CN102010334A - Method for preparing fluorine-containing acrylate - Google Patents
Method for preparing fluorine-containing acrylate Download PDFInfo
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Abstract
The invention belongs to the technical field of textile fabric finishing agents, and relates to a method for preparing an intermediate fluorine-containing acrylate monomer of a water-proof and oil-proof organic fluorine fabric finishing agent. The method is characterized by comprising the following steps of: (1) in the presence of a reducing agent, preparing polyfluoroalcohol by using a perfluoroalkylacyl compound as a raw material; and (2) slowly dripping (methyl) acryloyl chloride to prepare fluorine-containing acrylate in the presence of a catalyst by using the polyfluoroalcohol prepared in the step (1) and using phenothiazine as a polymerization inhibitor. The number of long-chain perfluoroalkyl carbon atoms in the prepared fluorine-containing acrylate is less than 8, and the fluorine-containing acrylate can be degraded and has no biological accumulation. The fluorine-containing acrylate has no hidden dangers of long-chain perfluoroalkyl to destroy the environment and harm human health. Fluorine-containing acrylate copolymer emulsion prepared by using the prepared fluorine-containing acrylate monomer is used as a water-proof and oil-proof finishing agent for textiles, and the finished textiles have excellent water-proof and oil-proof performance.
Description
Technical field
The invention belongs to the fabric finishing agent technical field, relate to a kind of fluorine-containing comonomer---preparation method of fluorinated acrylate of acrylate containing fluorine waterproof and oilproof organic fluorine fabric finishing agent.
Background technology
At present, along with the needs of the development of domestic and international textiles and people's life, people are to development of new, the cry of fabric finishing agent is more and more stronger efficiently.The organic fluorine fabric finishing agent has the excellent hydrophobic oleophobic performance that can give the fabric excellence, simultaneously because the electronegativity of its F atom is big, diameter is little, the C-F key can be shielded, under various environment such as strong acid, highly basic, high temperature and high radiation, all demonstrate very high stability, also, make the fabric of handling keep the ventilation property and the water vapour permeability of good hand feeling, excellence because it has the characteristics of lower concentration, high effect.Fluorine-containing textile finishing agent is compared with the finishing composition of other type in each side such as water and oil-resistant, didirtresistance, washing fastness, rub resistance, erosion resistances all has incomparable advantage.Therefore, in numerous fabric finishing agents, the organic fluorine fabric finishing agent just causes the great interest of people and constantly developed once coming out, and becomes the main flow of current waterproof oil-proof finishing agent.
The good film-forming property of polyacrylic ester family macromolecule own, network structure are comparatively loose, and good water-repellancy is arranged, and raw material is easy to get, and method for making is simple, the characteristics that cost is low, but do not possess oil preventing performance.On the polyacrylic ester polymer side chain, introduce fluoro-containing group, can obtain the acrylate containing fluorine fabric finishing agent of waterproof and oilproof.The fluorine-containing comonomer of acrylate containing fluorine fabric finishing agent is a fluorinated acrylate, and the fluorocarbon in the fluorinated acrylate monomer partly is the key component of giving the fabric waterproof oil preventing performance, is the core of whole fluorine-contained finishing agent.
The fluorine-containing comonomer of fluorine-containing waterproof oil-proof finishing agent both domestic and external at present mainly is the acrylate of belt length chain perfluoroalkyl, mostly is carbonatoms at 6～10 perfluoroalkyl, and the waterproof and oilproof performance when wherein perfluor segmental carbonatoms is 8 is best.And the research report of EPA is pointed out: the perfluoroalkyl of long-chain (carbonatoms is 8 or more) may decompose or be degraded to PFOA (Perfluorocaprylic Acid and its esters) or PFOS (PFO sulfonyl compound).EPA is at present still in the hazardness that continues assessment PFOA, and the roughly conclusion that draws now is that zooscopy only finds that " hint property evidence " shows that PFOA is a potential carcinogen matter.Any decomposition does not take place in PFOA and PFOS in environment He in the organism, have the biological accumulation of height, and therefore, the harm to HUMAN HEALTH can not be ignored the long-chain perfluoroalkyl acrylate as toxic chemical.
