CN102531889B - Preparation method for fluorine-containing acrylic ester - Google Patents
Preparation method for fluorine-containing acrylic ester Download PDFInfo
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- CN102531889B CN102531889B CN201110417006.5A CN201110417006A CN102531889B CN 102531889 B CN102531889 B CN 102531889B CN 201110417006 A CN201110417006 A CN 201110417006A CN 102531889 B CN102531889 B CN 102531889B
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Abstract
The invention relates to a preparation method for fluorine-containing acrylic ester. The method comprises the following step of: esterifying perfluoro alkyl ethyl iodine and alkali metal and/or alkaline earth metal of acrylic acid or methyl acrylic acid or halogenated acrylic ester in a polar non-proton organic solvent with boiling point of 140-400 DEG C in the presence of a phase transfer catalyst at the temperature of 140-200 DEG C. According to the method, the polar non-proton organic solvent with high boiling point is used as a solvent for the esterification, and the phase transfer catalyst is used in a matching way, so that the selectivity for the reaction is greatly improved; after the esterification is finished, a target product with the content being greater than 98 percent can be obtained through simple filtration and reduced pressure distillation treatment; meanwhile, the molar yield of the product reaches up to over 80 percent. Meanwhile, according to the method provided by the invention, a high-pressure reaction kettle and a special distillation tower are not required, so that the method has the advantages of low equipment requirement, easiness in operation, high safety, easiness in control and low production cost and is particularly suitable for industrial production of the fluorine-containing acrylic ester.
Description
Technical field
The present invention relates to a kind of preparation method of fluorinated acrylate, particularly the preparation method of perfluor alkyl ethyl acrylate, perfluor alkyl ethide methacrylic ester and perfluor alkyl ethide haloacrylic acid esters.
Background technology
Perfluoroalkylethyl Acrylate Polymer, perfluor alkyl ethide methacrylate polymers can be widely used in anticorrosion and antifouling coating, as anticorrosion in bridge construction, naval vessel anticorrosion and antifouling; Also may be used for the fields such as the functional treatment of fiber surface, the waterproof and oilproof of leather and tensio-active agent, there is important development and application and be worth.
Fluorinated acrylate shown in following formula (1), is used as monomer in the manufacture of the acrylate containing fluorine polymkeric substance of the effective constituent as water and oil repellent agent:
C
2F
5(CF
2CF
2)
nCH
2CH
2OCOCR
1＝CH
2 (1)
In formula (1), R
1represent hydrogen, methyl or halogen, n be greater than 0 integer.As the method for this monomer of preparation, proposed various method in the past.
Daikin has applied for two sections of patents of invention about fluorine-containing Lipase absobed in China in 2005, and publication number is respectively CN 1946668A and CN 1946669A.Wherein, method described in CN 1946668A with the fluoroalkyl alcohol shown in formula (2) for raw material, with the fluorinated acrylate shown in acrylic compound Reactive Synthesis general formula (1).
C
2F
5(CF
2CF
2)
nCH
2CH
2OH (2) C
2F
5(CF
2CF
2)
nCH
2CH
2I (3)
The economically viable synthetic route of raw material fluoroalkyl alcohol used in the method is still and obtains with the perfluor alkyl ethide iodine synthesis shown in general formula (3), namely the finished product fluorinated acrylate is obtained via two-step reaction by perfluor alkyl ethide iodine, thus affect overall yield, and complex operation, thus production cost is higher.
CN 1946669A discloses the manufacture method of the mixture of fluorinated acrylate, first it obtain the mixture containing the fluorinated acrylate shown in general formula (1), concrete grammar is: by the Addition on ethylene thing of fluoro-alkyl iodide, potassium acrylate, the trimethyl carbinol, add in autoclave as the quinhydrones of stopper and Hydroquinone monomethylether, be heated to 180 DEG C ~ 190 DEG C, react 6 hours, cooling, cross and filter KI, subsequently filtrate is distilled, the removing trimethyl carbinol, obtain reaction mixture, the total mol ratio of the perfluoro alkyl ethylene contained in this reaction mixture reaches 17.99%, the molar ratio of fluorine-containing alcohol reaches 2.22% (see its Instructions Page 10 table 1), secondly reaction mixture obtained above is distilled, to reduce perfluoro alkyl ethylene contained in mixture and the ratio of fluorine-containing alcohol, described distillation uses the weighting material and/or internal structure with exotic materials formation, as seen from Table 1, in mixture after distillation process, the total mol ratio of fluorinated acrylate is up to 99%.The esterification of the method at high temperature under high pressure, carry out in low boiling point solvent, equipment requirements is high, security risk is larger, reaction preference is poor, although improve the purity of fluorinated acrylate by the distillation of follow-up specific distillation tower, but the requirement further increased equipment, and yield is caused to reduce.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of preparation method of fluorinated acrylate of improvement.
