CN102731348A - Bisperfluoroalkylsulfonylimino-ethyl acrylate monomer and preparation method thereof - Google Patents
Bisperfluoroalkylsulfonylimino-ethyl acrylate monomer and preparation method thereof Download PDFInfo
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- CN102731348A CN102731348A CN2012101711321A CN201210171132A CN102731348A CN 102731348 A CN102731348 A CN 102731348A CN 2012101711321 A CN2012101711321 A CN 2012101711321A CN 201210171132 A CN201210171132 A CN 201210171132A CN 102731348 A CN102731348 A CN 102731348A
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Abstract
The invention provides a bisperfluoroalkylsulfonylimino-ethyl acrylate monomer and a preparation method thereof. The monomer has a structural formula as described in the specification; and in the structural formula, Rf1 and Rf2 are perfluoroalkyl groups with a molecular formula of CnF2n+1 and groups of Rf1 and Rf2 are identical or different, wherein n is a positive integer in a range of 1 to 6. The bisperfluoroalkylsulfonylimino-ethyl acrylate monomer provided in the invention has the advantages of low surface energy, good water and oil repellency, degradability, high efficiency and environment friendliness.
Description
Technical field
The invention belongs to polymeric material field, specifically be meant a kind of fluoroalkyl sulfimide base ethyl propenoate monomer and preparation method thereof of enjoying a double blessing.
Background technology
Fluoropolymer is the macromolecular material that present known surface can be minimum; Side chain is not only being kept the primary characteristic of common propenoate by the substituted propenoate of fluorocarbon chain (FA) polymkeric substance; Also give its special low surface energy characteristic simultaneously; The critical surface tension that contains the Voncoat R 3310 of longer fluorine carbon side group can reach 10-11mN/m, and this is because by the critical surface tension (6mN/m) on-closelypacked surface of CF3, far below by-CF
2The surface (18mN/m) of-accumulation, the motivating force of thermodynamic(al)equilibrium forces-CF
3Be separated on the surface and form surface enrichment; Show extremely low surface energy, good chemicalstability; Special optics and electric property etc.; This type material is widely used as surface modifying material, like the refusing water, refuse oil of different substrate materials surface fabric, paper, leather, carpet etc., soil retardant.
Low surface energy and stability thereof mainly receive the structure of fluorine carbon side chain to form decision in the fluoro acrylic ester polymer, and fluorine carbon side chain is piled up closely more, lip-deep like this end group-CF
3Just arrange intensively more.Fluorocarbon chain length is that the surface energy of 8 perfluoroalkyl acrylate polymkeric substance can be low to moderate 10mN/m, is the synthesis material of ideal low surface energy polymeric.But the fluorochemical monomer that generally uses at present has long perfluoroalkyl chain (>=8), and their easy oxidative degradation in physical environment generates corresponding perfluorocarboxylic acid or sulfonyl compound (like PFOA, PFOS etc.).Extensive investigations research shows that the perfluorochemical of chain long number >=8 is one of organic pollutants of the difficult degradation found at present, has organism cumulative bad and remote migration possibility, and human health and living environment are had certain harm.Research shows that there is not tangible biological accumulation phenomenon in the fluorocarbon chain long number less than 7 perfluoroalkyl derivatives.Therefore, how to utilize the perfluoroalkyl acrylate of short chain to be raw material, the fluorinated acrylate monomer through molecular designing synthesizing new structure is the key factor that preparation has the water and oil repellant coated material of lasting low surface energy.
A lot of patent documentations of the patent No. such as US 2007015867, US 2007023216, CN 101006149 point out that the fluorine-containing derivant of fluorocarbon chain long number≤6 can not bring negative effect to environment basically.At present existing a lot of literature research environmentally friendly side chain fluorochemical monomer and polymkeric substance synthetic, characterize and use.But owing to contain the shortening of fluorocarbon chain; The crystallinity of side chain is damaged; All not ideal enough (like Macromolecules by perfluoro hexyl (C6) or perfluoro butyl (C4) as the water and oil repellant performance of fluorine carbon side chain synthetic fluoro-acrylate copolymer; 2005,38:5699-5705 is said).
