CN104262617A - Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator - Google Patents
Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator Download PDFInfo
- Publication number
- CN104262617A CN104262617A CN201410497295.8A CN201410497295A CN104262617A CN 104262617 A CN104262617 A CN 104262617A CN 201410497295 A CN201410497295 A CN 201410497295A CN 104262617 A CN104262617 A CN 104262617A
- Authority
- CN
- China
- Prior art keywords
- pfcb
- methylene dichloride
- ratio
- novel
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and a preparation method and application of the novel perfluorocyclobutyl-containing macroinitiator. The preparation method comprises the following main steps: (1) taking methoxydiphenol and 1, 2-dibromotetrafluoroethane as raw materials, and synthesizing novel trifluorovinyl aryl ether; (2) synthesizing polymers, namely PFCB-OMe with different molecular weights by utilizing (2 phi + 2 phi) thermal cyclization polymerization of novel trifluorovinyl aryl ether; (3) exploring deprotection reaction conditions to obtain polymers, namely PFCB-OH with different degrees of deprotection, and simultaneously preparing a macroinitiator PFCB-BA; and (4) preparing a grafted copolymer, namely PFCB-P tBMA by utilizing ATRP reaction between commercial tert-butyl methacrylate and PFCB-BA.
Description
Technical field
The present invention relates to organic chemistry and technical field of polymer synthetic chemistry, particularly relate to a kind of preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl for atom transfer radical polymerization.
Background technology
1993, the researchist of Dow Chemical company developed a class novel fluoropolymers---perfluorocyclobutanearyl (PFCB) aryl ethers polymkeric substance.This base polymer combines the engineered thermoplastic of polyarylether and the stability of fluorine carbon part, there is the advantages such as low specific inductivity, high heat and thermo-oxidative stability, excellent optical property and good workability, have in wave guide, optics and spacecraft coating etc. and have broad application prospects.PFCB type polymkeric substance is generally obtained by the polymerization of (2 π+2 π) thermal cyclization by Trifluorovinyl Aryl Ethers.The step-growth polymerization of this thermal initiation, without any need for catalyzer or initiator, and can not produce condensation product.In addition, simply by removing thermal source to control polyreaction, the polymkeric substance of different molecular weight can be obtained.Due to relatively high polymerization temperature (>150 DEG C) and unique polymerization mechanism, mainly concentrating on the research of PFCB type polymkeric substance at present utilizes different Trifluorovinyl Aryl Ethers monomer to carry out thermal cyclization polymerization preparation containing the homopolymer of PFCB or random copolymers, simultaneously, by the design of functional group and the restriction of synthesis that link trifluoro vinyl in monomer, be difficult to general commercialization monomer to be incorporated in Trifluorovinyl Aryl Ethers monomer obtain compound fluoropolymer, the factor of these two aspects limits the development of PFCB type polymkeric substance.In order to expand the application of this base polymer, by high performance PFCB type polymkeric substance with other business-like polymer scales altogether, be significantly.The prepared novel polymkeric substance containing PFCB will not only retain the performance of commercial polymerization thing, also has some premium propertiess of PFCB type polymkeric substance simultaneously.And by synthesis block or graft copolymer, be a kind of desirable route realizing this imagination.
Recent two decades comes, and active free radical polymerization can either keep ionic living polymerization to control the ability of reaction because of it, does not lose again the superiority of radical polymerization, is developed rapidly.The applicable monomer scope of atom transfer radical polymerization (ATRP) is wherein wide, reaction conditions is gentle, uses the most extensive.Because ATRP can control the molecular weight and molecualr weight distribution of polymkeric substance, obtain the polymkeric substance of specified molecular weight and narrow molecular weight distributions, thus can control effectively to the chemical structure of polymkeric substance, be widely used in the synthesis of segmented copolymer and graft copolymer.In ATRP system, select suitable initiator to have vital effect for the controllability of polymerization system, thus develop the extensive concern that effective initiator causes people.
Based on this, the present invention, from molecular designing angle, designs and synthesizes the macromole evocating agent (PFCB-BA) that a class contains the atom transfer radical polymerization of PFCB.Utilize the atom transfer radical polymerization of such macromole evocating agent trigger monomer methacrylic acid tertiary butyl ester, obtain the novel graft copolymer (PFCB-PtBMA) containing perfluorocyclobutanearyl.
Summary of the invention
The object of this invention is to provide a kind of novel macromolecule initiator PFCB-BA of the atom transfer radical polymerization containing PFCB;
Object of the present invention also provides the preparation method of a kind of novel macromolecule initiator PFCB-BA of the above-mentioned atom transfer radical polymerization containing PFCB;
Another object of the present invention be to provide a kind of above-mentioned containing PFCB the purposes of novel macromolecule initiator PFCB-BA of atom transfer radical polymerization, prepare with PFCB type polymkeric substance be main chain, the acrylic polymer new graft copolymers that is side chain.
Content of the present invention is with the fragrant diphenolic compound and 1 containing methoxyl group; 2-dibromotetrafluoroethane raw material is raw material; first react through fluoroalkylation; again through eliminative reaction, the polymerization of (2 π+2 π) thermal cyclization and protective reaction, preparation is containing the PFCB type polymkeric substance (PFCB-OH) of reactive group (hydroxyl).The effect of PFCB-OH and 2-bromo propionyl chloro, obtains macromole evocating agent (PFCB-BA).PFCB-BA and business-like acrylic ester monomer, by radical polymerization or active free radical polymerization method copolymerization, obtain the new graft copolymers (PFCB-g-PtBMA) containing PFCB.
