CN101274982A - Bisphenol A type sulfonated polysulfone copolymer and synthetic method thereof - Google Patents
Bisphenol A type sulfonated polysulfone copolymer and synthetic method thereof Download PDFInfo
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- CN101274982A CN101274982A CNA2008100645260A CN200810064526A CN101274982A CN 101274982 A CN101274982 A CN 101274982A CN A2008100645260 A CNA2008100645260 A CN A2008100645260A CN 200810064526 A CN200810064526 A CN 200810064526A CN 101274982 A CN101274982 A CN 101274982A
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- diphenyl sulfone
- dichloro diphenyl
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Abstract
The invention provides a bisphenol A sulfonated polysulfone copolymer and a synthesis method thereof, which relates to a polysulfone copolymer and a synthesis method. The invention solves the problem that the synthesis by using the existing method has difficulties in controlling the degree of sulphonation of polysulfone copolymer and the side reactions occur easily. The molecular formula of the product of the invention is as the above formula, wherein, n and m represent degree of polymerization. The steps of the method are as follows: A. 4, 4'-dichlorodiphenyl sulfone, sulfonation dichlorodiphenyl sulfone and bisphenol A are dissolved in N-cymene-2- ketopyrrolidine, adding potassium carbonate and toluene; B. under the condition with temperature of 150 to 160 DEG C, toluene is removed after 4-hour refluxing ; the temperature is increased to 190 DEG C and the reaction is incubated for 16 to 35 hours with heat preservation; C. water or N is added and solid is precipitated in the N'-dimethylacetamide; then the precipitated solid is ground and filtered and washed by water; the precipitate is put into boiling deionized water, washed again and dried in vacuum, thus the steps are all finished. The polysulfone copolymer and the synthesis method of the invention effectively control the degree of sulphonation and have no occurrence of the side reactions and the production rate of the product of the invention is over 90 percent.
Description
Technical field
The present invention relates to a kind of polysulfone copolymer and synthetic method thereof.
Background technology
Sulfonation is widely used as the effective ways of aromatic ring polymer modification.The route of synthesis of SPSF multipolymer has two kinds, is respectively polymkeric substance Direct Sulfonation and monomer sulfonation.At present, people take the method for Direct Sulfonation polymkeric substance to synthesize mostly.For example some documents had been reported with different sulphonating agent sulfonated polyether-ether-ketones, polyethersulfone, and as the vitriol oil, chlorsulfonic acid etc., the sulfonation degree of every repeating unit can reach 1.0.But, still there are some problems in existing sulfonated polymer, as: the reaction meeting is because the raising of sulfonation degree is difficult to control, and the product that will expect highly sulfonated must adopt strict more condition, such as the rising temperature of reaction, improve sulphonating agent concentration etc., but will inevitably cause the generation of some side reactions like this, such as intramolecular crosslinking or degraded.
Summary of the invention
The objective of the invention is to be difficult to control and easily take place the problem of side reaction, and a kind of bisphenol A-type SPSF multipolymer and synthetic method thereof are provided for the sulfonation degree that solves the synthetic polysulfone copolymer of existing method.The present invention has obtained having the SPSF of different sulfonation degree by adjusting the ratio of sulfonated monomers and non-sulfonated monomers, and product of the present invention can be used as the material of proton exchange membrane.
The molecular formula of bisphenol A-type SPSF multipolymer of the present invention is as follows:
N and m in the formula represent the polymerization degree; It is by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make, wherein 4,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
The synthetic method step of bisphenol A-type SPSF multipolymer of the present invention is as follows: one, with 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone, dihydroxyphenyl propane be dissolved in the N-N-methyl-2-2-pyrrolidone N-, adds salt of wormwood and toluene again; Two, under 150～160 ℃ of conditions,, be warming up to 190 ℃ then gradually, insulation reaction 16～35h with steaming toluene behind the above-mentioned reaction solution backflow 4h; Three, the product of step 2 is put into water or N, in N '-N,N-DIMETHYLACETAMIDE, separate out solid; Again the solid of separating out is pulverized after-filtration, use washed with de-ionized water three to five times, throw out is put into the ebullient deionized water and is boiled 2～3 times, boil 10min at every turn, use washed with de-ionized water again three to five times, vacuum-drying 24h under 120 ℃ of conditions obtains bisphenol A-type SPSF multipolymer then; Wherein in the step 14,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
The molecular formula of described sulfonation dichloro diphenyl sulfone is
N-N-methyl-2-2-pyrrolidone N-(NMP) is a solvent in the step 1, salt of wormwood is salt forming agent, toluene is the band aqua, the N-N-methyl-2-2-pyrrolidone N-is 2: 1 with the volume of toluene ratio, the consumption of salt of wormwood is with respect to excessive 15% (weight) of dihydroxyphenyl propane, N-N-methyl-2-2-pyrrolidone N-and 4,4 '-ratio of the total mass of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone, dihydroxyphenyl propane is 7～9: 3.