Summary of the invention
The objective of the invention is provides a kind of not only water and oil repellant property good according to above-mentioned deficiency, and the fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing that can degrade.
Technical scheme of the present invention is following: a kind of fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing, and it has following structural formula:
, wherein, R
F1And R
F2Be that molecular formula is C
nF
2n+1Perfluoroalkyl, n is the positive integer of 1-6, R
F1And R
F2Group is identical or different.
Preferably, said R
F1And R
F2Be that molecular formula is C
4F
9Perfluoro butyl.
Another object of the present invention provides the above-mentioned monomeric preparation method of fluoroalkyl sulfimide base ethyl propenoate that enjoys a double blessing.
The said fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing of a kind of preparation claim 1, its step comprises: be R with structural formula 1)
F1SO
2The perfluoroalkyl sulfonyl fluoride of F and liquefied ammonia reaction, obtaining structural formula is R
F1SO
2NH
2The perfluoroalkyl sulphonamide; 2) be R with structural formula
F1SO
2NH
2Perfluoroalkyl sulphonamide and structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F reacts, and obtains structural formula and does
The fluoroalkyl sulfimide of enjoying a double blessing; 3) with structural formula do
Fluoroalkyl sulfimide and the ethylene bromohyrin reaction of enjoying a double blessing obtain structural formula and do
Fluorine alcohol; 4) with structural formula do at last
Fluorine alcohol obtain structural formula with the acrylate chloride reaction and do
The fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing; Wherein, R
F1And R
F2Be that molecular formula is C
nF
2n+1Perfluoroalkyl, n is the positive integer of 1-6.
The said the 1st) step reaction is to be R with structural formula
F1SO
2The perfluoroalkyl sulfonyl fluoride of F adds in the excessive liquefied ammonia, and room temperature reaction 1-5 hour, obtaining said structural formula behind separation and the purifying was R
F1SO
2NH
2The perfluoroalkyl sulphonamide.Preferably, the said the 1st) the reaction room temperature reaction times in step is 2-3 hour.
The said the 2nd) step reaction is to be 1 with mol ratio: (1-2): structural formula (1-3) is R
F1SO
2NH
2Perfluoroalkyl sulphonamide, structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F and triethylamine in acetonitrile back flow reaction 24-48 hour, separate and purifying after obtain said structural formula and do
The fluoroalkyl sulfimide of enjoying a double blessing.Preferably, the said the 2nd) structural formula is R in the step reaction
F1SO
2NH
2Perfluoroalkyl sulphonamide, structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F and the mol ratio of triethylamine are 1: (1-1.5): (1.1-2).
The said the 3rd) step reaction is to be 1 with mol ratio: (1-2): structural formula (1-3) does
Enjoy a double blessing fluoroalkyl sulfimide, ethylene bromohyrin and K
2CO
3, and the NaI of catalytic amount in acetone heating reflux reaction 2-3 hour, separate and purifying after obtain structural formula and do
Fluorine alcohol.Preferably, the said the 3rd) mol ratio of enjoy a double blessing fluoroalkyl sulfimide and the ethylene bromohyrin of structural formula for
is 1 in the step reaction: (1.1-1.8).
The said the 4th) step reaction is to be in the ether mixing solutions of the acrylate chloride of the 1-3 Resorcinol that in cooling bath, splashes into molfraction is a fluorine alcohol for
of 1 structural formula, molfraction is 1-4 triethylamine and catalytic amount with molfraction; Reflux 12-20 hour then, promptly obtain the enjoy a double blessing fluoroalkyl sulfimide base ethyl propenoate monomer of structural formula after the separation and purification for
.Preferably; The said the 4th) mol ratio of the fluorine pure and mild acrylate chloride of step reaction structure formula for
is 1: (1.2-2.5), the heating reflux reaction time is 15-18 hour.