Provided by the present invention containing PFCB the novel macromolecule initiator PFCB-BA of atom transfer radical polymerization there is following structure:
Wherein: X is C1 or Br;
Ar is:
The present invention adopts following technical scheme:
(1) with different methoxyl group diphenol and 1,2-dibromotetrafluoroethane raw material, a series of novel Trifluorovinyl Aryl Ethers monomer containing methoxyl group is synthesized;
(2) utilize (2 π+2 π) thermal cyclization polymerization of Trifluorovinyl Aryl Ethers monomer described in (1), prepare polymer P FCB-OMe;
(3) PFCB-OMe and boron tribromide effect, obtain polymer P FCB-OH.Utilize PFCB-OH and 2-bromo propionyl chloro, prepare macromole evocating agent PFCB-BA;
(4) utilize the ATRP between PFCB-BA and Tert-butyl Methacrylate to react, prepare graft copolymer PFCB-g-PtBMA.
Concrete grammar is as follows:
Of the present invention containing PFCB the preparation method of novel macromolecule initiator PFCB-BA of atom transfer radical polymerization as follows:
(1) in methoxyl group fragrance dihydric phenol, dimethyl sulfoxide (DMSO) is added, stirring makes it dissolve, the weightmeasurement ratio of methoxyl group fragrance dihydric phenol and dimethyl sulfoxide (DMSO) is 5-10:200g/mL, mixed solution oil pump is reduced pressure, with nitrogen to bubbling in solution to remove the oxygen in solution, under nitrogen protection, add cesium carbonate, the weight ratio of cesium carbonate and methoxyl group fragrance dihydric phenol is 45-55:5-10, with nitrogen after bubbling in solution, add 1, 2-dibromotetrafluoroethane, 1, the weight ratio of 2-dibromotetrafluoroethane and methoxyl group fragrance dihydric phenol is 35-45:5-10, be warming up to 40-60 DEG C, stir 1-3 days, stop heating, after reaction mixture cool to room temperature, add water to stir, the volume ratio of water and dimethyl sulfoxide (DMSO) is 100-300:200, then methylene dichloride is added, the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 50-150:200, separate organic phase, organic phase washes three times again with water, merge aqueous phase, with n-hexane extraction three times, merge organic phase, with anhydrous magnesium sulfate drying, suction filtration, with Rotary Evaporators except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid,
(2) in reactor, zinc granule is added, colourless transparent liquid prepared by step (1) and acetonitrile, the weight ratio of zinc granule and colourless transparent liquid is 1-2:4-6, the weightmeasurement ratio of zinc granule and acetonitrile is 1-2:100g/mL, then heating reflux reaction 18-36h, stop heating, be cooled to room temperature, leave standstill, incline and supernatant liquid, remaining salt precipitation mixture adds washing, with n-hexane extraction three times, organic phase anhydrous magnesium sulfate drying, merge organic phase, with rotary evaporation except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid, i.e. Trifluorovinyl Aryl Ethers,
(3) Trifluorovinyl Aryl Ethers prepared by step (2) is added in reactor, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, and circulates after three times, puts into 180 DEG C of oil baths heating 20-30h, then 190 DEG C of heating 10-15h are warming up to, after room temperature cooling, gained solid chloroform, dissolve, then with adding normal hexane, filter, filter cake is at 50-70 DEG C of vacuum-drying 10-15h, obtain white solid, i.e. polymer P FCB-OMe;
(4) methylene dichloride is added in the polymer P FCB-OMe prepared toward step (3), make it dissolve, the weightmeasurement ratio of PFCB-OMe and methylene dichloride is 5-8:100g/mL, then mixture is put into ice-water bath, slowly boron tribromide and methylene dichloride mixing solutions is dripped in mixture, the weightmeasurement ratio of PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 5-8:51g/mL, after stirring 0.5h after dropwising in ice-water bath, stirring at room temperature 6h, add ethanol cancellation reaction, the volume ratio of ethanol and methylene dichloride is 0.5-2:100, the cooling of gained mixture room temperature leaves standstill 1h, filter, three times are washed with methylene dichloride, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. polymer P FCB-OH,
(5) butanone is added in the polymer P FCB-OH prepared toward step (4), make it dissolve, and then add triethylamine, the weightmeasurement ratio of polymer P FCB-OH and butanone is 5-7:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 5-7:1-2g/mL, then mixture is put into ice-water bath, slow dropping 2-bromo propionyl chloro, the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 5-7:1-1.5g/mL, in ice-water bath, 1h is stirred after dropwising, the salt that suction filtration removing generates, with rotary evaporation except desolventizing, gained resistates dissolve with methanol, then with adding methylene dichloride, filter, filtrate is spin-dried for rotation steaming, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. macromole evocating agent PFCB-BA.
In step (1), the weightmeasurement ratio of preferred methoxyl group fragrance dihydric phenol and dimethyl sulfoxide (DMSO) is 7:200g/mL, the weight ratio of cesium carbonate and methoxyl group fragrance dihydric phenol is 48.9:7,1, the weight ratio of 2-dibromotetrafluoroethane and methoxyl group fragrance dihydric phenol is 38.9:7, the volume ratio of water and dimethyl sulfoxide (DMSO) is 200:200, and the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 100:200.
In step (1), be preferably warming up to 50 DEG C, stir 2 days.
In step (2), the weight ratio of preferred zinc granule and colourless transparent liquid is 1.56:4.98, and the weightmeasurement ratio of zinc granule and acetonitrile is 1.56:100g/mL, heating reflux reaction 24h.
In step (3), preferably put into 180 DEG C of oil bath heating 24h, be then warming up to 190 DEG C of heating 12h, after room temperature cooling, gained solid chloroform, dissolves, and then with adding normal hexane, filter, filter cake is at 60 DEG C of vacuum-drying 12h.
In step (4), the weightmeasurement ratio of preferred PFCB-OMe and methylene dichloride is the weightmeasurement ratio of 6.3:100g/mL, PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 6.3:51g/mL, and the volume ratio of ethanol and methylene dichloride is 1:100.
In step (4), in boron tribromide and methylene dichloride mixing solutions, both volume ratios are 1:50.
