG C, compound 2 and radical initiator heat polymerization reaction take place and obtain polymkeric substance 3 in 10 ~ 50 hours; The usage quantity of described radical initiator is 0.1% ~ 5% of compound 2 molar weight; Described radical initiator is azo compound, acyl peroxide, alkyl peroxide or hydroperoxide.
3. preparation method according to claim 2, is characterized in that described reaction is carried out under protection of inert gas.
4. preparation method according to claim 2, it is characterized in that step (1) or the organic solvent described in (2) are glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethyleneglycol dimethyl ether, tetrahydrofuran (THF), methylene dichloride, dimethyl formamide, benzene or 1,2-ethylene dichloride; Temperature of reaction is-10 DEG C ~ room temperature.
5. preparation method according to claim 2, is characterized in that the product of step (1) is followed successively by through aftertreatment: cancellation react, successively with deionized water and saturated ammonium chloride solution washing, organic phase again through anhydrous sodium sulfate drying, filtration, underpressure distillation.
6. preparation method according to claim 5, is characterized in that described quenching method is: with dilute sulphuric acid or dilute hydrochloric acid solution cancellation reaction under ice-water bath.
7. preparation method according to claim 2, is characterized in that the organic bases described in step (2) is triethylamine, pyridine, N, N-diisopropyl ethyl amine, diethylamine, piperidines or N-methyl piperidine.
8. preparation method according to claim 2, it is characterized in that the product of step (2) is through processing purifying as follows: with the dilute sulphuric acid cancellation reaction of 5% under ice-water bath, use deionized water and saturated common salt water washing successively, organic phase is through anhydrous sodium sulfate drying, filter, underpressure distillation.
9. preparation method according to claim 2, the radical initiator that it is characterized in that in step (3) is one of following: Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidation two (2,4-dichloro-benzoyl), diacetyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, isopropyl benzene hydroperoxide or tertbutyl peroxide.
10. preparation method according to claim 2, is characterized in that organic solvent described in step (3) is one of following or both mixtures: aliphatic hydrocrbon, clicyclic hydrocarbon, ether, ester, alcohol, ketone, dimethyl Asia Sulfone or dimethyl amide.
11. preparation methods according to claim 10, is characterized in that organic solvent described in step (3) is normal hexane, normal heptane, hexanaphthene, benzene,toluene,xylene, ether, glycol dimethyl ether, diethylene glycol dimethyl ether, ethyl acetate, butylacetate, ethanol, Virahol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), dimethyl Asia Sulfone, dimethyl amide, trichloroethane, phenylfluoroform or C
4f
90CH
3.
12. preparation methods according to claim 11, is characterized in that described organic solvent preferentially selects the solvent of low water solubility: ethyl acetate, butylacetate, methyl ethyl ketone, methyl iso-butyl ketone (MIBK).
13. preparation methods according to claim 2, is characterized in that the usage quantity of solvent described in step (3) is 5% ~ 90% of reaction system total mass.
14. preparation methods according to claim 2, is characterized in that the product of step (3) is through following aftertreatment and purifying: filter, solid priority methyl alcohol and washing with acetone, obtain polymkeric substance after drying.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028662A (en) * | 2019-04-22 | 2019-07-19 | 重庆玉瓶科技有限公司 | A kind of perfluoro liquid polymer and preparation method thereof, purposes |
| CN115746193A (en) * | 2022-11-30 | 2023-03-07 | 国网安徽省电力有限公司电力科学研究院 | Low-surface-energy fluorocarbon polymer for transformer substation fire protection and preparation method thereof |
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| WO2002016306A2 (en) * | 2000-08-18 | 2002-02-28 | 3M Innovative Properties Company | Degradable, amorphous, fluoroacrylate polymers |
| CN1465602A (en) * | 2002-06-17 | 2004-01-07 | 王存孝 | Silicofluoride containing acrylic copolyresin emulsion and paint |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
| CN102041681A (en) * | 2009-10-14 | 2011-05-04 | 江南大学 | Method for preparing short-chain branch water and oil repellent finishing agent containing modified nano-oxide and fluorine |
-
2014
- 2014-03-19 CN CN201410103201.4A patent/CN104926966A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016306A2 (en) * | 2000-08-18 | 2002-02-28 | 3M Innovative Properties Company | Degradable, amorphous, fluoroacrylate polymers |
| CN1465602A (en) * | 2002-06-17 | 2004-01-07 | 王存孝 | Silicofluoride containing acrylic copolyresin emulsion and paint |
| CN102041681A (en) * | 2009-10-14 | 2011-05-04 | 江南大学 | Method for preparing short-chain branch water and oil repellent finishing agent containing modified nano-oxide and fluorine |
| CN102010334A (en) * | 2010-10-25 | 2011-04-13 | 江苏梅兰化工有限公司 | Method for preparing fluorine-containing acrylate |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110028662A (en) * | 2019-04-22 | 2019-07-19 | 重庆玉瓶科技有限公司 | A kind of perfluoro liquid polymer and preparation method thereof, purposes |
| CN110028662B (en) * | 2019-04-22 | 2021-07-16 | 深圳市玉瓶科技有限公司 | Perfluoro liquid polymer and its preparation method and use |
| CN115746193A (en) * | 2022-11-30 | 2023-03-07 | 国网安徽省电力有限公司电力科学研究院 | Low-surface-energy fluorocarbon polymer for transformer substation fire protection and preparation method thereof |
| CN115746193B (en) * | 2022-11-30 | 2023-08-01 | 国网安徽省电力有限公司电力科学研究院 | Low-surface-energy fluorocarbon polymer for fire protection of transformer substation and preparation method thereof |
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