Existing in recent years report is attempted to substitute the long-chain perfluoroalkyl in the original structure with reducing perfluoroalkyl chain length way.As in patent US 2005027063, use the acrylate of the perfluoroalkyl of 3～4 carbon atoms, and in its multipolymer, introduce a plurality of solidification points, the waterproof oil-proof finishing agent is combined better with pending base material; In patent US 2006205864, the acrylate that fluorochemical monomer replaces for the α position, the group of substituted acrylate α position can be-F ,-Cl ,-Br ,-I ,-CN, contain fluoroalkyl, phenyl, phenylol etc.The carbonatoms of perfluoroalkyl is 1～6, though avoided PFOA or the PFOS harm to environment and organism.Reduce but correspondingly retreat dynamic contact angle, surface energy raises, and the waterproof and oilproof performance of gained multipolymer descends.
Summary of the invention
The objective of the invention is: fluorine-containing comonomer---the preparation method of fluorinated acrylate that the good organic fluorine fabric finishing agent of a kind of compliance with environmental protection requirements, waterproof and oilproof performance is provided.
For achieving the above object, the technical scheme of employing is: a kind of preparation method of fluorinated acrylate is characterized in that may further comprise the steps successively:
Step (1) preparation polyfluoro alcohol is raw material with the perfluoroalkyl acyl compound, in the presence of reductive agent, and by following reaction, preparation polyfluoro alcohol:
Wherein Y be-F ,-Cl or-OH; R
fFor-C
nF
2n+1Or
Wherein n is 1～6 integer, and p is 1～6 integer, and q is 1～10 integer, is preferably 0～2 integer, X is-F or-CF
3
The polyfluoro alcohol that step (2) preparation fluorinated acrylate is made by step (1) is stopper with the thiodiphenylamine, in the presence of catalyzer, obtains described fluorinated acrylate by following reaction:
R wherein
1For-H or-CH
3R
fFor-C
nF
2n+1Or
Wherein n is 1～6 integer, and p is 1～6 integer, and q is 1～10 integer, is preferably 0～2 integer, X is-F or-CF
3
Described step (1), temperature is controlled to be-10～20 ℃ in the reaction vessel, and reductive agent slowly is dissolved among the anhydrous solvent A, progressively drips the perfluoroalkyl acyl compound R then
f-CO-Y (Y=-F ,-Cl or-OH), dropwise back holding temperature-10～30 ℃, stirring reaction 4～10 hours.Stir then and simultaneously slowly add entry to remove excessive reductive agent, add 10% aqueous sodium hydroxide solution again, keep system temperature 5～10 ℃, filter after stirring 10～30min, filtrate concentrates with Rotary Evaporators in room temperature is bathed, obtain crude product, rectifying obtains polyfluoro alcohol R then
f-CH
2OH.
Described anhydrous solvent A is a kind of in ether, tetrahydrofuran (THF), the dioxane.The consumption of anhydrous solvent A is described perfluoroalkyl acyl compound R
f2～5 times of-CO-Y weight.
Described reductive agent is a kind of in lithium aluminum hydride, the sodium borohydride.Reductive agent and described perfluoroalkyl acyl compound R
fThe mol ratio of-CO-Y is 1.5～2.0.Excessive reductive agent adopts and slowly drips water earlier, is added dropwise to the 10%NaOH solution mode that doubles water again and removes.
