CN115926168B - Polyarylethersulfone resin and preparation method thereof - Google Patents
Polyarylethersulfone resin and preparation method thereof Download PDFInfo
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- CN115926168B CN115926168B CN202211510845.6A CN202211510845A CN115926168B CN 115926168 B CN115926168 B CN 115926168B CN 202211510845 A CN202211510845 A CN 202211510845A CN 115926168 B CN115926168 B CN 115926168B
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- 229920000110 poly(aryl ether sulfone) Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title abstract description 8
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 28
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 26
- OFCFYWOKHPOXKF-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-chlorobenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=CC=C1 OFCFYWOKHPOXKF-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000009477 glass transition Effects 0.000 claims abstract description 21
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 17
- 238000006297 dehydration reaction Methods 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 13
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 239000012024 dehydrating agents Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000007865 diluting Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 7
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000012634 fragment Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- OGTSHGYHILFRHD-UHFFFAOYSA-N (4-fluorophenyl)-phenylmethanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1 OGTSHGYHILFRHD-UHFFFAOYSA-N 0.000 claims description 3
- MONGUDQJUIVFPI-UHFFFAOYSA-N 1-(benzenesulfonyl)-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=CC=C1 MONGUDQJUIVFPI-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000012527 feed solution Substances 0.000 claims 1
- 238000002834 transmittance Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 13
- 125000000524 functional group Chemical group 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 238000003756 stirring Methods 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 238000009835 boiling Methods 0.000 description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000009833 condensation Methods 0.000 description 7
- 230000005494 condensation Effects 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003495 polar organic solvent Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229920012287 polyphenylene sulfone Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- QRFMXBKGNQEADL-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical class OC1=CC=CC=C1.OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 QRFMXBKGNQEADL-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012634 optical imaging Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention relates to the technical field of high polymer materials, and provides a polyarylethersulfone resin and a preparation method thereof. The invention creatively carries out ternary polymerization on the bi- (4-chlorodiphenylsulfone), the biphenol and the functional group (bisphenol fluorene) containing a torque structure, improves the transmittance and the solubility of the polyarylethersulfone material while improving the glass transition temperature of the polyarylethersulfone through the introduction of a small amount of rigid torque structure, and successfully prepares the high-temperature-resistant and high-transparency polyarylethersulfone resin, and meanwhile, the polyarylethersulfone resin also has excellent mechanical properties. The example results show that the glass transition temperature of the polyarylethersulfone resin provided by the invention can reach more than 280 ℃, and the application requirements of the polyarylethersulfone resin in a high-temperature environment can be met.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyarylethersulfone resin and a preparation method thereof.
Background
The polyarylethersulfone resin is a special engineering plastic with excellent comprehensive performance. Currently commercialized polyarylethersulfone resins are mainly three types, namely bisphenol a Polysulfone (PSF), polyethersulfone (PES) and polyphenylenesulfone (PPSU), respectively, wherein the highest continuous use temperature of PES and PPSU is about 180 ℃. The polyarylethersulfone has excellent mechanical property and better chemical stability, can resist hydrolysis and can also be subjected to high-pressure steam sterilization. Meanwhile, the polyarylethersulfone also has good light transmittance, and can be used as a window material.
In the patent CN101704951A, a poly (biphenyl sulfone ether) and polyether sulfone terpolymer with the glass transition temperature of 226-262 ℃ is prepared by ternary polymerization of 4,4' -dichloro-diphenyl sulfone, 4' -dichlorobenzene-diphenyl sulfone and 4,4' -dihydroxy-diphenyl sulfone; patent CN101735459A prepares a ternary copolymer of poly (biphenyl ether sulfone) and poly (biphenyl ether biphenyl sulfone) with the glass transition temperature of 220-268 ℃ through ternary polymerization of 4,4' -dihydroxybiphenyl, 4' -dichloro diphenyl sulfone and 4,4' -dichlorobenzene diphenyl sulfone. The above patent increases the use temperature of the poly (arylene ether sulfone) to about 270 ℃.
