CN104987508A - Polysulfone resin preparing method with microwaves as heat source - Google Patents
Polysulfone resin preparing method with microwaves as heat source Download PDFInfo
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Abstract
The invention discloses an efficient polysulfone resin preparing method with microwaves as a heat source. The preparing method includes the steps that 4,4'-dichloro(di)phenyl sulfone and bisphenol A serve as initial raw materials, carbonate with the mole number two times that of the bisphenol A is added to serve as alkali, and the mixture is heated and reacted for 2 hours to 5 hours through a microwave reactor in high-boiling-point aprotic polar solvents; then the reaction liquid is slowly poured into deionized water, white fiber-shaped polymers are obtained, then the polymers are soaked for 5 hours to 10 hours under the 60-DEG-C-to-80-DEG-C condition, the process is repeated three times to five times, filtering and drying are carried out, and polysulfone resin is obtained through vacuum drying. By means of the preparing method, the reaction time is shortened to a great degree, energy consumption is reduced, the cost for the production technology is reduced accordingly, and the working efficiency is improved.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to the preparation method of polysulfone resin, particularly adopt microwave as the high efficiency preparation method of the polysulfone resin of thermal source.The application obtains the subsidy of Tianjin State Scientific and Technological Commission science and technology support key special subjects project (contract number is: 12ZCDZSF07000) and national " 863 " project (project number is: 2012AA03A601) simultaneously.
Background technology
Polysulfones, as a kind of special engineering plastics, has a wide range of applications at numerous areas such as aerospace, automobile, electronic apparatus, precision optical machinery, food, industrial equipment and medicine equipments.Its production technique is mainly divided into two kinds: two-step approach and single stage method.Two-step approach adopts sodium hydroxide as highly basic, first dihydroxyphenyl propane is changed into sodium salt, then is polymerized in methyl-sulphoxide with 4,4 ˊ-dichloro diphenyl sulfone and obtains polysulfones.The advantage of the method is the with low cost of sodium hydroxide, but the accurate control of highly basic consumption is more complicated, and molecular weight product is difficult to reach higher level, and molecular weight distribution is very wide.Single stage method adopts salt of wormwood as middle highly basic, and toluene is a point aqua, at N, is polymerized in N ˊ-N,N-DIMETHYLACETAMIDE, can obtain molecular weight higher and can control, polysulfones product that molecular weight distribution is narrower.To the further improvement of this method, add 2-2.25 salt of wormwood doubly, can save toluene and divide Water flow-path, reduce the consumption of organic solvent and Reaction time shorten, enhance productivity (CN101544759B).The type of heating of all technique comprises heat-conducting oil heating, high pressure steam heating and FAR INFRARED HEATING etc. above.No matter any mode, all can run into that high viscosity medium heat transfer efficiency is low, the problem of conduct heat uneven, easy " being burned ".
Microwave heating mechanism is molecular vibration, there is not medium heat-transfer problem, therefore has homogeneous heating, heating rate high.Along with the maximization of microwave equipment, the synthesis of more organic synthesis and macromolecular material adopts microwave technology to provide thermal source for suitability for industrialized production.
Summary of the invention
The present invention is intended to further Reaction time shorten, avoids high viscosity medium to heat the uneven a series of production problems brought.
The invention discloses with microwave the high efficiency preparation method of the polysulfone resin being thermal source, it is characterized in that being undertaken by following step: it is with 4,4 ˊ-dichloro diphenyl sulfone and dihydroxyphenyl propane are starting raw material, add dihydroxyphenyl propane mole number 2-2.25 carbonate doubly as alkali, in high boiling aprotic polar solvent, microwave reactor is adopted to be heated to certain temperature, reaction 2-5 hour; Then by slow for reaction solution impouring deionized water, obtain white fibrous polymer, soak 5-10 hour subsequently under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum-drying obtains polysulfones.