In step (5), the weightmeasurement ratio of preferred polymers PFCB-OH and butanone is 6.05:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 6.05:1.4g/mL, and the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 6.05:1.2g/mL.
In step (1) and step (2), column chromatography uses normal hexane to carry out separating-purifying.
Utilize macromole evocating agent of the present invention for the preparation of be main chain with PFCB type polymkeric substance, a purposes for the acrylic polymer new graft copolymers that is side chain, concrete preparation method is as follows:
By macromole evocating agent PFCB-BA of the present invention, Tert-butyl Methacrylate and cuprous bromide join in reactor, macromole evocating agent PFCB-BA, the weight ratio of Tert-butyl Methacrylate and cuprous bromide is 3-4:0.05-0.15:0.015, substitute nitrogen three times, add methyl-phenoxide, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is 3-4:5-15g/mL, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, circulate after three times, add five methyl diethylentriamine, the weightmeasurement ratio of PFCB-BA and five methyl diethylentriamine is 3-4:0.01-0.03g/mL, freezing inflated with nitrogen of bleeding thaws three times again, reactor is put at once 65 DEG C of oil baths, stir 3h, reactor is taken out from oil bath, put into liquid nitrogen cancellation reaction, after gained mixture is warming up to room temperature, add THF to dissolve, cross neutral alumina column removing mantoquita, rotary evaporation is except after desolventizing, add THF to dissolve, precipitate in cold normal hexane, suction filtration obtains white polymer, again precipitate, after suction filtration, at 60 DEG C of vacuum-drying 24h, obtain white solid, be graft copolymer PFCB-g-PtBMA.
Preferred: the weight ratio of macromole evocating agent PFCB-BA, Tert-butyl Methacrylate and cuprous bromide is 3.07:0.106:0.015, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is the weightmeasurement ratio of 3.07:10g/mL, PFCB-BA and five methyl diethylentriamine is 3.07:0.02g/mL.
The structure of all new micromolecular compounds is confirmed through nucleus magnetic resonance, ultimate analysis and mass spectrum.The structure of all polymkeric substance is confirmed through nucleus magnetic resonance, gel chromatography, and partial results is shown in specific embodiment part.
Positively effect of the present invention is as follows:
The present invention is from molecular designing aspect, and have selected a class containing methoxyl group fragrance dihydric phenol is initial feed, through the typical itineraries of perfluorocyclobutanearyl aryl-ether Macroscopic single crystal, obtains polymer P FCB type polymer P FCB-OMe.PFCB-OMe boron tribromide obtains the PFCB-OH containing reactive group (-OH) with high yield after going protection.Utilize-the OH in PFCB-OH, small molecules initiator primitive 2-bromine propionyl be incorporated in PFCB type polymkeric substance, successfully synthesize a class contain PFCB the macromole evocating agent PFCB-g-BA of atom transfer radical polymerization.PFCB type polymkeric substance is obtained by the step-growth polymerization of thermal initiation, and polymerization process without any need for catalyzer or initiator, and can not produce condensation product.In addition, simply by removing thermal source to control polyreaction, the macromole evocating agent PFCB-g-BA of different molecular weight can be obtained, therefore can the Modulatory character of simple realization macromole evocating agent PFCB-g-BA molecular weight.
The structure that the PFCB-g-BA utilizing the present invention to prepare causes the graft copolymer PFCB-g-PtBMA prepared by ATRP polymerization of Tert-butyl Methacrylate is confirmed through nucleus magnetic resonance, gel chromatography test result shows that PFCB-g-PtBMA has narrower molecular weight distribution, illustrates that the macromole evocating agent PFCB-g-BA that the present invention obtains has good initiation performance.
The PFCB-g-BA initiating methacrylates class monomer utilizing the present invention to prepare carries out ATRP reaction, in PFCB type polymkeric substance, polyacrylate polymers is introduced by the method for grafting, successfully high performance PFCB type polymkeric substance is combined with business-like acrylic polymer, thus can give novel polymer some good performances, as high hydrophobic oleophobic performance, low surface energy, good solvent resistance and chemical-resistant stability etc.
Accompanying drawing explanation
Fig. 1 is the infrared spectra of PFCB-g-PtBMA.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of PFCB-g-PtBMA.