In recent years, as electronic and display technologies are advanced to higher speeds, higher integration, higher densities, and higher thicknesses, there is a demand for higher heat resistance, light transmittance, and other properties of materials. However, the existing polyarylethersulfone material is difficult to meet the requirements of flexible displays in the electronic information field, optical imaging of spacecrafts in the aerospace field, space optical telescopes and the like on material performance.
Disclosure of Invention
In view of the above, the invention provides a polyarylethersulfone resin and a preparation method thereof. The polyarylethersulfone resin provided by the invention has the characteristics of high temperature resistance, high transparency and high strength, and can meet the requirements of the increasingly developed electronic information field on the material performance.
In order to achieve the above object, the present invention provides the following technical solutions:
a polyarylethersulfone resin has a structural formula shown in formula I:
in formula I: n represents the mole fraction of bisphenol fluorene-containing fragments in the polyarylethersulfone resin, n is less than or equal to 10%.
Preferably, the reduced viscosity of the polyarylethersulfone resin is 0.32-0.48 dL.g -1 The glass transition temperature is 280-290 ℃.
The invention also provides a preparation method of the polyarylethersulfone resin, which comprises the following steps:
and mixing the bis- (4-chlorodiphenylsulfone), biphenol, bisphenol fluorene, a catalyst, an antioxidant, an azeotropic dehydrating agent and an organic solvent, sequentially carrying out azeotropic dehydration and polymerization reaction, and then adding a blocking agent into a reaction system for blocking to obtain the polyarylethersulfone resin.
Preferably, the mole ratio of the bi- (4-chlorodiphenyl sulfone), the biphenol and the bisphenol fluorene is (0.98-1.00): 0.95-0.98): 0.02-0.05.
Preferably, the catalyst is an alkali metal salt, and the molar amount of the catalyst is 1 to 1.2 times of that of the bis- (4-chlorodiphenyl sulfone);
the antioxidant comprises one or more of triphenyl phosphite and phosphite; the mass of the antioxidant is 0.5-1 wt% of the theoretical yield of the polyarylethersulfone resin;
the azeotropic dehydrating agent comprises one or more of toluene and xylene; the volume of the azeotropic dehydrating agent is 30-50% of the volume of the organic solvent.
Preferably, the azeotropic dehydration temperature is 140-180 ℃ and the azeotropic dehydration time is 2-4 h.
Preferably, the temperature of the polymerization reaction is 180-200 ℃ and the time is 3-5 h.
Preferably, the capping agent comprises one or more of 4, 4-difluorodiphenyl sulfone, 4-fluorobenzophenone and 4-fluorodiphenyl sulfone; the mole amount of the end capping agent is 1-3% of that of the di- (4-chlorodiphenyl sulfone).
Preferably, the end capping temperature is 190-200 ℃ and the time is 0.5-1 h.
Preferably, after the end capping, the method further comprises post-treatment of the obtained product feed liquid; the post-treatment comprises the following steps:
diluting the obtained product feed liquid to a solid content of 5-10wt%, and then filtering to obtain a polymer solution;
and adding the polymer solution into deionized water, separating out a solid product, crushing the solid product, and then washing and drying sequentially to obtain the polyarylethersulfone resin.
The invention provides a polyarylethersulfone resin, the structural formula of which is shown as formula I. The poly (arylene ether sulfone) resin is polymerized by the bi- (4-chlorodiphenyl sulfone), the biphenol and the bisphenol fluorene, wherein the bi- (4-chlorodiphenyl sulfone) can improve the rigidity of a poly (arylene ether sulfone) molecular chain, and the glass transition temperature, the heat resistance and the mechanical strength of the poly (arylene ether sulfone) resin are improved on the premise of not damaging the original performance of a resin material; meanwhile, bisphenol fluorene is a functional group containing a torque structure, and the light transmittance and the solubility of the material are increased by introducing a small amount of bisphenol fluorene groups, so that a novel high-heat-resistance high-light transmittance polyarylethersulfone resin material is obtained; in addition, the mechanical property and the glass transition temperature of the polyarylethersulfone resin are adjusted by adjusting the copolymerization ratio of the biphenol and the bisphenol fluorene serving as the functional group, and the copolymerization ratio of the bisphenol fluorene serving as the functional group is controlled within 10mol percent, so that the increase of brittleness of the polymer caused by introducing excessive functional groups is avoided, and the processability of the material is reduced.