The process of synthesis of bisphenol A type SPSF multipolymer of the present invention is as follows:
Find that after deliberation the present invention has controlled sulfonation degree effectively, and overcome existing method of sulfonating and cause intramolecular crosslinked and degraded, no side reaction generation.And the method for earlier sulfonation monomer repolymerization synthesis of bisphenol A type SPSF multipolymer is not seen the research report so far.The productive rate of product of the present invention is all more than 90%.
Description of drawings
Fig. 1 is the contrast figure of the bisphenol A-type SPSF infared spectrum of existing bisphenol-a polysulfone infared spectrum and embodiment seven, and a represents the infrared spectrum of bisphenol-a polysulfone among the figure, and b represents the infrared spectrum of sulfonation bisphenol-a polysulfone.Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of synthetic bisphenol A-type SPSF in the embodiment seven, and a-g represents the position of hydrogen correspondence in the molecular formula among Fig. 2.
Embodiment
Embodiment one: the molecular formula of bisphenol A-type SPSF multipolymer is as follows in the present embodiment:
N and m in the formula represent the polymerization degree; It is by 4,4 '-dichloro diphenyl sulfone (DCDPS), sulfonation dichloro diphenyl sulfone (SDCDPS) and dihydroxyphenyl propane make, wherein 4,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
The molecular formula of sulfonation dichloro diphenyl sulfone is in the present embodiment
Embodiment two: what present embodiment and embodiment one were different is: bisphenol A-type SPSF multipolymer be by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make by 9: 1: 10 mol ratio.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: bisphenol A-type SPSF multipolymer be by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make by 8: 2: 10 mol ratio.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is: bisphenol A-type SPSF multipolymer be by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make by 7: 3: 10 mol ratio.Other is identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is: bisphenol A-type SPSF multipolymer be by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make by 6: 4: 10 mol ratio.Other is identical with embodiment one.
Embodiment six: what present embodiment and embodiment one were different is: bisphenol A-type SPSF multipolymer be by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make by 5: 5: 10 mol ratio.Other is identical with embodiment one.
Embodiment seven: the synthetic method step of present embodiment bisphenol A-type SPSF multipolymer is as follows: one, with 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone, dihydroxyphenyl propane be dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP), adds salt of wormwood and toluene again; Two, under 150～160 ℃ of conditions,, be warming up to 190 ℃ then gradually, insulation reaction 16～35h with steaming toluene behind the above-mentioned reaction solution backflow 4h; Three, the product with step 2 adds entry or N, in N '-N,N-DIMETHYLACETAMIDE, separate out solid, again the solid of separating out is pulverized after-filtration, use washed with de-ionized water three to five times, throw out is put into the ebullient deionized water and is boiled 2～3 times, boil 10min at every turn, use washed with de-ionized water again three to five times, vacuum-drying 24h under 120 ℃ of conditions obtains bisphenol A-type SPSF multipolymer then; Wherein in the step 14,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
The molecular formula of the sulfonation dichloro diphenyl sulfone described in the present embodiment step 1 is
The N-N-methyl-2-2-pyrrolidone N-is a solvent, salt of wormwood is salt forming agent, toluene is the band aqua, the N-N-methyl-2-2-pyrrolidone N-is 2: 1 with the volume of toluene ratio, the consumption of salt of wormwood is with respect to excessive 15% (weight) of dihydroxyphenyl propane, N-N-methyl-2-2-pyrrolidone N-and 4,4 '-ratio of the total mass of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 7～9: 3.The productive rate of product is all more than 90% in the present embodiment.