Preparation method described in the present invention, carbonate is wherein sodium carbonate, salt of wormwood or cesium carbonate, preferred salt of wormwood.
Preparation method described in the present invention, high boiling point aprotic polar solvent is wherein methyl-sulphoxide (DMSO), N,N-dimethylacetamide (DMAc), DMF (DMF) or N-Methyl pyrrolidone (NMP), preferred DMAc.
Preparation method described in the present invention, wherein temperature of reaction is 150-185 DEG C.
Preparation method described in the present invention, wherein the power of microwave heater is 1-4 kilowatt, preferably 3 kilowatts.
Disclosed by the invention with microwave for the positively effect that the preparation method of the polysulfone resin of thermal source is compared with prior art had is:
(1) preparation method of the present invention efficiently solves that high viscosity medium heat transfer efficiency is low, uneven problem of conducting heat, and avoids " being burned " phenomenon.
(2) adopt preparation method of the present invention, within the very short reaction times, the intrinsic viscosity of polymkeric substance just can reach higher level, substantially increases production efficiency.
embodiment:
In order to simple and clearly object, the hereafter appropriate description eliminating known technology, in order to avoid the description of those unnecessary details impact to the technical program.Below in conjunction with example, the present invention is described further.Raw materials used as do not illustrated especially, by commercially available.Such as: dihydroxyphenyl propane, 4,4 ˊ-dichloro diphenyl sulfone, salt of wormwood, N, N ˊ-N,N-DIMETHYLACETAMIDE etc. are by commercially available.
Intrinsic viscosity adopts Ubbelohde viscosimetry to measure, and probe temperature is 25 DEG C, and solvent is the nmp solution containing 0.05M lithiumbromide.The power of microwave heater is 1-4 kilowatt.
Comparative example:
By 4,4 '-dichloro diphenyl sulfone (DCDPS, 28.7160g, 100mmol), 4,4 '-'-biphenyl diphenol (BP, 18.6210g, 100mmol), Anhydrous potassium carbonate (K
2cO
3, 27.6420g, 200mmol), 237mL N,N-dimethylacetamide (DMAc) mixing, oil bath heat, temperature of reaction rises to 180 DEG C, reacts 12 hours.Stop heating and stir, naturally cooling to room temperature.In reaction solution slow impouring 2L deionized water, obtain white fibrous polymer, 4L deionized water soaks 8 hours under 80 DEG C of conditions, in triplicate, filters, dry, vacuum-drying 24 hours at 100 DEG C again, obtains white fibrous polymer, 39.6g, yield: 99%, intrinsic viscosity: 0.71dL/g.
Embodiment 1
By 4,4 '-dichloro diphenyl sulfone (DCDPS, 28.7160g, 100mmol), 4,4 '-'-biphenyl diphenol (BP, 18.6210g, 100mmol), Anhydrous potassium carbonate (K
2cO
3, 27.6420g, 200mmol), 237mL N,N-dimethylacetamide (DMAc) mixing, microwave reactor power is opened to 3 kilowatts, and temperature of reaction rises to 180 DEG C, reacts 3 hours.Close microwave reactor and agitator, naturally cool to room temperature.In reaction solution slow impouring 2L deionized water, obtain white fibrous polymer, 4L deionized water soaks 8 hours under 80 DEG C of conditions, in triplicate, filters, dry, vacuum-drying 24 hours at 100 DEG C again, obtains white fibrous polymer, 39.7g, yield: 99%, intrinsic viscosity: 0.73dL/g.
Embodiment 2-8
With reference to the method for embodiment 1, adopt the consumption of different microwave reactor power, reaction times, solvent and salt of wormwood, all can synthesize polysulfones, concrete outcome sees the following form:
Result illustrates:
(1) experimental technique of the present invention is adopted, all without " being burned " phenomenon, reacting balance.
(2) adopt experimental technique of the present invention, in a short period of time, the intrinsic viscosity of polymkeric substance just can reach the level that in comparative example, 12 little the reaction times reach, and substantially reduces the reaction times.