Fig. 3 is the fluorine nmr spectrogram of PFCB-g-PtBMA.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
The concrete steps of the preparation method of the amphipathic graft copolymer containing perfluorocyclobutanearyl of the present invention are as follows:
(1) in 5-methoxyl group Resorcinol, dimethyl sulfoxide (DMSO) is added, stirring makes it dissolve, the weightmeasurement ratio of 5-methoxyl group Resorcinol and dimethyl sulfoxide (DMSO) is 5:200g/mL, mixed solution oil pump is reduced pressure, with nitrogen to bubbling in solution to remove the oxygen in solution, under nitrogen protection, add cesium carbonate, the weight ratio of cesium carbonate and 5-methoxyl group Resorcinol is 45:5, with nitrogen after bubbling in solution, add 1, 2-dibromotetrafluoroethane, 1, the weight ratio of 2-dibromotetrafluoroethane and 5-methoxyl group Resorcinol is 35:5, be warming up to 40 DEG C, stir 3 days, stop heating, after reaction mixture cool to room temperature, add water to stir, the volume ratio of water and dimethyl sulfoxide (DMSO) is 100:200, then methylene dichloride is added, the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 50:200, separate organic phase, organic phase washes three times again with water, merge aqueous phase, with n-hexane extraction three times, merge organic phase, with anhydrous magnesium sulfate drying, suction filtration, with Rotary Evaporators except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid,
(2) in reactor, zinc granule is added, colourless transparent liquid prepared by step (1) and acetonitrile, the weight ratio of zinc granule and colourless transparent liquid is 1:4, the weightmeasurement ratio of zinc granule and acetonitrile is 1:100g/mL, then heating reflux reaction 18h, stop heating, be cooled to room temperature, leave standstill, incline and supernatant liquid, remaining salt precipitation mixture adds washing, with n-hexane extraction three times, organic phase anhydrous magnesium sulfate drying, merge organic phase, with rotary evaporation except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid, i.e. Trifluorovinyl Aryl Ethers,
(3) Trifluorovinyl Aryl Ethers prepared by step (2) is added in reactor, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, and circulates after three times, puts into 180 DEG C of oil baths heating 20h, then 190 DEG C of heating 10h are warming up to, after room temperature cooling, gained solid chloroform, dissolve, then with adding normal hexane, filter, filter cake is at 50 DEG C of vacuum-drying 15h, obtain white solid, i.e. polymer P FCB-OMe;
(4) methylene dichloride is added in the polymer P FCB-OMe prepared toward step (3), make it dissolve, the weightmeasurement ratio of PFCB-OMe and methylene dichloride is 5:100g/mL, then mixture is put into ice-water bath, slowly boron tribromide and methylene dichloride mixing solutions is dripped in mixture, the weightmeasurement ratio of PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 5:51g/mL, after stirring 0.5h after dropwising in ice-water bath, stirring at room temperature 6h, add ethanol cancellation reaction, the volume ratio of ethanol and methylene dichloride is 0.5:100, the cooling of gained mixture room temperature leaves standstill 1h, filter, three times are washed with methylene dichloride, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. polymer P FCB-OH,
(5) butanone is added in the polymer P FCB-OH prepared toward step (4), make it dissolve, and then add triethylamine, the weightmeasurement ratio of polymer P FCB-OH and butanone is 5:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 5:1g/mL, then mixture is put into ice-water bath, slow dropping 2-bromo propionyl chloro, the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 5:1g/mL, in ice-water bath, 1h is stirred after dropwising, the salt that suction filtration removing generates, with rotary evaporation except desolventizing, gained resistates dissolve with methanol, then with adding methylene dichloride, filter, filtrate is spin-dried for rotation steaming, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. macromole evocating agent PFCB-BA,
(6) by macromole evocating agent PFCB-BA prepared by step (5), Tert-butyl Methacrylate and cuprous bromide join in reactor, macromole evocating agent PFCB-BA, the weight ratio of Tert-butyl Methacrylate and cuprous bromide is 3:0.05:0.015, substitute nitrogen three times, add methyl-phenoxide, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is 3:5g/mL, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, circulate after three times, add five methyl diethylentriamine, the weightmeasurement ratio of PFCB-BA and five methyl diethylentriamine is 3:0.01g/mL, freezing inflated with nitrogen of bleeding thaws three times again, reactor is put at once 65 DEG C of oil baths, stir 3h, reactor is taken out from oil bath, put into liquid nitrogen cancellation reaction, after gained mixture is warming up to room temperature, add THF to dissolve, cross neutral alumina column removing mantoquita, rotary evaporation is except after desolventizing, add THF to dissolve, precipitate in cold normal hexane, suction filtration obtains white polymer, again precipitate, after suction filtration, at 60 DEG C of vacuum-drying 24h, obtain white solid, be polymer P FCB-g-PtBMA.
In step (4), in boron tribromide and methylene dichloride mixing solutions, both volume ratios are 1:50.
In step (1) and step (2), column chromatography uses normal hexane to carry out separating-purifying.
Embodiment 2
The concrete steps of the preparation method of the amphipathic graft copolymer containing perfluorocyclobutanearyl of the present invention are as follows:
(1) in 5-methoxyl group Resorcinol, dimethyl sulfoxide (DMSO) is added, stirring makes it dissolve, the weightmeasurement ratio of 5-methoxyl group Resorcinol and dimethyl sulfoxide (DMSO) is 10:200g/mL, mixed solution oil pump is reduced pressure, with nitrogen to bubbling in solution to remove the oxygen in solution, under nitrogen protection, add cesium carbonate, the weight ratio of cesium carbonate and 5-methoxyl group Resorcinol is 55:10, with nitrogen after bubbling in solution, add 1, 2-dibromotetrafluoroethane, 1, the weight ratio of 2-dibromotetrafluoroethane and 5-methoxyl group Resorcinol is 45:10, be warming up to 60 DEG C, stir 1 day, stop heating, after reaction mixture cool to room temperature, add water to stir, the volume ratio of water and dimethyl sulfoxide (DMSO) is 300:200, then methylene dichloride is added, the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 150:200, separate organic phase, organic phase washes three times again with water, merge aqueous phase, with n-hexane extraction three times, merge organic phase, with anhydrous magnesium sulfate drying, suction filtration, with Rotary Evaporators except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid,