For solving above technical problem, the present invention takes following technical scheme:
A preparation method for fluorinated acrylate, wherein fluorinated acrylate is for having one or more mixture of the compound of the structure shown in formula (1):
C
2F
5(CF
2CF
2)
nCH
2CH
2OCOCR
1＝CH
2 (1)，
In formula (1), R
1represent hydrogen, methyl or halogen, n be greater than 0 integer,
Described preparation method comprises makes the basic metal of perfluor alkyl ethide iodine and acrylic or methacrylic acid or haloacrylic acid and/or alkaline earth salt under boiling point is in the polar non-proton organic solvent of 140 DEG C ~ 400 DEG C and phase-transfer catalyst exists, at temperature 140 DEG C ~ 200 DEG C, carry out the step of esterification, and described perfluor alkyl ethide iodine is for having one or more the mixture in the compound of formula (3) structure:
C
2F
5(CF
2CF
2)
nCH
2CH
2I (3)，
In formula (3), n be greater than 0 integer.
According to the present invention, described esterification, without the need under high pressure carrying out, carries out can carrying out and obtaining desirable effect under pressure-0.01MPa ~ 1atm, and preferably, esterification is carried out at ambient pressure, and easy to operate, equipment requirements is low.
According to the present invention, above-mentioned basic metal is preferably lithium, sodium or potassium; Alkaline-earth metal is preferably magnesium or calcium.Specifically, basic metal and/or the alkaline earth salt of described acrylic or methacrylic acid or haloacrylic acid comprise Lithium acrylate, sodium acrylate, potassium acrylate, calcium acrylate, Magnesium Acrylate Prepared, lithium methacrylate, sodium methacrylate, methacrylic acid potassium, methacrylic acid calcium, magnesinm methacrylate, haloacrylic acid lithium, haloacrylic acid sodium, haloacrylic acid potassium, haloacrylic acid calcium, haloacrylic acid magnesium, the wherein preferably sodium salt of acrylic or methacrylic acid or haloacrylic acid or sylvite, halogen in described haloacrylic acid is preferably fluorine, chlorine, one in bromine and iodine.
According to the present invention, described polar non-proton organic solvent includes but not limited to dimethyl formamide, N,N-DIMETHYLACETAMIDE, HMPA, quinoline, isoquinoline 99.9, tetramethylene sulfone, dimethyl sulfoxide (DMSO) and N-Methyl pyrrolidone etc., solvent for esterification can be selected from these solvents one or more, be not particularly limited.
According to the present invention, described phase-transfer catalyst is that to be selected from quaternary ammonium salt-type phase transfer catalyst, quaternary phosphine salt phase-transfer catalyst and weight-average molecular weight be one or more combination in the polyoxyethylene glycol of 200 ~ 6000.Wherein: quaternary ammonium salt-type phase transfer catalyst includes but not limited to 4 bromide, Tetrabutyl amonium bromide, benzyl trimethyl ammonium chloride, tri-n-octyl methyl ammonium chloride and cetyl trimethylammonium bromide.Described quaternary phosphine salt phase-transfer catalyst includes but not limited to tri-phenyl-ethyl phosphonium bromide, tetraphenyl phosphonium chloride, benzyl three phenyl phosphonium bromide, benzyltriphenyl phosphonium phosphonium chloride, 4-phenyl phosphonium bromide, four (diethylin) phosphonium bromide, triphenyl butyl phosphonium bromide and tri-phenyl-ethyl phosphonium bromide.When using polyoxyethylene glycol as phase-transfer catalyst, its preferable weight-average molecular weight is 400 ~ 1000.Phase-transfer catalyst for esterification can be one or more combination, is not particularly limited.