Of the present inventionly enjoy a double blessing that not only surface energy is low, water and oil repellant property is good for fluoroalkyl sulfimide base ethyl propenoate monomer, also can degrade high-efficiency environment friendly simultaneously.The fluorine side chain of enjoying a double blessing that the present invention enjoys a double blessing in the fluoroalkyl sulfimide base ethyl propenoate monomer can guarantee effectively that fluoro-containing group is in the long-pending density of the richness on surface; The present invention has simultaneously introduced sulfoamido between perfluor side chain and acrylate backbone; Further promote the crystallinity of fluorine-containing short-side chain, improve the water and oil repellant performance on the surface.The fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing of the present invention can be used for preparing the fluorine-containing three-proof finishing agent of environment-friendly type of water and oil repellant excellent performance.
Description of drawings
Fig. 1-7 is gc (GC) figure of embodiment of the invention product.
Embodiment
Below further specify the present invention through specific embodiment:
Embodiment 1
1) (30.2g 0.1mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 3h, room temperature volatilization liquefied ammonia with perfluoro butyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white perfluoro butyl sulphonamide (22g, 0.073mol), yield is 73%;
2) with the perfluoro butyl sulphonamide (20g, 0.066mol) with triethylamine (6.67g 0.066mol) is dissolved in the 50mL acetonitrile, drip gradually under the normal temperature perfluoro butyl sulfonic acid fluoride (20.2g, 0.066mol) in acetonitrile solution, heating reflux reaction 48h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (perfluoro butyl sulphonyl) imines of white (30g, 0.052mol), yield is about 80%;
3) will two (perfluoro butyl sulphonyl) imines (10g, 0.017mol) with ethylene bromohyrin (2.4g, 0.019mol), dry K
2CO
3(4.7g, 0.034mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (9.6g, 0.015mol), yield is 90% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (9.6g, 0.015mol), (6.06g 0.06mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (1.78g, 0.02mol) in diethyl ether solution, reflux 12h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 8.3g of the fluoroalkyl sulfimide base ethyl propenoate monomer 1 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 1, product purity 96.4%, and yield is 80%.
Embodiment 2
1) (30.2g 0.1mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 2h, room temperature volatilization liquefied ammonia with perfluoro butyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white perfluoro butyl sulphonamide (21g, 0.07mol), yield is 70%;
2) with the perfluoro butyl sulphonamide (20g, 0.066mol) with triethylamine (6.67g 0.066mol) is dissolved in the 50mL acetonitrile, drip gradually under the normal temperature perfluoro butyl sulfonic acid fluoride (30.3g, 0.1mol) in acetonitrile solution, heating reflux reaction 24h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (perfluoro butyl sulphonyl) imines of white (35g, 0.06mol), yield is about 92%;
3) will two (perfluoro butyl sulphonyl) imines (10g, 0.017mol) with ethylene bromohyrin (2.4g, 0.019mol), dry K
2CO
3(2.4g, 0.017mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 3h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (9.6g, 0.015mol), yield is 90% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (9.6g, 0.015mol), (3.03g 0.03mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (1.63g, 0.018mol) in diethyl ether solution, reflux 18h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 8.1g of the fluoroalkyl sulfimide base ethyl propenoate monomer 2 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 2, product purity 97.2%, and yield is 78%.
1) (30.2g 0.1mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 1h, room temperature volatilization liquefied ammonia with perfluoro butyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white perfluoro butyl sulphonamide (20g, 0.066mol), yield is 66%;
2) with the perfluoro butyl sulphonamide (20g, 0.066mol) with triethylamine (20.2g 0.2mol) is dissolved in the 50mL acetonitrile, drip gradually under the normal temperature perfluoro butyl sulfonic acid fluoride (40.4g, 0.134mol) in acetonitrile solution, heating reflux reaction 36h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (perfluoro butyl sulphonyl) imines of white (35g, 0.06mol), yield is about 92%;
3) will two (perfluoro butyl sulphonyl) imines (10g, 0.017mol) with ethylene bromohyrin (3.9g, 0.031mol), dry K
2CO
3(7g, 0.051mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2.5h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (10.2g, 0.016mol), yield is 96% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (10.2g, 0.016mol), (1.62g 0.016mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (2.9g, 0.032mol) in diethyl ether solution, reflux 15h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 9.5g of the fluoroalkyl sulfimide base ethyl propenoate monomer 3 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 3, product purity 96.8%, and yield is 85%.