In summary, the invention creatively carries out ternary polymerization on the bi- (4-chlorodiphenylsulfone), the rigid bisphenol monomer (biphenol) and the functional group (bisphenol fluorene) containing a torque structure, improves the light transmittance and the solubility of the polyarylethersulfone material while improving the glass transition temperature of the polyarylethersulfone through the introduction of a small amount of the rigid torque structure, and successfully prepares the high-temperature-resistant and high-transparency polyarylethersulfone material resin, and meanwhile, the polyarylethersulfone material resin also has excellent mechanical properties. The example results show that the glass transition temperature of the polyarylethersulfone resin provided by the invention can reach more than 280 ℃, and the application requirements of the polyarylethersulfone resin in a high-temperature environment can be met.
The invention also provides a preparation method of the polyarylethersulfone resin, which is simple in steps and easy to operate.
Drawings
FIG. 1 is an infrared spectrum of a polyarylethersulfone resin obtained in example 2;
FIG. 2 is a TGA test curve of the polyarylethersulfone resin obtained in example 2;
FIG. 3 is a DSC curve of the polyarylethersulfone resin obtained in example 2;
FIG. 4 shows the transmittance test result of the polyarylethersulfone resin obtained in example 2 in the visible light range.
Detailed Description
The invention provides a polyarylethersulfone resin, the structural formula of which is shown as formula I:
in formula I: n represents the mole fraction of bisphenol fluorene-containing fragments in the polyarylethersulfone resin (i.e. the ratio of the mole amount of bisphenol fluorene-containing fragments to the mole amount of all fragments in the resin), n is less than or equal to 10%.
In the present invention, n is preferably 0.1 to 10%, more preferably 1 to 8%, and still more preferably 2 to 5%.
In the present invention, the reduced viscosity of the polyarylethersulfone resin is preferably 0.32 to 0.48 dL.g -1 The number average molecular weight of the polyarylethersulfone resin is 31.80 kDa-42.60 kDa, the PDI is 1.6-1.8, and the glass transition temperature is preferably 280-290 ℃; the light transmittance of the polyarylethersulfone resin is preferably not less than 89%, the tensile strength is preferably 90MPa or more, more preferably 90-95 MPa, and the elongation at break is preferably 10% or more, more preferably 10-15%.
The invention also provides a preparation method of the polyarylethersulfone resin, which comprises the following steps:
and mixing the bis- (4-chlorodiphenylsulfone), biphenol, bisphenol fluorene, a catalyst, an antioxidant, an azeotropic dehydrating agent and an organic solvent, sequentially carrying out azeotropic dehydration and polymerization reaction, and then adding a blocking agent into a reaction system for blocking to obtain the polyarylethersulfone resin.
In the present invention, the molar ratio of the bis- (4-chlorodiphenylsulfone), the biphenol and the bisphenol fluorene is preferably (0.98-1.00): 0.95-0.98): 0.02-0.05, more preferably (0.98-1.00): 0.96-0.97): 0.03-0.04; the catalyst is preferably an alkali metal salt, preferably an alkali metal carbonate, more preferably one or more of potassium carbonate and sodium carbonate; the molar amount of the catalyst is preferably 1 to 1.2 times, more preferably 1.05 to 1.1 times the molar amount of bis- (4-chlorodiphenyl sulfone); the antioxidant preferably comprises one or more of triphenyl phosphite and a phosphite; the mass of the antioxidant is preferably 0.5-1 wt% of the theoretical yield of the polyarylethersulfone resin, more preferably 0.6-0.8 wt%; the antioxidant can avoid oxidation of reactants in the reaction process, and a polymer with lighter color is obtained; the azeotropic dehydrating agent preferably comprises one or both of toluene and xylene; the volume of the azeotropic dehydrating agent is preferably 30 to 50% of the volume of the organic solvent, more preferably 35 to 45%; the organic solvent is preferably an aprotic polar solvent, preferably one or more of sulfolane, diphenyl sulfone and N-methylpyrrolidone; the amount of the organic solvent is preferably controlled to be 10 to 25wt%, preferably 15 to 25wt% based on the solid content of the mixed solution obtained by mixing. In the invention, the purity of the bi- (4-chlorodiphenylsulfone), the biphenol monomer and the bisphenol fluorene is preferably higher than 99.5%, and the rest reagents are preferably ultra-pure and ultra-dry reagents.