According to further embodiment of the present invention: described esterification is also carried out under stopper exists.The stopper be applicable to has such as quinhydrones (Resorcinol) or Hydroquinone monomethylether etc.Described preparation method is also included in before esterification carries out, and carries out processed to reaction system.Processed is by adding dewatering agent to carry out.The inventive method specific implementation process is: in reactor, add described perfluor alkyl ethide iodine, acrylic or methacrylic acid or the basic metal of haloacrylic acid and/or alkaline earth salt, polar non-proton organic solvent, phase-transfer catalyst, stopper and dewatering agent; nitrogen replacement and continuing nitrogen protection; after processed; be warming up to 140 ~ 200 DEG C; insulation reaction 4 ~ 10 hours; terminate reaction, filter reaction solution, namely rectification under vacuum obtains described fluorinated acrylate.Containing phase-transfer catalyst in the raffinate of rectifying, can overlap for lower batch reaction.
Preferably, the consumption mol ratio of perfluor alkyl ethide iodine, acrylic or methacrylic acid or the basic metal of haloacrylic acid and/or alkaline earth salt, phase-transfer catalyst is 1: 1 ~ 3: 0.001 ~ 0.5.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
The present invention adopts high boiling polar aprotic solvent as the solvent of esterification, and with the use of phase-transfer catalyst, substantially increase the selectivity of reaction, after esterification terminates, by simply to filter and underpressure distillation process can obtain the target product that content is greater than 98%, while molar product yield up to more than 80%.In addition, the inventive method is without the need to using autoclave and special distillation tower, and thus equipment requirements is lower, simple to operate, and security is high, easily controls, and production cost is low, is specially adapted to the suitability for industrialized production of fluorinated acrylate.
Embodiment
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention is not limited to following examples.
Embodiment 1
Be furnished with in four mouthfuls of round-bottomed flasks of thermometer, water trap, prolong and whipping appts to 250ml, add 75.5g perfluor alkyl ethide iodine mixture (C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6, 2wt%), 17.25g potassium acrylate, 1.5g 4-phenyl phosphonium bromide, 112mg Resorcinol, 100ml tetramethylene sulfone, 50ml dewatering agent (hexanaphthene), nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 180 DEG C of synthesis under normal pressure 6h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethyl acrylate mixture 53.7g of effective content 98.3% through rectification under vacuum, molar yield 82.6%, distillation residual liquid (containing phase-transfer catalyst) is waited until lower batch reaction and is applied mechanically.
Perfluor alkyl ethyl acrylate mixture composed as follows:
C
2F
5(CF
2CF
2)
3CH
2CH
2OCOCH＝CH
2 19wt％；
C
2F
5(CF
2CF
2)
4CH
2CH
2OCOCH＝CH
2 40wt％；
C
2F
5(CF
2CF
2)
5CH
2CH
2OCOCH＝CH
2 39wt％；
C
2f
5(CF
2cF
2)
ncH
2cH
2oCOCH=CH
2, wherein n>=6 2wt%.
Embodiment 2
Except using the distillation residual liquid of embodiment 1 to substitute 4-phenyl phosphonium bromide, obtain the perfluor alkyl ethyl acrylate mixture 52.3g of effective content 98.5% with embodiment 1 same operation, molar yield 80.5%.
Embodiment 3
Use the distillation residual liquid of embodiment 2 to substitute 4-phenyl phosphonium bromide, and add 0.2g 4-phenyl phosphonium bromide, obtain the perfluor alkyl ethyl acrylate mixture 53.9g of effective content 98.5% with embodiment 1 same operation, molar yield 82.9%.
Embodiment 4
Thermometer is furnished with to 250ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 70.4g perfluorooctylethyl group iodine, 19.0g methacrylic acid potassium, 1.5g tetra-(diethylin) phosphonium bromide, 112mg Resorcinol, 100ml dimethyl sulfoxide (DMSO), 50ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C, reflux dewatering 2h, steam and remove water trap except after dewatering agent, be warming up to 155 DEG C, reaction is terminated after synthesis under normal pressure 9h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluorooctylethyl group methacrylic ester 51.8g of effective content 98.1% through rectification under vacuum, molar yield 83.0%.
Embodiment 5
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 1), 34.4g methacrylic acid potassium, 3g benzyl three phenyl phosphonium bromide, 220mg Resorcinol, 200ml N,N-DIMETHYLACETAMIDE, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.1g of effective content 98.5% through rectification under vacuum, molar yield 81.0%.