(2) in reactor, zinc granule is added, colourless transparent liquid prepared by step (1) and acetonitrile, the weight ratio of zinc granule and colourless transparent liquid is 2:6, the weightmeasurement ratio of zinc granule and acetonitrile is 2:100g/mL, then heating reflux reaction 36h, stop heating, be cooled to room temperature, leave standstill, incline and supernatant liquid, remaining salt precipitation mixture adds washing, with n-hexane extraction three times, organic phase anhydrous magnesium sulfate drying, merge organic phase, with rotary evaporation except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid, i.e. Trifluorovinyl Aryl Ethers,
(3) Trifluorovinyl Aryl Ethers prepared by step (2) is added in reactor, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, and circulates after three times, puts into 180 DEG C of oil baths heating 30h, then 190 DEG C of heating 15h are warming up to, after room temperature cooling, gained solid chloroform, dissolve, then with adding normal hexane, filter, filter cake is at 70 DEG C of vacuum-drying 10h, obtain white solid, i.e. polymer P FCB-OMe;
(4) methylene dichloride is added in the polymer P FCB-OMe prepared toward step (3), make it dissolve, the weightmeasurement ratio of PFCB-OMe and methylene dichloride is 8:100g/mL, then mixture is put into ice-water bath, slowly boron tribromide and methylene dichloride mixing solutions is dripped in mixture, the weightmeasurement ratio of PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 8:51g/mL, after stirring 0.5h after dropwising in ice-water bath, stirring at room temperature 6h, add ethanol cancellation reaction, the volume ratio of ethanol and methylene dichloride is 2:100, the cooling of gained mixture room temperature leaves standstill 1h, filter, three times are washed with methylene dichloride, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. polymer P FCB-OH,
(5) butanone is added in the polymer P FCB-OH prepared toward step (4), make it dissolve, and then add triethylamine, the weightmeasurement ratio of polymer P FCB-OH and butanone is 7:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 7:2g/mL, then mixture is put into ice-water bath, slow dropping 2-bromo propionyl chloro, the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 7:1.5g/mL, in ice-water bath, 1h is stirred after dropwising, the salt that suction filtration removing generates, with rotary evaporation except desolventizing, gained resistates dissolve with methanol, then with adding methylene dichloride, filter, filtrate is spin-dried for rotation steaming, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. macromole evocating agent PFCB-BA,
(6) by macromole evocating agent PFCB-BA prepared by step (5), Tert-butyl Methacrylate and cuprous bromide join in reactor, macromole evocating agent PFCB-BA, the weight ratio of Tert-butyl Methacrylate and cuprous bromide is 4:0.15:0.015, substitute nitrogen three times, add methyl-phenoxide, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is 4:15g/mL, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, circulate after three times, add five methyl diethylentriamine, the weightmeasurement ratio of PFCB-BA and five methyl diethylentriamine is 4:0.03g/mL, freezing inflated with nitrogen of bleeding thaws three times again, reactor is put at once 65 DEG C of oil baths, stir 3h, reactor is taken out from oil bath, put into liquid nitrogen cancellation reaction, after gained mixture is warming up to room temperature, add THF to dissolve, cross neutral alumina column removing mantoquita, rotary evaporation is except after desolventizing, add THF to dissolve, precipitate in cold normal hexane, suction filtration obtains white polymer, again precipitate, after suction filtration, at 60 DEG C of vacuum-drying 24h, obtain white solid, be graft copolymer PFCB-g-PtBMA.
In step (4), in boron tribromide and methylene dichloride mixing solutions, both volume ratios are 1:50.
In step (1) and step (2), column chromatography uses normal hexane to carry out separating-purifying.
Embodiment 3
(1) in 500mL three-necked bottle, add 5-methoxyl group Resorcinol (7.0g, 0.05mol) and methyl-sulphoxide (200mL), stir and dihydroxy-benzene is dissolved.With oil pump decompression 30min after, with nitrogen to bubbling 30min in solution to remove the oxygen in solution.Under nitrogen protection, cesium carbonate (48.9g, 0.15mol) is added.With nitrogen after bubbling 30min in solution, add 1,2-dibromotetrafluoroethane (38.9g, 0.15mol).Be warming up to 50 DEG C, stir 2 days.Stop heating, reaction mixture is transferred to 1L beaker can only in, after system cool to room temperature, add water (200mL), stir 10min, then add methylene dichloride (100mL), separate organic phase, organic phase washes with water again (50mL × 3).Merge aqueous phase, with n-hexane extraction (50mL × 3).Merge organic phase, use anhydrous magnesium sulfate drying.Suction filtration, with Rotary Evaporators except desolventizing.Remaining liquid column chromatography carries out separating-purifying (normal hexane), and obtain 15.1g colourless transparent liquid (compound 1), productive rate is 61%.
1H?NMR(400MHz,CDCl
3):δ6.71(s,3H),3.82(s,3H).
13C?NMR(100MHz,CDCl
3):δ161.1,149.8,115.8(tt,-CF
2Br),113.4(tt,-OCF
2),107.5,106.3,56.0.
19F?NMR(376MHz,CDCl
3):δ–67.9(t,–OCF
2),–86.0(t,–CF
2Br).MS(EI):m/z500,498,496.Anal.Calcd?for?C
11H
6Br
2F
8O
3:C,26.53％；H,1.21％.Found:C,26.47％；H,1.17％.
(2) on the three-necked bottle of 250mL, fill reflux condensing tube, add zinc granule (1.56g, 0.024mol), compound 1 (4.98g, 0.010mol) and the new acetonitrile (100mL) steamed, heating reflux reaction 24h.Stop heating, room temperature cooling leaves standstill 1h.The salt generated is deposited in three-necked bottle bottom, inclines and supernatant liquid.Remaining mixture adds washing, with n-hexane extraction (30mL × 3), and organic phase anhydrous magnesium sulfate drying.Merge organic phase, with rotary evaporation except desolventizing, remaining liquid column chromatography carries out separating-purifying (normal hexane), obtains 2.13g colourless transparent liquid (compound 2), productive rate 71%.
1H?NMR(400MHz,CDCl
3):δ6.71(s,3H),3.79(s,3H).
13C?NMR(100MHz,CDCl
3):δ153.4,150.2,136.6,118.9,115.4,110.2,108.1,104.0,56.2.
19F?NMR(376MHz,CDC1
3):δ–134.1(dd,1F),–128.0(dd,1F)，–120.8(dd,1F).MS(EI):m/z300,301.Anal.Calcd?for?C
11H
6F
6O
3:C,44.02％；H,2.01％.Found:C,44.03％；H,2.03％.
(3) in the 50mL three-necked bottle of drying, add compound 2 (3g, 0.01mol), put into liquid nitrogen freezing, bleed 10min, and inflated with nitrogen thaws.Circulate after three times, put into 180 DEG C of oil baths heating 24h, be then warming up to 190 DEG C of heating 12h.After room temperature cooling, gained solid chloroform (30mL) dissolves, and then with adding normal hexane, filter, filter cake, at 60 DEG C of vacuum-drying 12h, obtains white solid 2.85g (PFCB-OMe), and productive rate is 95%.GPC:M
n=6,320g/mol, M
w/ M
n=1.08.