Described step (2), the polyfluoro that makes with step (1) alcohol R
f-CH
2OH is a raw material, is dissolved among the solvent B in the reaction vessel, and be stopper with the thiodiphenylamine, in the presence of catalyzer, maintain the temperature in-20～10 ℃, slowly drip (methyl) acrylate chloride.Dropwise the back and stirred 0.5～2 hour, be warming up to 30～60 ℃, stirring and refluxing 2～8 hours.Then mother liquor is poured in the frozen water, it is neutral washing to organic phase with frozen water, obtains crude product, carries out obtaining fluorinated acrylate after the rectification under vacuum.
The mol ratio of described (methyl) acrylate chloride and described polyfluoro alcohol is 1.1～1.5.
Described solvent B is methylene dichloride, ether, trichloromethane, acetone, 1,1, a kind of in the 2-Freon 113.The consumption of solvent B is 2～5 times of described polyfluoro alcohol weight.
Described catalyzer is pyridine, triethylamine, N, a kind of in accelerine, yellow soda ash, salt of wormwood, Sodium Fluoride, the Potassium monofluoride.The mol ratio of catalyzer and described polyfluoro alcohol is 1.2～1.5.
Long-chain perfluoroalkyl institute carbon atom quantity is less than 8 in the prepared fluorinated acrylate of the present invention, and degradable, the lifeless matter cumulative bad.There is not the hidden danger of destroying environment, influencing human health.Utilize the prepared fluorinated acrylate of the present invention, preparation fluoro-acrylate copolymer emulsion, as the waterproof oil-proof finishing agent of textiles, processed fabric shows excellent waterproof and oilproof performance.
Embodiment
Provide embodiment below, the invention will be further described.
Embodiment 1～embodiment 5 in the presence of reductive agent, prepares polyfluoro alcohol for being raw material by step of the present invention (1) with the perfluoroalkyl acyl compound.Polyfluoro alcohol by step (1) makes prepares fluorinated acrylate by step (2) again.
The fluorinated acrylate of embodiment 6～embodiment 10 for making by embodiment 1～embodiment 5 respectively, the preparation fluoro-acrylate copolymer, method is carried out pre-emulsification for after polymer monomers, emulsifying agent, water, organic solvent are fed intake together with homogeneous emulsifying machine, forms pre-emulsion; Under the nitrogen protection inert conditions, the mode of initiator with the aqueous solution is added dropwise in the pre-emulsion, under 50～80 ℃, carried out emulsion copolymerization 4～15 hours.Wherein said polymer monomers is made up of fluorinated acrylate, non-fluorinated comonomers, cross-linking monomer three parts.Fluorinated acrylate described in the embodiment is made by embodiment 1～embodiment 5 respectively, and non-fluorinated comonomers is (methyl) octadecyl acrylate, and cross-linking monomer is methacrylic acid hydroxyl ethyl ester or N hydroxymethyl acrylamide.
Copolymer emulsion with gained is diluted to 3% at last, employing pads-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, adopted U.S.'s AATCC 22-2005 testing method and AATCC118-2002 testing method, fabric waterproof grade and grease proofing grade after the evaluation arrangement.
Embodiment 1
Preparation vinylformic acid 2,2,3,3,4,4,4-seven fluorine butyl esters
Under 5～10 ℃ of conditions, 7.57g (0.200mol) sodium borohydride slowly is dissolved in the 71.34g anhydrous diethyl ether, slowly drips 21.41g (0.100mol) perfluorobutyric acid again, after dropwising, at-10～-5 ℃ of following stirring reaction 10h.(consumption of water is greater than the amount of used reductive agent to remove excessive sodium borohydride to stir the slow simultaneously 10.0g of adding water then, less than total organic phase 1/5th), liquid agglutination this moment material, be added dropwise to 10% aqueous sodium hydroxide solution of 20.0g again, gelatinoid slowly forms particulate solid, whole process is emitted big heat, keeps system temperature at 5～10 ℃, stirring 30mi n after-filtration, and filtrate concentrates with Rotary Evaporators in room temperature is bathed, get crude product, rectifying obtains 16.59g 2,2,3 then, 3,4,4,4-seven fluoro-1-butanols CF
3CF
2CF
2CH
2OH, productive rate 82.9%.