After the preferred embodiment described in detail, be familiar with this technology personage can be well understood to, do not departing under above-mentioned claim and spirit and can carry out various change and amendment, all above embodiment is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all belong to the scope of technical solution of the present invention.
Claims (5)
1. one kind take microwave as the high efficiency preparation method of the polysulfone resin of thermal source, it is characterized in that being undertaken by following step: it is with 4,4 ˊ-dichloro diphenyl sulfone and dihydroxyphenyl propane are starting raw material, add dihydroxyphenyl propane mole number 2-2.25 carbonate doubly as alkali, microwave reactor is adopted in high boiling aprotic polar solvent, be heated to 150-185 DEG C, reaction 2-5 hour; Then by slow for reaction solution impouring deionized water, obtain white fibrous polymer, soak 5-10 hour subsequently under 60-80 DEG C of condition, repeat 3-5 time, filter, dry, vacuum-drying obtains polysulfones; Wherein 4,4 ˊ-dichloro diphenyl sulfone: the mol ratio of dihydroxyphenyl propane is 1:1.
2. preparation method according to claim 1, carbonate is wherein sodium carbonate, salt of wormwood or cesium carbonate.
3. preparation method according to claim 1, high boiling point aprotic polar solvent is wherein methyl-sulphoxide, N,N-dimethylacetamide, DMF or N-Methyl pyrrolidone.
4. preparation method according to claim 1, wherein temperature of reaction is 150-180 DEG C.
5. preparation method according to claim 1, wherein the power of microwave heater is 1-4 kilowatt.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510361661.1A CN104987508A (en) | 2015-06-26 | 2015-06-26 | Polysulfone resin preparing method with microwaves as heat source |
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| CN201510361661.1A CN104987508A (en) | 2015-06-26 | 2015-06-26 | Polysulfone resin preparing method with microwaves as heat source |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801324A (en) * | 2021-10-14 | 2021-12-17 | 富海(东营)新材料科技有限公司 | Polyether sulfone synthesis method with high batch stability |
| CN115058007A (en) * | 2022-06-28 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of polysulfone with low amino content |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008364A (en) * | 1987-06-27 | 1991-04-16 | Basf Aktiengesellschaft | Thermoplastic molding materials which are stable at high temperatures and have improved melt stability |
| CN101544759A (en) * | 2009-04-29 | 2009-09-30 | 天津师范大学 | Method for preparing irregular sulfonated poly aromatic (sulfur) ether with high efficiency |
| CN101855271A (en) * | 2007-11-13 | 2010-10-06 | 巴斯夫欧洲公司 | Method for producing polyaryl ethers |
-
2015
- 2015-06-26 CN CN201510361661.1A patent/CN104987508A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008364A (en) * | 1987-06-27 | 1991-04-16 | Basf Aktiengesellschaft | Thermoplastic molding materials which are stable at high temperatures and have improved melt stability |
| CN101855271A (en) * | 2007-11-13 | 2010-10-06 | 巴斯夫欧洲公司 | Method for producing polyaryl ethers |
| CN101544759A (en) * | 2009-04-29 | 2009-09-30 | 天津师范大学 | Method for preparing irregular sulfonated poly aromatic (sulfur) ether with high efficiency |
Non-Patent Citations (1)
| Title |
|---|
| HURDUC NICOLAE ET AL.: ""MICROWAVE EFFECTS IN THE SYNTHESIS OF POLYETHERS BY PHASE TRANSFER CATALYSIS"", 《EUR. POLYM. J.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113801324A (en) * | 2021-10-14 | 2021-12-17 | 富海(东营)新材料科技有限公司 | Polyether sulfone synthesis method with high batch stability |
| CN115058007A (en) * | 2022-06-28 | 2022-09-16 | 万华化学集团股份有限公司 | Preparation method of polysulfone with low amino content |
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