In the present invention, the temperature of the azeotropic dehydration is preferably 140 to 180 ℃, more preferably 150 to 170 ℃, and the time of the azeotropic dehydration is preferably 2 to 4 hours, more preferably 2.5 to 3.5 hours; the temperature of the polymerization reaction is preferably 180 to 200 ℃, more preferably 185 to 195 ℃, and the time of the polymerization reaction is preferably 3 to 5 hours, more preferably 3.5 to 4.5 hours.
In the present invention, the end-capping agent preferably comprises one or more of 4, 4-difluorodiphenyl sulfone, 4-fluorobenzophenone and 4-fluorodiphenyl sulfone; the molar amount of the end-capping agent is preferably 1 to 3%, more preferably 1.5 to 2.5% of the molar amount of bis- (4-chlorodiphenyl sulfone); the temperature of the end capping is preferably 190 to 200 ℃, more preferably 190 to 195 ℃, and the time of the end capping is preferably 0.5 to 1h.
In the present invention, the azeotropic dehydration, polymerization and capping are preferably performed under the protection of an inert gas, preferably argon.
In the specific embodiment of the invention, the bis- (4-chlorodiphenyl sulfone), the biphenol and the bisphenol fluorene are preferably added into a reaction device, then a catalyst, an organic solvent and an azeotropic dehydrating agent are added, then stirring is carried out for 1h under an argon atmosphere, then the temperature is increased to the temperature of azeotropic dehydration, azeotropic dehydration is carried out under a reflux condition, after the azeotropic dehydrating agent is completely evaporated, the temperature is continuously increased to the temperature of polymerization reaction for reaction, after the polymerization reaction is finished, the temperature is increased to the end-capping temperature, then an end-capping agent is added into a reaction system, and the reaction is continued for 0.5-1 h for end-capping. In the present invention, the reaction apparatus is preferably a three-necked flask with an inert gas pipe, a condensation water separator, and a stirring device.
After the end capping, the invention preferably further comprises post-treatment of the obtained product feed liquid; the post-treatment comprises the following steps:
diluting the obtained product feed liquid to a solid content of 5-10wt%, and then filtering to obtain a polymer solution;
and adding the polymer solution into deionized water, separating out a solid product, crushing the solid product, and then washing and drying sequentially to obtain the polyarylethersulfone resin.
In the present invention, the diluting agent is preferably an organic solvent, more preferably an aprotic polar organic solvent, and the type of the aprotic polar organic solvent is the same as that of the above-described scheme, and will not be described in detail herein; the invention can dilute the product feed liquid and then filter the product feed liquid, thereby improving the filtering speed; filtering to remove residual alkali metal salt and potassium chloride, sodium chloride, etc.
The volume ratio of the polymer solution to the deionized water is not particularly required, and any ratio can be adopted, and in the specific embodiment of the invention, the more the deionized water is used, the better the ratio is; the invention is not particularly limited to such comminution, in particular embodiments of the invention, the solid product is preferably comminuted to less than 300 mesh; the washing is preferably boiling washing by sequentially adopting deionized water and a low-boiling-point organic solvent, wherein the low-boiling-point organic solvent is preferably an alcohol solvent, and more preferably methanol or ethanol; the number of times of boiling washing of the deionized water is preferably 5 times, and the number of times of boiling washing of the low boiling point organic solvent is preferably 5 times; the invention removes residual solvent and byproduct salt by the washing; the drying is preferably carried out in a vacuum oven; the invention has no special requirement on the specific operation condition of vacuum drying, and can dry the polyarylethersulfone resin until the moisture content is lower than 0.5% by weight, and the product obtained after drying is white powder.