With 15.00g (0.075mol) 2,2,3,3,4,4,4-seven fluoro-1-butanols, 7.84g pyridine, 59.70g methylene dichloride and 0.010g thiodiphenylamine add in the flask of band condenser.Temperature is 5 ℃ in cooling and the maintenance flask, drips 8.23g (0.091mol) acrylate chloride.Dropwise back restir 30min, be warming up to 30 ℃ of stirring and refluxing 2h.Then mother liquor is poured in the frozen water, it is neutral washing to organic phase with frozen water, obtains crude product (the fluorinated acrylate dichloromethane solution that contains a small amount of pyridine), gets 16.76g vinylformic acid 2,2,3,3,4,4,4-seven fluorine butyl ester CF after the rectification under vacuum
3CF
2CF
2CH
2OOCCH=CH
2, productive rate 88.0%.
Embodiment 2
Preparation methacrylic acid 1H, the own ester of 1H-perfluor
5.68g (0.150mol) lithium aluminum hydride slowly is dissolved in 0～5 ℃ in the 106.72g anhydrous tetrahydro furan, slowly drips 29.28g (0.088mol) perfluor caproyl chloride again, dropwise the back at-5～0 ℃ of following stirring reaction 8h.Stirring slowly adds 10.0g water down then, adds 10% aqueous sodium hydroxide solution of 20.0g again, keeps system temperature to filter behind 5～10 ℃ of stirring 20min, filtrate concentrates with Rotary Evaporators in room temperature is bathed, obtain crude product, rectifying obtains 22.93g 1H then, 1H-perfluor-1-hexanol CF
3(CF
2)
4CH
2OH, productive rate 86.8%.
With 21.14g (0.070mol) 1H, 1H-perfluor-1-hexanol, 10.11g triethylamine, 49.95g ether and 0.011g thiodiphenylamine add in the flask of band condenser. and the temperature in cooling and the maintenance flask is 0 ℃, begins to drip 9.70g (0.093mol) methacrylic chloride.Dropwise back restir 1h, be warming up to 40 ℃ of stirring and refluxing 3h.Then mother liquor is poured in the frozen water, it is neutral washing to organic phase with frozen water, obtains crude product, and rectification under vacuum gets 20.97g methacrylic acid 1H again, the own ester CF of 1H-perfluor
3(CF
2)
4CH
2OOCC (CH
3)=CH
2, productive rate 80.9%.
Embodiment 3
Preparation vinylformic acid 1H, the 1H-2-trifluoromethyl-own ester of 3-oxa-perfluor
In-5～0 ℃, slowly be dissolved into 3.63g (0.096mol) lithium aluminum hydride in the 92.94g dioxane, slowly drip 19.58g (0.059mol) 2-trifluoromethyl-3-oxa-octafluoro hexanoyl fluorine again, dropwise the back at 0～5 ℃ of following stirring reaction 6h, stir then and slowly add 10.0g water down, add 20.0g 10% aqueous sodium hydroxide solution again, keep system temperature at 5～10 ℃, stir the 15min after-filtration, filtrate concentrates with Rotary Evaporators in room temperature is bathed, obtain crude product, rectifying obtains 16.82g 1H then, 1H-2-trifluoromethyl-3-oxa-perfluor-1-hexanol CF
3CF
2CF
2OCF (CF
3) CH
2OH, productive rate 89.3%.