Perfluor alkyl ethide methacrylate mixtures composed as follows:
C
2F
5(CF
2CF
2)
3CH
2CH
2OCOC(CH
3)＝CH
2 19wt％；
C
2F
5(CF
2CF
2)
4CH
2CH
2OCOC(CH
3)＝CH
2 40wt％；
C
2F
5(CF
2CF
2)
5CH
2CH
2OCOC(CH
3)＝CH
2 39wt％；
C
2f
5(CF
2cF
2)
ncH
2cH
2oCOC (CH
3)=CH
2, wherein n>=6 2wt%.
Embodiment 6
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 1), 34.4g methacrylic acid potassium, 3g tri-phenyl-ethyl phosphonium bromide, 220mg Resorcinol, 200ml quinoline, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 185 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 107.4g of effective content 99.1% through rectification under vacuum, and (n=3 accounts for 19%, n=4 accounts for 40%, n=5 accounts for 39%, n >=6 account for 2%), molar yield 82.6%.
Embodiment 7
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 1), 34.4g methacrylic acid potassium, 3g polyoxyethylene glycol (weight-average molecular weight 600), 220m g Resorcinol, 200ml HMPA, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 108.5g of effective content 98.7% through rectification under vacuum, molar yield 83.5%.
Perfluor alkyl ethide methacrylate mixtures composed as follows:
C
2F
5(CF
2CF
2)
3CH
2CH
2OCOC(CH
3)＝CH
2 19wt％；
C
2F
5(CF
2CF
2)
4CH
2CH
2OCOC(CH
3)＝CH
2 40wt％；
C
2F
5(CF
2CF
2)
5CH
2CH
2OCOC(CH
3)＝CH
2 39wt％；
C
2f
5(CF
2cF
2)
ncH
2cH
2oCOC (CH
3)=CH
2, wherein n>=6 2wt%.
Embodiment 8
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 1), 34.4g methacrylic acid potassium, 3g cetyl trimethylammonium bromide, 220mg Resorcinol, 200ml DMF, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 155 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.3g of effective content 98.3% through rectification under vacuum, molar yield 81.0%.
Perfluor alkyl ethide methacrylate mixtures composed as follows:
C
2F
5(CF
2CF
2)
3CH
2CH
2OCOC(CH
3)＝CH
2 19wt％；
C
2F
5(CF
2CF
2)
4CH
2CH
2OCOC(CH
3)＝CH
2 40wt％；
C
2F
5(CF
2CF
2)
5CH
2CH
2OCOC(CH
3)＝CH
2 39wt％；
C
2f
5(CF
2cF
2)
ncH
2cH
2oCOC (CH
3)=CH
2, wherein n>=6 2wt%.
Embodiment 9
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 1), 34.4g methacrylic acid potassium, 3g cetyl trimethylammonium bromide, 220mg Resorcinol, 200ml N-Methyl pyrrolidone, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.6g of effective content 99.5% through rectification under vacuum, molar yield 81.2%.
Perfluor alkyl ethide methacrylate mixtures composed as follows:
C
2F
5(CF
2CF
2)
3CH
2CH
2OCOC(CH
3)＝CH
2 19wt％；
C
2F
5(CF
2CF
2)
4CH
2CH
2OCOC(CH
3)＝CH
2 40wt％；
C
2F
5(CF
2CF
2)
5CH
2CH
2OCOC(CH
3)＝CH
2 39wt％；
C
2f
5(CF
2cF
2)
ncH
2cH
2oCOC (CH
3)=CH
2, wherein n>=6 2wt%.
Comparative example 1
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 5), 34.4g methacrylic acid potassium, 220mg Resorcinol, the 200ml trimethyl carbinol, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, material is transferred in 1L autoclave, be warming up to 180 ~ 190 DEG C (still internal pressure 1.3MPa), reaction is terminated after reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 97.0g (forming same embodiment 5) of effective content 95.5% through rectification under vacuum, molar yield 74.6%.
Comparative example 2
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 5), 34.4g methacrylic acid potassium, 220mg Resorcinol, the 200ml trimethyl carbinol, 3g cetyl trimethylammonium bromide, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, material is transferred in 1L autoclave, be warming up to 180 ~ 190 DEG C (still internal pressure 1.2MPa), reaction is terminated after reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 97.5g (forming same embodiment 5) of effective content 95.3% through rectification under vacuum, molar yield 75.0%.