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, a polyarylethersulfone resin was prepared into a film having a thickness of 100 μm and then tested in performing light transmittance, tensile strength and elongation at break; tensile strength and elongation at break were tested according to the method in GB/T1040.3-2006; the transmittance was measured in the visible range using ultraviolet spectroscopy.
Example 1
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 0.98mol of biphenol, 0.02mol of bisphenol fluorene and 1.2mol of potassium carbonate, adding 3000mL of sulfolane and 360mL of toluene, mechanically stirring for 1h under argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after all toluene is evaporated, mechanically stirring for 2.5h, adding 0.02mol of end-capping agent (4, 4-difluorodiphenyl sulfone), and continuously reacting for 0.5h.
And adding sulfolane into the obtained product feed liquid to dilute until the solid content is 5-10wt% and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1h, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the high-temperature-resistant high-transparency polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like, and the reduced viscosity in NMP is 0.38 dL.g -1 The number average molecular weight was 37.20kDa and the PDI was 1.7; the glass transition temperature is 282 ℃, the light transmittance is 89%, the tensile strength is 92MPa, and the elongation at break is 15%.
Example 2
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 0.95mol of biphenol, 0.05mol of bisphenol fluorene and 1.2mol of potassium carbonate, adding 3000mL of sulfolane and 360mL of toluene, mechanically stirring for 1h under argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after all toluene is evaporated, mechanically stirring for 2.5h, adding 0.02mol of end-capping agent (4, 4-difluorodiphenyl sulfone), and continuously reacting for 0.5h.
Adding aprotic polar organic solvent into the obtained product liquid, diluting to solid content of 5-10wt%, and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1 hour, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the high-temperature-resistant high-transparency polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like. Its reduced viscosity in NMP is 0.38 dL.g -1 The number average molecular weight was 37.80kDa and the PDI was 1.68; the glass transition temperature is 285 ℃, the light transmittance is 92%, the tensile strength is 95MPa, and the elongation at break is 14%.
FIG. 1 is an infrared spectrum of a polyarylethersulfone resin obtained in example 2; as can be seen from the graph, the flexural vibration absorption peak of the biphenyl structure appears at 1015cm -1 The position of the sulfonyl stretching vibration absorption peak is 1305cm -1 And 1152cm -1 At 1234cm -1 The characteristic absorption peak of ether bond appears, which shows that we successfully prepare the high-temperature-resistant and high-transparency polyarylethersulfone.
FIG. 2 is a TGA test curve of the polyarylethersulfone resin obtained in example 2; as can be seen from the figure, the high temperature and high transparency poly (arylene ether sulfone) prepared in example 3 was not decomposed before 450 ℃ and the 5% thermal decomposition temperature reached 515 ℃.
FIG. 3 is a DSC curve of the polyarylethersulfone resin obtained in example 2; as can be seen from the figure, the high temperature and high transparency resistant polyarylethersulfone prepared in example 3 has a glass transition temperature of 285 ℃.
FIG. 4 shows the transmittance test result of the polyarylethersulfone resin obtained in example 2 in the visible light range; as can be seen from the graph, the high-temperature-resistant and high-transparency polyarylethersulfone film prepared in the example 2 has the light transmittance exceeding 90% and has good light transmittance.
Example 3
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 0.93mol of biphenol, 0.07mol of bisphenol fluorene and 1.2mol of potassium carbonate, adding 3000mL of sulfolane and 360mL of toluene, mechanically stirring for 1h under argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after the toluene is completely distilled, mechanically stirring for 2.5h, adding 0.02mol of end-capping agent (4, 4-difluorodiphenyl sulfone), and continuously reacting for 0.5h.