To be dissolved in 16.09g (0.050mol) 1H in the 79.62g methylene dichloride, 1H-2-trifluoromethyl-3-oxa-perfluor-1-hexanol, 7.574g (0.062mol) N, accelerine and 0.008g thiodiphenylamine add in the flask of band condenser, cooling and maintenance temperature are-15 ℃, Dropwise 5 .29g (0.058mol) acrylate chloride.Dropwise back restir 1h, be warming up to 35 ℃ of stirring and refluxing 7h.Then mother liquor is poured in the frozen water, be washed with water to organic phase for neutral, crude product rectification under vacuum again obtains 16.05g vinylformic acid 1H, the own ester CF of 1H-2-trifluoromethyl-3-oxa-perfluor
3CF
2CF
2OCF (CF
3) CH
2OOCCH=CH
2, productive rate 85.3%.
Embodiment 4
Preparation methacrylic acid 1H, 1H-2, two (trifluoromethyl)-3 of 5-, 6-two oxa-perfluor esters in the ninth of the ten Heavenly Stems
In 5～10 ℃, slowly be dissolved into 4.63g (0.122mol) lithium aluminum hydride in the 88.90g anhydrous tetrahydro furan, slowly drip 33.35g (0.067mol) 2 again, two (trifluoromethyl)-3 of 5-, 6-two oxa-s 11 fluorine nonanoyl fluorine dropwise the back at 10～15 ℃ of following stirring reaction 5h.Stir then and slowly add 10.0g water down, add 20.0g 10% aqueous sodium hydroxide solution again, keep system temperature at 5～10 ℃, filter after stirring 10min, filtrate concentrates with Rotary Evaporators in room temperature is bathed, and obtains crude product, rectifying obtains 26.40g1H then, 1H-2, two (trifluoromethyl)-3 of 5-, 6-two oxa-s perfluor-1 nonyl alcohol CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) CH
2OH, productive rate 81.2%.
To be dissolved in 55.32g 1,1,23.48g in the 2-Freon 113 (0.048mol) 1H, 1H-2, two (trifluoromethyl)-3 of 5-, 6-two oxa-perfluor-1 nonyl alcohols, 4.07g (0.070mol) Potassium monofluoride and 0.010g thiodiphenylamine add in the flask of band condenser, and cooling and maintenance temperature are-10 ℃, begin to drip the methacrylic chloride of 6.01g (0.057mol).Dropwise back restir 1h, be warming up to 45 ℃ of stirring and refluxing 6h.Then mother liquor is poured in the frozen water, be washed with water to organic phase for neutral, obtain crude product, rectification under vacuum obtains 24.06g methacrylic acid 1H again, 1H-2, two (trifluoromethyl)-3 of 5-, 6-two oxa-perfluor ester in ninth of the ten Heavenly Stems CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) CH
2OOCC (CH
3)=CH
2, productive rate 89.9%.
Embodiment 5
Preparation methacrylic acid 1H, 1H-2,5,8-three (trifluoromethyl)-3,6,9-trioxa perfluor ten diester
3.08g (0.081mol) lithium aluminum hydride slowly is dissolved in 10～15 ℃ in the 57.08g anhydrous diethyl ether, slowly drips 27.88g (0.042mol) 2,5 again, 8-three (trifluoromethyl)-3,6,9-trioxa ten tetrafluoro dodecane acyl fluorides dropwise the back at 20～25 ℃ of following stirring reaction 4h.Stir then and slowly add 10.0g water down, add 20.0g 10% aqueous sodium hydroxide solution again, keep system temperature to filter behind 5～10 ℃ of stirring 10min, filtrate concentrates with Rotary Evaporators in room temperature is bathed, and obtains crude product, rectifying obtains 23.81g1H then, 1H-2,5,8-three (trifluoromethyl)-3,6,9-trioxa perfluor-1-dodecanol CF
3CF
2CF
2O[CF (CF
3) CF
2O]
2CF (CF
3) CH
2OH, productive rate 87.1%.