1h NMR (400MHz, CDCl
3): δ 6.68 (s, 3H), 3.66 (s, 3H).
19f NMR (376MHz, CDC1
3): δ-133.0-126.0 (m, 6F). (4) are by compound PFCB-OMe (6.30g, 1mmol) put into the 250mL three-necked bottle of the drying that dropping funnel is housed, add 100mL methylene dichloride and dissolve, in dropping funnel, add BBr
3methylene dichloride (50mL) solution of (1mL, 4mmol).Reaction flask is put into ice-water bath, slowly drips Boron tribromide solution, after stirring 0.5h after dropwising in ice-water bath, stirring at room temperature 6h.Add ethanol (1mL) cancellation reaction, the cooling of gained mixture room temperature leaves standstill 1h.Filter, wash (10mL × 3) with methylene dichloride.Filter cake, at 60 DEG C of vacuum-drying 12h, obtains white solid (PFCB-OH).GPC:M
n＝5,120g/mol,M
w/M
n＝1.27.
1H?NMR(400MHz,CDCl
3):δ6.65,3.76,5.85.
19F?NMR(376MHz,CDC13):δ-133.0-126.0(m,6F).
(5) PFCB-OH (6.05g, 1mmol) is placed in dry 100mL three-necked bottle, after adding the dissolving of 30mL butanone, adds triethylamine (1.4mL, 13mmol).Reaction flask is put into ice-water bath, slowly drips 2-bromo propionyl chloro (1.2mL, 12mmol).In ice-water bath, 1h is stirred, the salt that suction filtration removing generates, with rotary evaporation except desolventizing after dropwising.Gained resistates is with dissolve with methanol (20mL), and then with adding methylene dichloride, filter, be spin-dried for filtrate with rotation steaming, filter cake, at 60 DEG C of vacuum-drying 12h, obtains white solid (PFCB-BA).GPC:M
n＝7,760g/mol,M
w/M
n＝1.23.
1H?NMR(400MHz,CDCl
3):δ6.71,3.78,4.45,1.95.
19F?NMR(376MHz,CDC13):δ-133.0-126.0.
(6) by monomer PFCB-BA (3.07g, 0.50mmol), Tert-butyl Methacrylate (t-BMA) (0.106g, 0.75mmol) add in dry reaction tubes with cuprous bromide (0.015g, 0.001mmol), substitute nitrogen three times.Add new two methyl-phenoxides (10mL) steamed, put into liquid nitrogen freezing, bleed 10min, and inflated with nitrogen thaws.Circulate after three times, add five methyl diethylentriamine (0.020mL, 0.001mmol), freezing inflated with nitrogen of bleeding thaws three times again.Reaction tubes is put at once 65 DEG C of oil baths, stir 3h.Reaction tubes is taken out from oil bath, puts into liquid nitrogen cancellation reaction.After gained mixture is warming up to room temperature, adds THF and dissolve, cross neutral alumina column removing mantoquita.Rotary evaporation is except after desolventizing, and add THF (10mL) and dissolve, precipitate in cold normal hexane, suction filtration obtains white polymer.Again precipitate, after suction filtration,
60 DEG C of vacuum-drying 24h, obtain white solid and obtain 2.93g (PFCB-PtBMA).GPC:M
n＝22,650g/mol,M
w/M
n＝1.34.
1H?NMR(400MHz,CDCl
3):δ6.61,2.53,2.30,2.10,1.43,1.24.
19F?NMR(376MHz,CDC13):δ-133.0-126.0(m,6F).
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (10)
1., for a novel macromole evocating agent containing perfluorocyclobutanearyl for atom transfer radical polymerization, it is characterized in that: described initiator has following chemical structure:
Wherein: X is C1 or Br;
Ar is the one in following compounds:
2., as claimed in claim 1 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: concrete steps are as follows:
(1) in methoxyl group fragrance dihydric phenol, dimethyl sulfoxide (DMSO) is added, stirring makes it dissolve, the weightmeasurement ratio of methoxyl group fragrance dihydric phenol and dimethyl sulfoxide (DMSO) is 5 ~ 10:200g/mL, mixed solution oil pump is reduced pressure, with nitrogen to bubbling in solution to remove the oxygen in solution, under nitrogen protection, add cesium carbonate, the weight ratio of cesium carbonate and methoxyl group fragrance dihydric phenol is 45 ~ 55:5 ~ 10, with nitrogen after bubbling in solution, add 1, 2-dibromotetrafluoroethane, 1, the weight ratio of 2-dibromotetrafluoroethane and methoxyl group fragrance dihydric phenol is 35 ~ 45:5 ~ 10, be warming up to 40 ~ 60 DEG C, stir 1 ~ 3 day, stop heating, after reaction mixture cool to room temperature, add water to stir, the volume ratio of water and dimethyl sulfoxide (DMSO) is 100 ~ 300:200, then methylene dichloride is added, the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 50 ~ 150:200, separate organic phase, organic phase washes three times again with water, merge aqueous phase, with n-hexane extraction three times, merge organic phase, with anhydrous magnesium sulfate drying, suction filtration, with Rotary Evaporators except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid,
(2) in reactor, zinc granule is added, colourless transparent liquid prepared by step (1) and acetonitrile, the weight ratio of zinc granule and colourless transparent liquid is 1 ~ 2:4 ~ 6, the weightmeasurement ratio of zinc granule and acetonitrile is 1 ~ 2:100g/mL, then heating reflux reaction 18 ~ 36h, stop heating, be cooled to room temperature, leave standstill, incline and supernatant liquid, remaining salt precipitation mixture adds washing, with n-hexane extraction three times, organic phase anhydrous magnesium sulfate drying, merge organic phase, with rotary evaporation except desolventizing, remaining liquid column chromatography carries out separating-purifying, obtain colourless transparent liquid, i.e. Trifluorovinyl Aryl Ethers,
(3) Trifluorovinyl Aryl Ethers prepared by step (2) is added in reactor, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, and circulates after three times, puts into 180 DEG C of oil baths heating 20 ~ 30h, then 190 DEG C of heating 10 ~ 15h are warming up to, after room temperature cooling, gained solid chloroform, dissolve, then with adding normal hexane, filter, filter cake is at 50 ~ 70 DEG C of vacuum-drying 10 ~ 15h, obtain white solid, i.e. polymer P FCB-OMe;