Adding aprotic polar organic solvent into the obtained product liquid, diluting to solid content of 5-10wt%, and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1h, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the high-temperature-resistant high-transparency polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like. Its reduced viscosity in NMP is 0.36 dL.g -1 The number average molecular weight was 34.20kDa and the PDI was 1.74; the glass transition temperature is 287 ℃, the light transmittance is 90%, the tensile strength is 95MPa, and the elongation at break is 13%
Example 4
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 0.90mol of biphenol, 0.10mol of bisphenol fluorene and 1.2mol of potassium carbonate, adding 3000mL of sulfolane and 360mL of toluene, mechanically stirring for 1h under argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after all toluene is evaporated, mechanically stirring for 2.5h, adding 0.02mol of end-capping agent (4, 4-difluorodiphenyl sulfone), and continuously reacting for 0.5h.
Adding aprotic polar organic solvent into the obtained product liquid, diluting to solid content of 5-10wt%, and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1h, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the high-temperature-resistant high-transparency polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like. Its reduced viscosity in NMP was 0.34 dL.g -1 The number average molecular weight was 33.80kDa and the PDI was 1.66; the glass transition temperature is 290 ℃, the light transmittance is 89%, the tensile strength is 95MPa, and the elongation at break is 10%.
Comparative example 1 omitted bisphenol fluorene
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 1mol of diphenyl diphenol and 1.2mol of potassium carbonate, adding 3000mL of diphenyl sulfone and 360mL of toluene, mechanically stirring for 1h under an argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after the toluene is completely distilled, mechanically stirring for 2.5h, adding 0.02mol of end-capping agent (4, 4-difluorodiphenyl sulfone), and continuously reacting for 0.5h.
Adding diphenyl sulfone into the obtained product liquid, diluting until the solid content is 5-10wt%, and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1h, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the high-temperature-resistant high-transparency polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like. Its reduced viscosity in NMP is 0.42 dL.g -1 The number average molecular weight was 39.20kDa and the PDI was 1.68; the glass transition temperature is 280 ℃, the light transmittance is 82%, the tensile strength is 90MPa, and the elongation at break is 15%.
As can be seen from comparative example 1, the glass transition temperature and the light transmittance of the resulting polyarylethersulfone resin were reduced after bisphenol fluorene was omitted.
Comparative example 2 substitution of Biphenyl diphenol with hydroquinone
In a three-necked flask equipped with a nitrogen-introducing pipe, a condensation water separator and a stirring device, sequentially adding 1mol of bis- (4-chlorodiphenyl sulfone), 1mol of hydroquinone and 1.2mol of potassium carbonate, adding 3000mL of diphenyl sulfone and 360mL of toluene, mechanically stirring for 1h under an argon atmosphere, heating to 140 ℃, carrying out azeotropic dehydration and reflux for 3h, continuously heating to 190 ℃ after the toluene is completely distilled out, mechanically stirring for 2.5h, and adding 0.02mol of end-capping agent (4, 4-difluoro diphenyl sulfone), and continuously reacting for 0.5h.
Adding diphenyl sulfone into the obtained product liquid, diluting until the solid content is 5-10wt%, and filtering. Pouring the filtered polymer solution into deionized water, and crushing to obtain polymer powder; adding deionized water into the filtered powder, boiling for 1h, repeating for 5 times, adding absolute ethyl alcohol, boiling for 40min, repeating for 5 times, and vacuum drying the filtered polymer powder until the water content is lower than 0.5% to obtain the polyarylethersulfone resin.
Through tests, the obtained polyarylethersulfone resin has good solubility in solvents such as DMAC, NMP and the like. Its reduced viscosity in NMP is 0.44 dL.g -1 The number average molecular weight was 41.60kDa and the PDI was 1.80; the glass transition temperature is 258 ℃, the light transmittance is 82%, the tensile strength is 76MPa, and the elongation at break is 17%.
As can be seen from comparative example 2, after the biphenol is replaced by hydroquinone, the glass transition temperature and the tensile strength of the obtained polyarylethersulfone resin are reduced. Meanwhile, compared with comparative examples 1 and 2, the bisphenol fluorene groups added in examples 1 to 4 can greatly improve the transmittance of the film while increasing the glass transition temperature. This is probably due to the fact that the small amount of bisphenol fluorene twisted structure reduces the conjugation effect of the chain segment, so that the film has higher light transmittance.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The polyarylethersulfone resin is characterized in that the structural formula is shown as formula I:
in formula I: n represents the mole fraction of bisphenol fluorene-containing fragments in the polyarylethersulfone resin, n is less than or equal to 10%.