As seen from Figure 1, in the bisphenol A-type SPSF 1029 and 1098cm
-1The absorption peak at place is respectively SO
3Asymmetric and symmetrical stretching vibration peak in the Na group then do not have these two stretching vibration peaks in bisphenol-a polysulfone, and polymkeric substance is at 1140-1110cm
-1The charateristic avsorption band that does not have appearance to produce in the scope by crosslinking side reaction. illustrate and in sulfonated polymer, successfully introduced sulfonic group.And employing sulfonated monomers copolymerization mode, the degraded and the crosslinking reaction that have taken place when having eliminated the Direct Sulfonation polymkeric substance.This also provides good assurance for the performance of controlling polymers.
Present embodiment gained bisphenol A-type SPSF multipolymer is dissolved in to be made into mass percent concentration in the N,N-DIMETHYLACETAMIDE (DMAC) be 10% solution, after the strainer of 0.45 μ m filters, be tiled on the sheet glass, obtain the film that thickness is approximately the na form of 50～100 μ m.It is 2mol/L H that the film of na form is soaked into concentration
2SO
4Middle 24h uses the unnecessary H of deionized water flush away again
2SO
4Solution, vacuum-drying 24h under 100 ℃ of conditions then can obtain the film of sour form.The reduced viscosity of bisphenol A-type SPSF multipolymer is all more than 0.82 after tested, thereby can obtain toughness film preferably, thereby it is had broad application prospects in the fuel cell membranes field.
Embodiment eight: what present embodiment and embodiment seven were different is: in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 9: 1: 10.Other is identical with embodiment seven.
The theoretical sulfonation degree (Ds) of present embodiment synthetic bisphenol A-type SPSF multipolymer equals 0.2, and reduced viscosity is 0.82.
Embodiment nine: what present embodiment and embodiment seven were different is: in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 8: 2: 10.Other is identical with embodiment seven.
The theoretical sulfonation degree (Ds) of present embodiment synthetic bisphenol A-type SPSF multipolymer equals 0.4, and reduced viscosity is 1.24.
Embodiment ten: what present embodiment and embodiment seven were different is: in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 7: 3: 10.Other is identical with embodiment seven.
The theoretical sulfonation degree (Ds) of present embodiment synthetic bisphenol A-type SPSF multipolymer equals 0.6, and reduced viscosity is 1.32.
Embodiment 11: what present embodiment and embodiment seven were different is: in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 6: 4: 10.Other is identical with embodiment seven.
The theoretical sulfonation degree (Ds) of present embodiment synthetic bisphenol A-type SPSF multipolymer equals 0.8, and reduced viscosity is 1.54.
Embodiment 12: what present embodiment and embodiment seven were different is: 4,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 5: 5: 10.Other is identical with embodiment seven.
The theoretical sulfonation degree (Ds) of present embodiment synthetic bisphenol A-type SPSF multipolymer equals 1.0, and reduced viscosity is 1.68.
Claims (10)
1, bisphenol A-type SPSF multipolymer is characterized in that the molecular formula of bisphenol A-type SPSF multipolymer is as follows:
N and m in the formula represent the polymerization degree; It is by 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane make, wherein 4,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
2, bisphenol A-type SPSF multipolymer according to claim 1 is characterized in that the molecular formula of sulfonation dichloro diphenyl sulfone is
3, the synthetic method of bisphenol A-type SPSF multipolymer according to claim 1, the synthetic method step that it is characterized in that bisphenol A-type SPSF multipolymer is as follows: one, with 4,4 '-dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone, dihydroxyphenyl propane be dissolved in the N-N-methyl-2-2-pyrrolidone N-, adds salt of wormwood and toluene again; Two, under 150～160 ℃ of conditions,, be warming up to 190 ℃ then gradually, insulation reaction 16～35h with steaming toluene behind the above-mentioned reaction solution backflow 4h; Three, the product of step 2 is put into water or N, in N '-N,N-DIMETHYLACETAMIDE, separate out solid; Again the solid of separating out is pulverized after-filtration, use washed with de-ionized water three to five times, throw out is put into the ebullient deionized water and is boiled 2～3 times, boil 10min at every turn, use washed with de-ionized water again three to five times, vacuum-drying 24h under 120 ℃ of conditions obtains bisphenol A-type SPSF multipolymer then; Wherein in the step 14,4 '-mol ratio of dichloro diphenyl sulfone and dihydroxyphenyl propane is 5～9: 10, the mol ratio of sulfonation dichloro diphenyl sulfone dihydroxyphenyl propane is 1～5: 10.
4, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 9: 1: 10.
5, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 8: 2: 10.
6, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 7: 3: 10.
7, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 6: 4: 10.
8, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that in the step 14,4 '-mol ratio of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 5: 5: 10.
9,, it is characterized in that the molecular formula of sulfonation dichloro diphenyl sulfone in the step 1 is according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer
10, according to the synthetic method of the described bisphenol A-type SPSF of claim 3 multipolymer, it is characterized in that the N-N-methyl-2-2-pyrrolidone N-is 2: 1 with the volume of toluene ratio in the step 1, the consumption of salt of wormwood is with respect to excessive 15% (weight) of dihydroxyphenyl propane, N-N-methyl-2-2-pyrrolidone N-and 4,4 '-ratio of the total mass of dichloro diphenyl sulfone, sulfonation dichloro diphenyl sulfone and dihydroxyphenyl propane is 7～9: 3.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690412A (en) * | 2012-06-12 | 2012-09-26 | 江苏苏净集团有限公司 | Method for preparing sulfonated polysulfone copolymer |
| WO2013041062A1 (en) * | 2011-09-23 | 2013-03-28 | Beijing Normal University | Process for preparing polysulfone |
| CN103772706A (en) * | 2013-12-25 | 2014-05-07 | 济南开发区星火科学技术研究院 | Method for preparing bisphenol F-type sulfonated polysulfone copolymer |
| CN103788374A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Sulfonated polyarylether sulfone and preparation method thereof, and reverse osmosis membrane and making method thereof |
| CN104151552A (en) * | 2014-07-17 | 2014-11-19 | 天津师范大学 | Polyarylene (sulfide) sulfone material containing phosphonic acid groups as well as preparation method and application of polyarylene (sulfide) sulfone material |
| CN107075110A (en) * | 2014-10-31 | 2017-08-18 | 巴斯夫欧洲公司 | Prepare the copolymer of film |
| CN110079091A (en) * | 2019-03-25 | 2019-08-02 | 常州达奥新材料科技有限公司 | A kind of preparation method of resistance to ablation composite insulation material |
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2008
- 2008-05-16 CN CNA2008100645260A patent/CN101274982A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013041062A1 (en) * | 2011-09-23 | 2013-03-28 | Beijing Normal University | Process for preparing polysulfone |
| CN103012796A (en) * | 2011-09-23 | 2013-04-03 | 北京师范大学 | Method for preparing polysulfones |
| CN103012796B (en) * | 2011-09-23 | 2014-07-16 | 北京师范大学 | Method for preparing polysulfones |
| CN102690412A (en) * | 2012-06-12 | 2012-09-26 | 江苏苏净集团有限公司 | Method for preparing sulfonated polysulfone copolymer |
| CN103788374A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Sulfonated polyarylether sulfone and preparation method thereof, and reverse osmosis membrane and making method thereof |
| CN103772706A (en) * | 2013-12-25 | 2014-05-07 | 济南开发区星火科学技术研究院 | Method for preparing bisphenol F-type sulfonated polysulfone copolymer |
| CN103772706B (en) * | 2013-12-25 | 2016-05-04 | 济南开发区星火科学技术研究院 | A kind of preparation method of Bisphenol F type sulfonated polysulfone copolymer |
| CN104151552A (en) * | 2014-07-17 | 2014-11-19 | 天津师范大学 | Polyarylene (sulfide) sulfone material containing phosphonic acid groups as well as preparation method and application of polyarylene (sulfide) sulfone material |
| CN104151552B (en) * | 2014-07-17 | 2016-07-06 | 天津师范大学 | Poly aromatic (sulfur) ether sulfone material containing phosphonyl group and preparation method and application |
| CN107075110A (en) * | 2014-10-31 | 2017-08-18 | 巴斯夫欧洲公司 | Prepare the copolymer of film |
| CN110079091A (en) * | 2019-03-25 | 2019-08-02 | 常州达奥新材料科技有限公司 | A kind of preparation method of resistance to ablation composite insulation material |
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