To be dissolved in 22.56g (0.035mol) 1H in the 47.40g acetone, 1H-2,5,8-three (trifluoromethyl)-3,6,9-trioxa perfluor-1-dodecanol, 3.76g (0.048mol) pyridine and 0.008g thiodiphenylamine add in the flask of band condenser, and cooling and maintenance temperature are-5 ℃, begin to drip the methacrylic chloride of 4.46g (0.043mol).Dropwise back restir 1h, be warming up to 50 ℃ of stirring and refluxing 6h.Then mother liquor is poured in the frozen water, be washed with water to organic phase, obtain crude product, carry out rectification under vacuum to obtain 20.84g methacrylic acid 1H 1H-2,5,8-three (trifluoromethyl)-3,6,9-trioxa perfluor ten diester CF for neutral
3CF
2CF
2O[CF (CF
3) CF
2O]
2CF (CF
3) CH
2OOCC (CH
3)=CH
2, productive rate 83.6%.
Embodiment 6
Preparation vinylformic acid 2,2,3,3,4,4, the multipolymer of 4-seven fluorine butyl ester/stearyl methacrylates/methacrylic acid hydroxyl ethyl ester
Vinylformic acid 2 with 16.0g, 2,3,3,4,4,4-seven fluorine butyl esters, 24.0g stearyl methacrylate, 2.5g methacrylic acid hydroxyl ethyl ester, 10.0g acetone, 0.7g octadecyl trimethyl ammonium chloride, 2.1g polyoxyethylene lauryl ether add in the 110g water, carry out pre-emulsification with homogeneous emulsifying machine, form pre-emulsion.The pre-emulsion of gained is transferred in the flask of 500ml, under the inert conditions of nitrogen protection, dripped continuously the 20g aqueous solution that contains 0.24g initiator azo two NSC 18620 dihydrochlorides, 50 ℃ of following copolymer-1s 5 hours.
The copolymer emulsion of gained is diluted to 3%, adopts to pad-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, classification of waterproof reaches 80 fens, grease proofing grade reaches 4 grades.
Embodiment 7
Preparation methacrylic acid 1H, the multipolymer of the own ester/octadecyl acrylate of 1H-perfluor/Hydroxyethyl Acrylate
Methacrylic acid 1H with 10.0g, the own ester of 1H-perfluor, 30.0g octadecyl acrylate, 3.0g Hydroxyethyl Acrylate, 5.0g Virahol, 0.8g cetyl trimethylammonium bromide, 2.4g polyoxyethylene cetyl ether add in the 110g water, carry out pre-emulsification with homogeneous emulsifying machine, form pre-emulsion.The pre-emulsion of gained is transferred in the flask of 500ml, under the inert conditions of nitrogen protection, dripped the 20g aqueous solution that contains 0.12g initiator azo two NSC 18620 dihydrochlorides continuously, 60 ℃ of following copolymerization 8 hours.
The copolymer emulsion of gained is diluted to 3%, adopts to pad-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, classification of waterproof reaches 80 fens, grease proofing grade reaches 4 grades.
Embodiment 8
Preparation vinylformic acid 1H, the multipolymer of the 1H-2-trifluoromethyl-own ester/octadecyl acrylate of 3-oxa-perfluor/N hydroxymethyl acrylamide
Vinylformic acid 1H with 28.0g, 1H-2-trifluoromethyl-own the ester of 3-oxa-perfluor, 12.0g octadecyl acrylate, 2.0g N hydroxymethyl acrylamide, 20.0g methyl glycol, 0.6g octadecyl trimethyl ammonium chloride, 1.8g polyoxyethylene sorbitan monostearate add in the 140g water, carry out pre-emulsification with homogeneous emulsifying machine, form pre-emulsion.The pre-emulsion of gained is transferred in the flask of 500ml, under the inert conditions of nitrogen protection, dripped continuously the 20g aqueous solution that contains 0.28g initiator azo two NSC 18620 dihydrochlorides, 55 ℃ of following copolymer-1s 2 hours.
The copolymer emulsion of gained is diluted to 3%, adopts to pad-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, classification of waterproof reaches 80 fens, grease proofing grade reaches 5 grades.