Comparative example 3
Thermometer is furnished with to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture (with embodiment 5), 34.4g methacrylic acid potassium, 220mg Resorcinol, 200mlN-methyl-2-pyrrolidone, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, material is transferred in 1L autoclave, be warming up to 180 ~ 190 DEG C (normal pressures), reaction is terminated after reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 102.4g (forming same embodiment 5) of effective content 95.3% through rectification under vacuum, molar yield 77.6%.
By the above embodiment of the present invention and comparative example are compared visible, the present invention use high boiling polar aprotic solvent and phase-transfer catalyst with the use of method, high selectivity can be obtained at ambient pressure with in common reaction vessel.Compared with the prior art, present device requires lower, simple to operate, and security is high, easily controls, and production cost is low, is specially adapted to the suitability for industrialized production of fluorinated acrylate.
Above-described embodiment, only for technical conceive of the present invention and feature are described, its object is to person skilled in the art can be understood content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences done according to spirit of the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Claims (7)
1. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 250ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 75.5g perfluor alkyl ethide iodine mixture, 17.25g potassium acrylate, 1.5g 4-phenyl phosphonium bromide, 112mg Resorcinol, 100ml tetramethylene sulfone, 50ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 180 DEG C of synthesis under normal pressure 6h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethyl acrylate mixture 53.7g of effective content 98.3% through rectification under vacuum, distillation residual liquid is waited until lower batch reaction and is applied mechanically, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
2. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 250ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 70.4g perfluorooctylethyl group iodine, 19.0g methacrylic acid potassium, 1.5g tetra-(diethylin) phosphonium bromide, 112mg Resorcinol, 100ml dimethyl sulfoxide (DMSO), 50ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C, reflux dewatering 2h, steam and remove water trap except after dewatering agent, be warming up to 155 DEG C, reaction is terminated after synthesis under normal pressure 9h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluorooctylethyl group methacrylic ester 51.8g of effective content 98.1% through rectification under vacuum.
3. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture, 34.4g methacrylic acid potassium, 3g benzyl three phenyl phosphonium bromide, 220mg Resorcinol, 200ml N,N-DIMETHYLACETAMIDE, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.1g of effective content 98.5% through rectification under vacuum, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
4. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture, 34.4g methacrylic acid potassium, 3g tri-phenyl-ethyl phosphonium bromide, 220mg Resorcinol, 200ml quinoline, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 185 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 107.4g of effective content 99.1% through rectification under vacuum, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
5. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture, 34.4g methacrylic acid potassium, the polyoxyethylene glycol of 3g weight-average molecular weight 600, 220mg Resorcinol, 200ml HMPA, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 108.5g of effective content 98.7% through rectification under vacuum, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
6. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture, 34.4g methacrylic acid potassium, 3g cetyl trimethylammonium bromide, 220mg Resorcinol, 200ml DMF, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 155 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.3g of effective content 98.3% through rectification under vacuum, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
7. the preparation method of a fluorinated acrylate, it is characterized in that: be furnished with thermometer to 500ml, water trap, in four mouthfuls of round-bottomed flasks of prolong and whipping appts, add 150g perfluor alkyl ethide iodine mixture, 34.4g methacrylic acid potassium, 3g cetyl trimethylammonium bromide, 220mg Resorcinol, 200ml N-Methyl pyrrolidone, 100ml hexanaphthene, nitrogen replacement and continuing nitrogen protection, be warming up to 85 DEG C of reflux dewatering 2h, steam and remove water trap except after dewatering agent, reaction is terminated after being warming up to 165 DEG C of reaction 7h, treat that temperature drops to 30 DEG C, filtering reacting liquid, filtrate obtains the perfluor alkyl ethide methacrylate mixtures 105.6g of effective content 99.5% through rectification under vacuum, described perfluor alkyl ethide iodine mixture is by C
2f
5(CF
2cF
2)
3cH
2cH
2i 20wt%, C
2f
5(CF
2cF
2)
4cH
2cH
2i 40wt%, C
2f
5(CF
2cF
2)
5cH
2cH
2i 38wt%, C
2f
5(CF
2cF
2)
ncH
2cH
2i, wherein n>=6,2wt% forms.
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