1) (15.2g 0.1mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 3h, room temperature volatilization liquefied ammonia with the trifluoromethyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white trifluoromethyl sulphonamide (10.73g, 0.072mol), yield is 72%;
2) with the trifluoromethyl sulphonamide (10g, 0.067mol) with triethylamine (10.1g 0.1mol) is dissolved in the 50mL acetonitrile, drip gradually under the normal temperature perfluoro-methyl sulfonic acid fluoride (20.2g, 0.133mol) in acetonitrile solution, heating reflux reaction 48h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (trifluoromethyl sulphonyl) imines of white (30g, 0.052mol), yield is about 84%;
3) will two (trifluoromethyl sulphonyl) imines (10g, 0.036mol) with ethylene bromohyrin (6.7g, 0.054mol), dry K
2CO
3(5g, 0.036mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (11g, 0.034mol), yield is 94% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (11g, 0.034mol), (6.06g 0.06mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (7.7g, 0.085mol) in diethyl ether solution, reflux 20h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 11.4g of the fluoroalkyl sulfimide base ethyl propenoate monomer 4 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 4, product purity 96.3%, and yield is 85%.
1) (50g 0.124mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 3h, room temperature volatilization liquefied ammonia with the perfluoro hexyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white trifluoromethyl sulphonamide (36.23g, 0.091mol), yield is 73%;
2) with the perfluoro hexyl sulphonamide (30g, 0.075mol) with triethylamine (15.2g 0.15mol) is dissolved in the 60mL acetonitrile, drip gradually under the normal temperature perfluoro hexyl sulfonic acid fluoride (36.3g, 0.09mol) in acetonitrile solution, heating reflux reaction 48h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (perfluoro hexyl sulphonyl) imines of white (56.2g, 0.072mol), yield is about 96%;
3) will two (perfluoro hexyl sulphonyl) imines (10g, 0.013mol) with ethylene bromohyrin (3.25g, 0.026mol), dry K
2CO
3(5g, 0.036mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2.5h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (10g, 0.012mol), yield is 94% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (10g, 0.012mol), (3.64g 0.036mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (3.26g, 0.036mol) in diethyl ether solution, reflux 15h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 8.8g of the fluoroalkyl sulfimide base ethyl propenoate monomer 5 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 5, product purity 95.6%, and yield is 80%.
1) (50g 0.124mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 5h, room temperature volatilization liquefied ammonia with the perfluoro hexyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white trifluoromethyl sulphonamide (36.23g, 0.091mol), yield is 73%;
2) with the perfluoro hexyl sulphonamide (30g, 0.075mol) with triethylamine (8.33g 0.083mol) is dissolved in the 60mL acetonitrile, drip gradually under the normal temperature perfluoro hexyl sulfonic acid fluoride (36.3g, 0.09mol) in acetonitrile solution, heating reflux reaction 48h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again, oil pump decompression distillation obtain two (the trifluoro hexyl sulphonyl) imines of white (58g, 0.074mol), yield is about 99%;
3) will two (perfluoro hexyl sulphonyl) imines (20g, 0.026mol) with ethylene bromohyrin (3.25g, 0.026mol), dry K
2CO
3(5g, 0.036mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (20.8g, 0.025mol), yield is 97% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (20.8g, 0.025mol), (3.64g 0.036mol) is dissolved in the ether with a small amount of Resorcinol triethylamine; Under ice-water bath; Drip gradually acrylate chloride (2.26g, 0.025mol) in diethyl ether solution, reflux 16h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 19.4g of the fluoroalkyl sulfimide base ethyl propenoate monomer 6 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 6, product purity 96.2%, and yield is 85%.