Embodiment 9
Preparation methacrylic acid 1H, 1H-2, two (trifluoromethyl)-3 of 5-, the multipolymer of 6-two oxa-perfluor ester/stearyl methacrylates in the ninth of the ten Heavenly Stems/methacrylic acid hydroxyl ethyl ester
Methacrylic acid 1H with 20.0g, 1H-2, two (trifluoromethyl)-3 of 5-, 6-two oxa-perfluor esters in the ninth of the ten Heavenly Stems, 20.0g stearyl methacrylate, 2.0g methacrylic acid hydroxyl ethyl ester, 10.0g propylene glycol, 0.6g octadecyl trimethyl ammonium chloride, 1.8g polyoxyethylene sorbitan trioleate add in the 140g water, carry out pre-emulsification with homogeneous emulsifying machine, form pre-emulsion.The pre-emulsion of gained is transferred in the flask of 500ml, under the inert conditions of nitrogen protection, dripped the 20g aqueous solution that contains 0.20g initiator azo two NSC 18620 dihydrochlorides continuously, 65 ℃ of following copolymerization 6 hours.
The copolymer emulsion of gained is diluted to 3%, adopts to pad-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, classification of waterproof reaches 90 fens, grease proofing grade reaches 6 grades.
Embodiment 10
Preparation methacrylic acid 1H, 1H-2,5,8-three (trifluoromethyl)-3,6, the multipolymer of 9-trioxa perfluor ten diester/octadecyl acrylate/N hydroxymethyl acrylamide
Methacrylic acid 1H with 12.0g, 1H-2,5,8-three (trifluoromethyl)-3,6,9-trioxa perfluor ten diester, 28.0g octadecyl acrylate, 4.0g N hydroxymethyl acrylamide, 5.0g acetone, 0.5g cetyl trimethylammonium bromide, 1.5g polyoxyl 40 stearate add in the 110g water, carry out pre-emulsification with homogeneous emulsifying machine, form pre-emulsion.The pre-emulsion of gained is transferred in the flask of 500ml, under the inert conditions of nitrogen protection, dripped the 20g aqueous solution that contains 0.24g initiator azo two NSC 18620 dihydrochlorides continuously, 70 ℃ of following copolymerization 5 hours.
The copolymer emulsion of gained is diluted to 3%, adopts to pad-dry-fabric finishing process of baking and banking up with earth, cotton fabric is put in order, classification of waterproof reaches 90 fens, grease proofing grade reaches 6 grades.
By embodiment 6～embodiment 10 evaluating results as seen, the copolymer emulsion for preparing the fluorinated acrylate gained by the present invention, be diluted to 3% as the organic fluorine fabric finishing agent, fabric waterproof grade after the arrangement reached more than 80 minutes, grease proofing grade reaches more than 4 grades, and the goal of the invention fabric that has reached expection has the excellent waterproof oil preventing performance.
Though the present invention with the preferred embodiment publicity as above, so it is not in order to restriction the present invention.It should be noted that the present invention is not limited to above embodiment, based on the present invention enlightenment, any those of ordinary skills to any conspicuous change that the present invention did, or are equal to alternatively, also should be considered to fall within protection scope of the present invention.
Claims (6)
1. the preparation method of a fluorinated acrylate is characterized in that may further comprise the steps successively:
(1) be raw material with the perfluoroalkyl acyl compound, in the preparation polyfluoro alcohol reaction vessel reductive agent slowly is dissolved among the anhydrous solvent A, temperature is controlled to be-10～20 ℃, progressively drip the perfluoroalkyl acyl compound then, dropwise the back-10～30 ℃ of following stirring reactions 4～10 hours, stir then down and slowly add entry to remove excessive reductive agent, add 10% aqueous sodium hydroxide solution again, keep 5～10 ℃ of system temperatures, filter after stirring 10～30min, filtrate concentrates with Rotary Evaporators in room temperature is bathed, get crude product, and then rectifying obtains polyfluoro alcohol;
(2) by being dissolved in the polyfluoro alcohol that step (1) makes among the solvent B in the polyfluoro alcohol preparation fluorinated acrylate reaction vessel, with the thiodiphenylamine is stopper, in the presence of catalyzer, maintains the temperature in-20～10 ℃, slowly drip (methyl) acrylate chloride, dropwise the back and stirred 0.5～2 hour, be warming up to 30～60 ℃, stirring and refluxing 2～8 hours, then mother liquor is poured in the frozen water, it is neutral washing to organic phase with frozen water, obtains crude product, and rectification under vacuum obtains fluorinated acrylate again.
2. the preparation method of fluorinated acrylate according to claim 1 is characterized in that: the described anhydrous solvent A of step (1) is a kind of in ether, tetrahydrofuran (THF), the dioxane, and consumption is 2～5 times of described perfluoroalkyl acyl compound weight.
3. the preparation method of fluorinated acrylate according to claim 1 is characterized in that: the described reductive agent of step (1) is a kind of in lithium aluminum hydride, the sodium borohydride, and the mol ratio of described reductive agent and described perfluoroalkyl acyl compound is 1.5～2.0.
4. the preparation method of fluorinated acrylate according to claim 1, it is characterized in that: the mol ratio of described (methyl) acrylate chloride of step (2) and described polyfluoro alcohol is 1.1～1.5.
5. the preparation method of fluorinated acrylate according to claim 1, it is characterized in that: the described solvent B of step (2) is methylene dichloride, ether, trichloromethane, acetone, 1,1, a kind of in the 2-Freon 113, consumption is 2～5 times of described polyfluoro alcohol weight.
6. the preparation method of fluorinated acrylate according to claim 1, it is characterized in that: the described catalyzer of step (2) is pyridine, triethylamine, N, a kind of in accelerine, yellow soda ash, salt of wormwood, Sodium Fluoride, the Potassium monofluoride, the mol ratio of described catalyzer and described polyfluoro alcohol is 1.2～1.5.
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| CN 201010520150 Active CN102010334B (en) | 2010-10-25 | 2010-10-25 | Method for preparing fluorine-containing acrylate |
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| CN103524346A (en) * | 2013-10-22 | 2014-01-22 | 太仓中化环保化工有限公司 | Method for synthesizing perfluoroalkylethyl acrylate |
| CN104926966A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院上海有机化学研究所 | Fluorine-containing polymer for low-energy surface coating and preparation method thereof |
| CN105622359A (en) * | 2015-12-31 | 2016-06-01 | 天津市长芦化工新材料有限公司 | Preparation method and application of fluorocarbon alcohol |
| CN108795239A (en) * | 2018-06-26 | 2018-11-13 | 南京信息工程大学 | It is a kind of using poly- perfluoroalkyl ethanol acrylic acid derivative as the preparation method of the aqueous epoxide resin paint of hydrophobing agent |
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| CN103524346A (en) * | 2013-10-22 | 2014-01-22 | 太仓中化环保化工有限公司 | Method for synthesizing perfluoroalkylethyl acrylate |
| CN104926966A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院上海有机化学研究所 | Fluorine-containing polymer for low-energy surface coating and preparation method thereof |
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| CN109534993A (en) * | 2018-11-15 | 2019-03-29 | 广东广山新材料股份有限公司 | A kind of unsaturation fluorocarbons and its preparation method and application |
| CN109456193A (en) * | 2018-11-15 | 2019-03-12 | 广东广山新材料股份有限公司 | A kind of unsaturation fluorocarbons and its preparation method and application |
| CN112409875A (en) * | 2019-08-23 | 2021-02-26 | 天津科技大学 | Corrosion-resistant acrylic fluororesin modified coating |
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