(4) methylene dichloride is added in the polymer P FCB-OMe prepared toward step (3), make it dissolve, the weightmeasurement ratio of PFCB-OMe and methylene dichloride is 5 ~ 8:100g/mL, then mixture is put into ice-water bath, slowly boron tribromide and methylene dichloride mixing solutions is dripped in mixture, the weightmeasurement ratio of PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 5 ~ 8:51g/mL, after stirring 0.5h after dropwising in ice-water bath, stirring at room temperature 6h, add ethanol cancellation reaction, the volume ratio of ethanol and methylene dichloride is 0.5 ~ 2:100, the cooling of gained mixture room temperature leaves standstill 1h, filter, three times are washed with methylene dichloride, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, i.e. polymer P FCB-OH,
(5) butanone is added in the polymer P FCB-OH prepared toward step (4), make it dissolve, and then add triethylamine, the weightmeasurement ratio of polymer P FCB-OH and butanone is 5 ~ 7:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 5 ~ 7:1 ~ 2g/mL, then mixture is put into ice-water bath, slow dropping 2-bromo propionyl chloro, the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 5 ~ 7:1 ~ 1.5g/mL, in ice-water bath, 1h is stirred after dropwising, the salt that suction filtration removing generates, with rotary evaporation except desolventizing, gained resistates dissolve with methanol, then with adding methylene dichloride, filter, filtrate is spin-dried for rotation steaming, filter cake is at 60 DEG C of vacuum-drying 12h, obtain white solid, be macromole evocating agent PFCB-BA of the present invention.
3. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (1), the weightmeasurement ratio of methoxyl group fragrance dihydric phenol and dimethyl sulfoxide (DMSO) is 7:200g/mL, the weight ratio of cesium carbonate and methoxyl group fragrance dihydric phenol is 48.9:7,1, the weight ratio of 2-dibromotetrafluoroethane and methoxyl group fragrance dihydric phenol is 38.9:7, the volume ratio of water and dimethyl sulfoxide (DMSO) is 200:200, and the volume ratio of methylene dichloride and dimethyl sulfoxide (DMSO) is 100:200; Be warming up to 50 DEG C, stir 2 days.
4. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (2), the weight ratio of zinc granule and colourless transparent liquid is 1.56:4.98, the weightmeasurement ratio of zinc granule and acetonitrile is 1.56:100g/mL, heating reflux reaction 24h.
5. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (3), put into 180 DEG C of oil bath heating 24h, then 190 DEG C of heating 12h are warming up to, after room temperature cooling, gained solid chloroform, dissolve, then with adding normal hexane, filter, filter cake is at 60 DEG C of vacuum-drying 12h.
6. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (4), the weightmeasurement ratio of PFCB-OMe and methylene dichloride is 6.3:100g/mL, the weightmeasurement ratio of PFCB-OMe and boron tribromide and methylene dichloride mixing solutions is 6.3:51g/mL, and the volume ratio of ethanol and methylene dichloride is 1:100; In boron tribromide and methylene dichloride mixing solutions, both volume ratios are 1:50.
7. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (5), the weightmeasurement ratio of polymer P FCB-OH and butanone is 6.05:30g/mL, the weightmeasurement ratio of polymer P FCB-OH and triethylamine is 6.05:1.4g/mL, and the weightmeasurement ratio of polymer P FCB-OH and 2-bromo propionyl chloro is 6.05:1.2g/mL.
8. as claimed in claim 2 for the preparation method of the novel macromole evocating agent containing perfluorocyclobutanearyl of atom transfer radical polymerization, it is characterized in that: in step (1) and step (2), column chromatography uses normal hexane to carry out separating-purifying.
9. the macromole evocating agent as described in any one of claim 1-8 for the preparation of be main chain with PFCB type polymkeric substance, the purposes of the acrylic polymer new graft copolymers that is side chain, it is characterized in that: concrete preparation method is as follows:
By macromole evocating agent PFCB-BA of the present invention, Tert-butyl Methacrylate and cuprous bromide join in reactor, macromole evocating agent PFCB-BA, the weight ratio of Tert-butyl Methacrylate and cuprous bromide is 3 ~ 4:0.05 ~ 0.15:0.015, substitute nitrogen three times, add methyl-phenoxide, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is 3 ~ 4:5 ~ 15g/mL, put into liquid nitrogen freezing, bleed, inflated with nitrogen thaws, circulate after three times, add five methyl diethylentriamine, the weightmeasurement ratio of PFCB-BA and five methyl diethylentriamine is 3 ~ 4:0.01 ~ 0.03g/mL, freezing inflated with nitrogen of bleeding thaws three times again, reactor is put at once 65 DEG C of oil baths, stir 3h, reactor is taken out from oil bath, put into liquid nitrogen cancellation reaction, after gained mixture is warming up to room temperature, add THF to dissolve, cross neutral alumina column removing mantoquita, rotary evaporation is except after desolventizing, add THF to dissolve, precipitate in cold normal hexane, suction filtration obtains white polymer, again precipitate, after suction filtration, at 60 DEG C of vacuum-drying 24h, obtain white solid, be graft copolymer PFCB-g-PtBMA.