1) (15.2g 0.1mol) dropwise adds in the 100mL liquefied ammonia, stirring reaction 4h, room temperature volatilization liquefied ammonia with the trifluoromethyl sulfonic acid fluoride; Add anhydrous diethyl ether and dilute sulphuric acid, be stirred to the solid dissolving; Divide the phase of anhydrating, with distilled water wash for several times, and use anhydrous sodium sulfate drying; Distillation removes desolvates, with the ethanol/water recrystallization and distil white trifluoromethyl sulphonamide (10.73g, 0.072mol), yield is 72%;
2) with the trifluoromethyl sulphonamide (10g, 0.067mol) with triethylamine (10.1g 0.1mol) is dissolved in the 50mL acetonitrile, drip gradually under the normal temperature perfluoro butyl sulfonic acid fluoride (30.2g, 0.1mol) in acetonitrile solution, heating reflux reaction 48h.Distillation removes and desolvates, and adds the methylene dichloride dissolving, with distilled water wash for several times, and with anhydrous magnesium sulfate drying, and removal of solvent under reduced pressure.Enriching sulfuric acid acidation again; Oil pump decompression distillation obtains the imines (23.1g of structural formula for
; 0.0536mol), yield is about 80%;
3) with structural formula do
Imines (10g, 0.023mol) with ethylene bromohyrin (5.6g, 0.045mol), dry K
2CO
3(5g, 0.036mol), little amount of N aI is dissolved in the acetone solvent, heating reflux reaction 2h under agitation condition.Be cooled to normal temperature then, solids removed by filtration, solids washed with acetone are for several times.The solvent of filtrating is removed in distillation, and crude product is purified with the ethanol/water recrystallization, and (10g, 0.021mol), yield is 92% to obtain fluorine alcohol.
4) with the fluorine that obtains in step 3) alcohol (10g, 0.021mol), triethylamine (6.06g 0.06mol) is dissolved in the ether with a small amount of Resorcinol, under ice-water bath, drip gradually acrylate chloride (4g, 0.045mol) in diethyl ether solution, reflux 20h.Mixture difference water and hydrochloric acid soln washing neutralize with saturated sodium bicarbonate solution several times then.Leave standstill, separate organic layer, ether solvent is removed in distillation.Product is with the methanol recrystallization purifying, the title product 9.3g of the fluoroalkyl sulfimide base ethyl propenoate monomer 7 that obtains enjoying a double blessing.Gc (GC) is analyzed as shown in Figure 7, product purity 97.1%, and yield is 83% acquisition.
Wherein, the gas chromatograph model is GC-1690, and the post type is a capillary column, and sample size is 0.2ul.
Claims (10)
1. fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing, it has following structural formula:
, wherein, R
F1And R
F2Be that molecular formula is C
nF
2n+1Perfluoroalkyl, n is the positive integer of 1-6, R
F1And R
F2Group is identical or different.
2. according to the said fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing of claim 1, it is characterized in that: said R
F1And R
F2Be that molecular formula is C
4F
9Perfluoro butyl.
3. one kind prepares the said fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing of claim 1, and its step comprises: be R with structural formula 1)
F1SO
2The perfluoroalkyl sulfonyl fluoride of F and liquefied ammonia reaction, obtaining structural formula is R
F1SO
2NH
2The perfluoroalkyl sulphonamide; 2) be R with structural formula
F1SO
2NH
2Perfluoroalkyl sulphonamide and structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F reacts, and obtains structural formula and does
The fluoroalkyl sulfimide of enjoying a double blessing; 3) with structural formula do
Fluoroalkyl sulfimide and the ethylene bromohyrin reaction of enjoying a double blessing obtain structural formula and do
Fluorine alcohol; 4) with structural formula do at last
Fluorine alcohol obtain structural formula with the acrylate chloride reaction and do
The fluoroalkyl sulfimide base ethyl propenoate monomer of enjoying a double blessing; Wherein, R
F1And R
F2Be that molecular formula is C
nF
2n+1Perfluoroalkyl, n is the positive integer of 1-6.
4. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 3 is characterized in that: the said the 1st) the step reaction is to be R with structural formula
F1SO
2The perfluoroalkyl sulfonyl fluoride of F adds in the excessive liquefied ammonia, and room temperature reaction 1-5 hour, obtaining said structural formula behind separation and the purifying was R
F1SO
2NH
2The perfluoroalkyl sulphonamide.
5. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 3 is characterized in that: the said the 2nd) the step reaction is to be 1 with mol ratio: (1-2): structural formula (1-3) is R
F1SO
2NH
2Perfluoroalkyl sulphonamide, structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F and triethylamine in acetonitrile back flow reaction 24-48 hour, separate and purifying after obtain said structural formula and do
The fluoroalkyl sulfimide of enjoying a double blessing.
6. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 5, it is characterized in that: the said the 2nd) structural formula is R in the step reaction
F1SO
2NH
2Perfluoroalkyl sulphonamide, structural formula be R
F2SO
2The perfluoroalkyl sulfonyl fluoride of F and the mol ratio of triethylamine are 1: (1-1.5): (1.1-2).
7. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 3 is characterized in that: the said the 3rd) the step reaction is to be 1 with mol ratio: (1-2): structural formula (1-3) does
Enjoy a double blessing fluoroalkyl sulfimide, ethylene bromohyrin and K
2CO
3, and the NaI of catalytic amount in acetone heating reflux reaction 2-3 hour, separate and purifying after obtain structural formula and do
Fluorine alcohol.
8. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 7, it is characterized in that: the said the 3rd) mol ratio of enjoy a double blessing fluoroalkyl sulfimide and the ethylene bromohyrin of structural formula for
is 1 in the step reaction: (1.1-1.8).
9. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 3; It is characterized in that: the said the 4th) step reaction is to be in the ether mixing solutions of the acrylate chloride of the 1-3 Resorcinol that in cooling bath, splashes into molfraction is a fluorine alcohol for
of 1 structural formula, molfraction is 1-4 triethylamine and catalytic amount with molfraction; Reflux 12-20 hour then, promptly obtain the enjoy a double blessing fluoroalkyl sulfimide base ethyl propenoate monomer of structural formula after the separation and purification for
.
10. the said preparation fluoroalkyl sulfimide base ethyl propenoate monomer methods of enjoying a double blessing according to claim 9; It is characterized in that: the said the 4th) mol ratio of the fluorine pure and mild acrylate chloride of structural formula for
is 1 in the step reaction: (1.2-2.5), the heating reflux reaction time is 15-18 hour.
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| CN107074753A (en) * | 2014-11-20 | 2017-08-18 | 中央硝子株式会社 | The manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt |
| CN108147981A (en) * | 2016-12-06 | 2018-06-12 | 中国科学院宁波材料技术与工程研究所 | A kind of method that anti-phase transfer catalysis prepares sulfonyl imide compounds |
| CN108409688A (en) * | 2018-02-12 | 2018-08-17 | 中山大学 | A kind of perfluorinated alkyl sulfonamide reactive amines acrylate compounds and preparation method |
| CN110229593A (en) * | 2019-05-20 | 2019-09-13 | 陈玲玲 | A kind of power transmission line coatings and preparation method thereof |
| CN115232033A (en) * | 2022-08-11 | 2022-10-25 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (trifluoromethyl) sulfonyl imide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107074753A (en) * | 2014-11-20 | 2017-08-18 | 中央硝子株式会社 | The manufacture method of (fluorine sulphonyl) perfluoro alkane sulfimide salt |
| CN107074753B (en) * | 2014-11-20 | 2019-09-06 | 中央硝子株式会社 | The manufacturing method of (fluorine sulphonyl) perfluoro alkane sulfimide salt |
| CN108147981A (en) * | 2016-12-06 | 2018-06-12 | 中国科学院宁波材料技术与工程研究所 | A kind of method that anti-phase transfer catalysis prepares sulfonyl imide compounds |
| CN108409688A (en) * | 2018-02-12 | 2018-08-17 | 中山大学 | A kind of perfluorinated alkyl sulfonamide reactive amines acrylate compounds and preparation method |
| CN110229593A (en) * | 2019-05-20 | 2019-09-13 | 陈玲玲 | A kind of power transmission line coatings and preparation method thereof |
| CN115232033A (en) * | 2022-08-11 | 2022-10-25 | 衢州市九洲化工有限公司 | Preparation method of lithium bis (trifluoromethyl) sulfonyl imide |
| CN115232033B (en) * | 2022-08-11 | 2023-08-25 | 衢州市九洲化工有限公司 | Preparation method of lithium bistrifluoromethylsulfonyl imide |
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