2. The polyarylethersulfone resin of claim 1, wherein the reduced viscosity of the polyarylethersulfone resin is from 0.32 to 0.48 dL-g -1 The glass transition temperature is 280-290 ℃.
3. The method for preparing the polyarylethersulfone resin as set forth in claim 1 or 2, comprising the steps of:
and mixing the bis- (4-chlorodiphenylsulfone), biphenol, bisphenol fluorene, a catalyst, an antioxidant, an azeotropic dehydrating agent and an organic solvent, sequentially carrying out azeotropic dehydration and polymerization reaction, and then adding a blocking agent into a reaction system for blocking to obtain the polyarylethersulfone resin.
4. The method according to claim 3, wherein the molar ratio of the bis- (4-chlorodiphenyl sulfone), the biphenol and the bisphenol fluorene is (0.98-1.00): 0.95-0.98): 0.02-0.05.
5. The process according to claim 3, wherein the catalyst is an alkali metal salt and the molar amount of the catalyst is 1 to 1.2 times the molar amount of bis- (4-chlorodiphenyl sulfone);
the antioxidant comprises one or more of triphenyl phosphite and phosphite; the mass of the antioxidant is 0.5-1 wt% of the theoretical yield of the polyarylethersulfone resin;
the azeotropic dehydrating agent comprises one or more of toluene and xylene; the volume of the azeotropic dehydrating agent is 30-50% of the volume of the organic solvent.
6. The process according to claim 3, wherein the azeotropic dehydration is carried out at a temperature of 140 to 180℃for a period of 2 to 4 hours.
7. The process according to claim 3, wherein the polymerization reaction is carried out at a temperature of 180 to 200℃for a period of 3 to 5 hours.
8. The method of claim 3, wherein the end-capping agent comprises one or more of 4, 4-difluorodiphenyl sulfone, 4-fluorobenzophenone, and 4-fluorodiphenyl sulfone; the mole amount of the end capping agent is 1-3% of that of the di- (4-chlorodiphenyl sulfone).
9. The method according to claim 3 or 8, wherein the capping temperature is 190 to 200 ℃ for 0.5 to 1 hour.
10. The method of claim 3, further comprising post-treating the resulting product feed solution after the capping; the post-treatment comprises the following steps:
diluting the obtained product feed liquid to a solid content of 5-10wt%, and then filtering to obtain a polymer solution;
and adding the polymer solution into deionized water, separating out a solid product, crushing the solid product, and then washing and drying sequentially to obtain the polyarylethersulfone resin.
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| DE19840224A1 (en) * | 1998-09-03 | 2000-03-09 | Consortium Elektrochem Ind | Process for the preparation of catalysts for the synthesis of maleic anhydride by gas phase oxidation |
| CN107778486A (en) * | 2017-10-31 | 2018-03-09 | 中国科学院长春应用化学研究所 | A kind of post-processing approach of soluble poly aromatic ether sulphone resin |
| CN107778504A (en) * | 2017-10-31 | 2018-03-09 | 中国科学院长春应用化学研究所 | A kind of continuous preparation method of soluble poly aromatic ether sulfone film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19840224A1 (en) * | 1998-09-03 | 2000-03-09 | Consortium Elektrochem Ind | Process for the preparation of catalysts for the synthesis of maleic anhydride by gas phase oxidation |
| CN107778486A (en) * | 2017-10-31 | 2018-03-09 | 中国科学院长春应用化学研究所 | A kind of post-processing approach of soluble poly aromatic ether sulphone resin |
| CN107778504A (en) * | 2017-10-31 | 2018-03-09 | 中国科学院长春应用化学研究所 | A kind of continuous preparation method of soluble poly aromatic ether sulfone film |
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