10. purposes as claimed in claim 8, it is characterized in that: the weight ratio of macromole evocating agent PFCB-BA, Tert-butyl Methacrylate and cuprous bromide is 3.07:0.106:0.015, the weightmeasurement ratio of PFCB-BA and methyl-phenoxide is the weightmeasurement ratio of 3.07:10g/mL, PFCB-BA and five methyl diethylentriamine is 3.07:0.02g/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410497295.8A CN104262617B (en) | 2014-09-25 | 2014-09-25 | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410497295.8A CN104262617B (en) | 2014-09-25 | 2014-09-25 | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104262617A true CN104262617A (en) | 2015-01-07 |
| CN104262617B CN104262617B (en) | 2017-05-10 |
Family
ID=52154219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410497295.8A Active CN104262617B (en) | 2014-09-25 | 2014-09-25 | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104262617B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400859A (en) * | 2018-10-19 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of the hydrophobic flexible polycarbonate of the structure containing perfluorocyclobutanearyl aryl-ether and application |
| CN113176707A (en) * | 2021-04-29 | 2021-07-27 | 苏州城邦达益材料科技有限公司 | Photosensitive dry film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362691A (en) * | 2008-09-19 | 2009-02-11 | 中国科学院上海有机化学研究所 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
| CN101445511A (en) * | 2008-12-26 | 2009-06-03 | 中国科学院上海有机化学研究所 | Perfluor cyclobutyl arylene oligopolymer, preparation method thereof by using iterative coupled reaction and usage |
| CN101492520A (en) * | 2009-03-04 | 2009-07-29 | 中国科学院上海有机化学研究所 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
| CN102643443A (en) * | 2011-02-17 | 2012-08-22 | 通用汽车环球科技运作有限责任公司 | Poly(perfluorocyclobutane) ionomer with phosphonic acid groups for high temperature fuel cells |
-
2014
- 2014-09-25 CN CN201410497295.8A patent/CN104262617B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101362691A (en) * | 2008-09-19 | 2009-02-11 | 中国科学院上海有机化学研究所 | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application |
| CN101445511A (en) * | 2008-12-26 | 2009-06-03 | 中国科学院上海有机化学研究所 | Perfluor cyclobutyl arylene oligopolymer, preparation method thereof by using iterative coupled reaction and usage |
| CN101492520A (en) * | 2009-03-04 | 2009-07-29 | 中国科学院上海有机化学研究所 | Diblock copolymer containing full-fluorine cyclobutyl aryl aether block and uses thereof |
| CN102643443A (en) * | 2011-02-17 | 2012-08-22 | 通用汽车环球科技运作有限责任公司 | Poly(perfluorocyclobutane) ionomer with phosphonic acid groups for high temperature fuel cells |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400859A (en) * | 2018-10-19 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and product of the hydrophobic flexible polycarbonate of the structure containing perfluorocyclobutanearyl aryl-ether and application |
| CN113176707A (en) * | 2021-04-29 | 2021-07-27 | 苏州城邦达益材料科技有限公司 | Photosensitive dry film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262617B (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103145918A (en) | Preparation method of cellulose-g-resin acid grafted copolymer | |
| CN106883114A (en) | A kind of fluorenes class polyfunctionality light trigger and its preparation and application | |
| CN104829771B (en) | A kind of side chain contains polymer of ring-type azobenzene binaphthyl structure and its production and use | |
| JPS6176519A (en) | Polymer substance showing liquid crystal phase | |
| CN105348532B (en) | A kind of high thermal stability blocks the Industrialized synthesis method of tree-like polyaryl ether sulphone resin | |
| CN109280002A (en) | A kind of benzophenone analog derivative photoinitiator and preparation method thereof | |
| CN107857846B (en) | A kind of preparation method of polyethylene glycol grafting polybutyl methacrylate amphipathic graft copolymer | |
| CN104262617A (en) | Novel perfluorocyclobutyl-containing macroinitiator for atom transfer radical polymerization (ATRP) and preparation method and application of novel perfluorocyclobutyl-containing macroinitiator | |
| CN109503735A (en) | Photoinitiator, the Photocurable composition comprising it and its application | |
| CN105198892A (en) | Synthetic method for isosorbide acrylic ester and application of isosorbide acrylic ester in improving thermal performance of polymer | |
| CN105859526B (en) | The monomer of diphenol containing pyrene, preparation method and its application in preparing polyether sulphone of the main chain containing pyrenyl group | |
| CN106700084B (en) | Bis-phenol acidic group fire retardant of polyphosphate of the structure containing DOPO and preparation method thereof | |
| CN104277216B (en) | A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application | |
| CN102351981B (en) | Fluorine-containing polyacrylate for photocuring and synthesis method thereof | |
| WO2016202192A1 (en) | Polycarbonate composition and preparation method and application thereof | |
| CN102964543B (en) | Amphiphilic fluorinated acrylate penta-block copolymer and preparation method thereof | |
| CN104910040A (en) | Methacrylate containing ortho-tetrafluoroazobenzene structure, polymer thereof, and preparation method and application thereof | |
| CN108641083A (en) | A kind of high temperature resistant Ultraluminescence polyarylether sulfone copolymer, preparation method and the copolymer film | |
| JP2000072705A (en) | Production of bromine compound | |
| CN101805419A (en) | Fluorine-containing photoinitiator and application thereof | |
| CN101362691B (en) | Functional acrylic esters monomers containing perfluorocyclobutane aryl-ether unit, preparation method and application | |
| CN110144031A (en) | A kind of method of photoinduction organic catalysis lignin graft modification | |
| CN103897203B (en) | A kind of method preparing amphiphilic nano microballoon composite network hydrogel | |
| JP4977099B2 (en) | Radical polymerizable group-containing cyclic polysulfide, process for producing the same, and polymer thereof | |
| CN104262616A (en) | Perfluoro-cyclobutyl polyarylether polymer containing 1H-1,2,3-triazole group, as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |