CN109721733A - A kind of preparation method of polysulfones resinoid - Google Patents
A kind of preparation method of polysulfones resinoid Download PDFInfo
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 73
- 229920000642 polymer Polymers 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 81
- 239000000178 monomer Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 31
- 150000002367 halogens Chemical class 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 238000009156 water cure Methods 0.000 claims abstract description 19
- 238000001291 vacuum drying Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000005469 granulation Methods 0.000 claims abstract description 8
- 230000003179 granulation Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 63
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 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 description 37
- 238000000034 method Methods 0.000 claims description 37
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229940106691 bisphenol a Drugs 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical group ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 claims 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical class C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 66
- 239000003960 organic solvent Substances 0.000 abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 5
- 238000003408 phase transfer catalysis Methods 0.000 abstract description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 239000002585 base Substances 0.000 description 70
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000010792 warming Methods 0.000 description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- 229920005989 resin Polymers 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000011033 desalting Methods 0.000 description 10
- 229920002313 fluoropolymer Polymers 0.000 description 10
- 239000004811 fluoropolymer Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 102100028680 Protein patched homolog 1 Human genes 0.000 description 8
- 101710161390 Protein patched homolog 1 Proteins 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 101000974343 Homo sapiens Nuclear receptor coactivator 4 Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 102100022927 Nuclear receptor coactivator 4 Human genes 0.000 description 6
- 102100036894 Protein patched homolog 2 Human genes 0.000 description 6
- 101710161395 Protein patched homolog 2 Proteins 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 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 5
- 229920000491 Polyphenylsulfone Polymers 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 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 4
- 101001134861 Homo sapiens Pericentriolar material 1 protein Proteins 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 102100033422 Pericentriolar material 1 protein Human genes 0.000 description 4
- 101100189627 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PTC5 gene Proteins 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 101100189632 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PTC6 gene Proteins 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Ether sulfone Chemical class 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- 241000208340 Araliaceae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- RMNIZOOYFMNEJJ-UHFFFAOYSA-K tripotassium;phosphate;hydrate Chemical compound O.[K+].[K+].[K+].[O-]P([O-])([O-])=O RMNIZOOYFMNEJJ-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention provides a kind of preparation methods of polysulfones resinoid, comprising the following steps: a) biphenol monomer, salt forming agent, compound base catalyst and double halogen monomers is carried out polymerization reaction in a solvent, obtains polymer solution；The compound base catalyst contains structure shown in formula (I) or formula (II)；Wherein ,-R1Selected from-CH3Or phenyl；-R2Selected from-CH3、‑CH2CH3Or isopropyl；-R3Selected from-CH3、‑CH2CH3；B) it is crushed after the obtained polymer solution of step a) being entered water cure, then successively obtains polysulfones resinoid through washing, vacuum drying and granulation.Compared with prior art, preparation method provided by the invention is using specific compound base catalyst, carry out polymerization reaction under phase transfer catalysis system, to realize the generation for reducing (or part inhibits) cyclic oligomer during the reaction, to reduce its content in a polymer solution, so that the polymer solution made is not necessarily to can be obtained the polysulfones resinoid of lower cyclic oligomer levels through additional organic solvent purifying.
Description
Technical field
The present invention relates to macromolecule synthesising technology fields, are to be related to a kind of preparation side of polysulfones resinoid more specifically
Method.
Background technique
Polysulfones resinoid (PSF) is a kind of thermoplastic special engineering plastic, and main Types include: polyphenylsulfone (PPSU), gather
Ether sulfone (PES) and polysulfones (PSU).Polysulfones resinoid has intensity height, good toughness, high temperature resistant, resistant to chemical etching, have both it is excellent at
The advantages that film property, can be processed into a variety of devices such as plate membrane, doughnut, ultrafiltration membrane, and is widely used in electronics, automobile and flies
The industrial circles such as machine and water treatment procedure.Moreover, polysulfones resinoid also has the excellent of nontoxic, radiation resistance and hydrolysis
Good mechanical performance and lower can still be maintained under the conditions of point, especially high temperature sustained load or under steam, sterile environment
Croop property, long-term use temperature reaches 160 DEG C or more, food hygiene, in terms of obtained extensively
Using.
By taking polysulfones as an example, 10% or more growth rate (global polysulfones resinoid annual output is presented in global usage amount every year
Amount is more than 40,000 tons), and China has been more than 20% for the average annual growth rate of demand of polysulfones.Cut-off 2017, the year of domestic polysulfones
Demand alreadys exceed 6000 tons, especially even more increases year by year in the demand of field of medical applications.However, current state cohesion
The production capacity of sulfone is about 1500~2000 tons/year.Compared with external similar polysulfones product, there is only production technologies to fall for domestic polysulfones
Afterwards, the impurity contents such as lot stability is poor, oligomer and metal ion are high, and there is also kinds or price all can not be with imported product
The problems such as competition；In particular for preparing the high-end medical product such as hemodialysis membrane, membrane oxygenator, artificial heart valve
Medical grade polysulfone material almost all rely on import.In addition, domestic polysulfone resin due to there are cyclic oligomer and metal from
The problems such as impurity contents such as son are high, easily causes not high through light rate when preparing thin-film device using it, and uneven color is even, adds
The problems such as work yield rate is low also limits it in the extensive use of advanced optical film applications.In conclusion polysulfones resinoid
Purity problem, especially cyclic oligomer impurity content are high, are to restrict polysulfones resinoid to lead in high-end medical field, advanced optical
The widely applied main bottleneck in domain.
Polysulfones resinoid is usually to be existed by biphenol monomer (bisphenol-A, bisphenol S, '-biphenyl diphenol etc.) and 4,4 '-dichloro diphenyl sulfones
Alkalinity (NaOH, KOH, K2CO3、K3PO4Deng) under the conditions of prepare through polycondensation reaction, common are two-step synthesis method --- method is received
Nurse (Farnham) nucleophilic substitution and one-step synthesis.Although both preparation processes and process have differences, but be with
The metal salt (NaOAr or KOAr) for preparing phenol is target, and completes sufficiently polymerization under the appropriate temperature conditions.It is synthesized with polysulfones
For: two-step synthesis method is usually to react bisphenol-A in dimethyl sulfoxide (DMSO) solvent with sodium hydroxide (or potassium hydroxide)
The sodium salt (or sylvite) for generating bisphenol-A, then distills out a point aqua (toluene, dimethylbenzene, hexamethylene etc.)；After dividing water, to
4,4 '-dichloro diphenyl sulfones are wherein added and carry out polycondensation reaction at 140-160 DEG C.United States Patent (USP) US1978/US4108837 is detailed
Describe this polycondensation process.However, the production process is more complex, height especially is required to the control of system water content,
And condition control is stringent etc. when secondary batching.One-step synthesis is usually to utilize inorganic middle highly basic (potassium carbonate, sodium carbonate, carbon
Sour caesium etc.) it is used as salt-forming reagent；The method may be implemented a step and feed intake, and enormously simplify production technology.But salt-forming reaction
The bicarbonate generated in journey is heated to generate water, and azeotropic is caused to divide water step essential.In recent years, Chinese patent
CN200910069382.2 discloses the new method that a kind of nothing point hydraulic art prepares polysulfones resinoid, since reaction process can produce
Raw stable potassium phosphate hydrate, thus the step of azeotropic divides water is eliminated, shorten the reaction time；Chinese patent
CN201110286532.2 discloses a kind of method that polysulfones is prepared in compound ion liquid solvent, shorten salt time and
Dewatering time, and realize the green reclaim of solvent；Chinese patent CN201410790045.3 and CN201510361661.1 points
It does not disclose and utilizes method high pressure (2.0~3.0MPa) synthesis technology and polysulfones resinoid is prepared as heat source using microwave, polymerization
Reaction time greatly shortens, and has saved energy consumption.
By semicentennial development, the production technology majority for the polysulfones resinoid developed concentrates on the tune of alkali type
Section, the optimization of reaction dissolvent system and the research of simplified dewatering process etc..And it is low to the ring-type in polymerization reaction system
Copolymer content but lacks effective control.Cyclic oligomer is also referred to as cyclic oligomer, and chemical structure (by taking polysulfones as an example) is referring to formula
(III) shown in；
Wherein, n=1~5.In the polycondensation reaction of polysulfones resinoid, the polymer of generation is same based on linear polymer
When there is also a small amount of cyclic oligomers, wherein cyclic oligomer is based on cyclic dimer, trimer and tetramer.Different is poly-
It closes monomer structure and different polymerisation process, the cyclic oligomer levels for eventually leading to polysulfones resinoid differs greatly.By
The containing there are larger difference and cyclic oligomer between these cyclic oligomer dissolubilities and rigidity and linear polymer backbone
Measuring excessively high is the major reason for leading to polysulfones resinoid opaque (or solution is muddy).For these reasons, high-purity polysulfones
Resinoid must control the content of cyclic oligomer.United States Patent (USP) US2001/0056175A1 discloses one kind with chlorobenzene
For solvent, methanol as precipitating solvent be used to reduce polysulfones resinoid middle ring shape oligomer method, but last handling process need
A large amount of organic solvent is used, and is faced with the difficult problem of ternary azeotropic system organic solvent recycling；Chinese patent
CN201210380356.3 discloses a kind of method for preparing polysulfone resin by flashing precipitating, effectively reduces polysulfone resin packet
The content for the inorganic salt particle wrapped up in improve product purity, and overcomes the high problem of solvent recovery energy consumption after precipitating；In
State patent CN201710625749.9, which is disclosed, a kind of to be centrifuged by dilution post-consumer polymer solution, high-purity is obtained by filtration gathers
The polymer solution of sulfone, then concentrated, extruding pelletization obtain the polysulfones resinoid of high-purity.
But the method majority of these preparation high-purity polysulfones resinoids is first to prepare corresponding polysulfones resinoid, then
It separated, purified again, to achieve the purpose that reduce cyclic oligomer levels；Its purification process needs a large amount of organic solvent
(such as methanol, ethyl alcohol, isopropanol, toluene, dimethylbenzene, chlorobenzene), or solvent identical with polymerization system as diluent (such as
DMSO, DMAc, NMP, sulfolane etc.).
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of polysulfones resinoid, it can be in reaction process
The middle generation for reducing (or part inhibits) cyclic oligomer, to reduce its content in a polymer solution, thus make
Polymer solution is not necessarily to can be obtained the polysulfones resinoid of lower cyclic oligomer levels through additional organic solvent purifying.
The present invention provides a kind of preparation methods of polysulfones resinoid, comprising the following steps:
A) biphenol monomer, salt forming agent, compound base catalyst and double halogen monomers are subjected to polymerization reaction in a solvent, gathered
Polymer solution；The compound base catalyst contains structure shown in formula (I) or formula (II)；
Wherein ,-R1Selected from-CH3Or-R2Selected from-CH3、-CH2CH3Or-R3Selected from-CH3、-
CH2CH3；
B) it is crushed after the obtained polymer solution of step a) being entered water cure, then successively through washing, vacuum drying and granulation,
Obtain polysulfones resinoid.
Preferably, biphenol monomer described in step a) is selected from bisphenol-A, bisphenol S or 4,4 '-'-biphenyl diphenols.
Preferably, salt forming agent described in step a) is selected from NaOH, KOH, K2CO3And K3PO4One of or it is a variety of.
Preferably, the dosage of compound base catalyst described in step a) is the 0.1%~3% of biphenol monomer mole.
Preferably, double halogen monomers described in step a) are selected from 4,4 '-dichloro diphenyl sulfones, 4,4 '-tetrafluoro diphenyl sulphone (DPS)s or 4, and 4 '-
Difluoro benzophenone.
Preferably, the molar ratio of biphenol monomer described in step a), salt forming agent and double halogen monomers is 1:(2~3): (0.8~
1.2)。
Preferably, the temperature of polymerization reaction described in step a) is 70 DEG C~220 DEG C, and the time is 1h~15h.
Preferably, the process of polymerization reaction described in step a) specifically:
In a solvent by biphenol monomer dissolution, it after addition salt forming agent and compound base catalyst carry out point water reaction, adds
Double halogen monomer heatings, carry out first polycondensation reaction, obtain polymer solution；
Or biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst are sequentially added in a solvent carry out point water and react
Afterwards, it heats up, carries out the second polycondensation reaction, obtain polymer solution；
Or after sequentially adding biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst in a solvent, heat up, carries out
Third polycondensation reaction obtains polymer solution after dilution.
Preferably, the temperature for dividing water to react is 110 DEG C~150 DEG C, and the time is 5h~7h.
Preferably, vacuum drying temperature described in step b) is 100 DEG C~150 DEG C, and the time is 20h~30h.
The present invention provides a kind of preparation methods of polysulfones resinoid, comprising the following steps: a) by biphenol monomer, at salt
Agent, compound base catalyst and double halogen monomers carry out polymerization reaction in a solvent, obtain polymer solution；The compound base catalyst
Contain structure shown in formula (I) or formula (II)；Wherein ,-R1Selected from-CH3Or phenyl；-R2Selected from-CH3、-CH2CH3Or isopropyl；-
R3Selected from-CH3、-CH2CH3；B) it is crushed after the obtained polymer solution of step a) being entered water cure, then successively through washing, vacuum
Dry and granulation, obtains polysulfones resinoid.Compared with prior art, preparation method provided by the invention is using specific compound alkali
Catalyst carries out polymerization reaction under phase transfer catalysis system, reduces (or part inhibits) during the reaction to realize
The generation of cyclic oligomer, to reduce its content in a polymer solution, so that the polymer solution made is not necessarily to through volume
Outer organic solvent purifying can be obtained the polysulfones resinoid of lower cyclic oligomer levels；Meanwhile preparation provided by the invention
Method avoids complicated organic solvent purifying process, simplifies preparation process.The experimental results showed that preparation side provided by the invention
Two cyclic oligomer contents of the polysulfones resinoid that method is prepared can reduce to 1.06%, and cyclic oligomer total content can drop
Down to 3.51%.
In addition, preparation method provided by the invention have extensive adaptability, can in conjunction with one-step synthesis, two steps synthesis and
Nothing divides the different types of polysulfones resinoids such as the preparation of the techniques such as water PPSU, PES and PSU.
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC1 used in the embodiment of the present invention；
Fig. 2 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC1 used in the embodiment of the present invention；
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC2 used in the embodiment of the present invention；
Fig. 4 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC2 used in the embodiment of the present invention；
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC3 used in the embodiment of the present invention；
Fig. 6 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC3 used in the embodiment of the present invention；
Fig. 7 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC4 used in the embodiment of the present invention；
Fig. 8 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC4 used in the embodiment of the present invention；
Fig. 9 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC5 used in the embodiment of the present invention；
Figure 10 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC5 used in the embodiment of the present invention；
Figure 11 is the hydrogen nuclear magnetic resonance spectrogram of the compound base catalyst of PTC6 used in the embodiment of the present invention；
Figure 12 is the carbon-13 nmr spectra figure of the compound base catalyst of PTC6 used in the embodiment of the present invention；
Figure 13 is the infrared spectrogram for the polysulfones that the preparation method that the embodiment of the present invention 5 provides is prepared；
Figure 14 is the hydrogen nuclear magnetic resonance spectrogram for the polysulfones that the preparation method that the embodiment of the present invention 5 provides is prepared；
Figure 15 is the gel chromatography figure for the polysulfones that the preparation method that the embodiment of the present invention 5 provides is prepared；
Figure 16 is the gel chromatography figure for the polysulfones that the preparation method that comparative example 1 provides is prepared.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Every other embodiment obtained by those of ordinary skill in the art without making creative efforts, belongs to this hair
The range of bright protection.
The present invention provides a kind of preparation methods of polysulfones resinoid, comprising the following steps:
A) biphenol monomer, salt forming agent, compound base catalyst and double halogen monomers are subjected to polymerization reaction in a solvent, gathered
Polymer solution；The compound base catalyst contains structure shown in formula (I) or formula (II)；
Wherein ,-R1Selected from-CH3Or-R2Selected from-CH3、-CH2CH3Or-R3Selected from-CH3、-
CH2CH3；
B) it is crushed after the obtained polymer solution of step a) being entered water cure, then successively through washing, vacuum drying and granulation,
Obtain polysulfones resinoid.
Biphenol monomer, salt forming agent, compound base catalyst and double halogen monomers are carried out polymerizeing anti-by the present invention in a solvent first
It answers, obtains polymer solution.In the present invention, the biphenol monomer is preferably selected from bisphenol-A, bisphenol S or 4,4 '-'-biphenyl diphenols；
Wherein, bisphenol-A is used to prepare PSU, and bisphenol S is used to prepare PES, and 4,4 '-'-biphenyl diphenols are used to prepare PPSU.Of the invention preferred
Embodiment in, the biphenol monomer be bisphenol-A.The present invention is not particularly limited the source of the biphenol monomer, using this
Above-mentioned bisphenol-A, the commercial goods of bisphenol S and 4,4 '-'-biphenyl diphenols known to the technical staff of field or laboratory own product.
In the present invention, the salt forming agent is preferably selected from NaOH, KOH, K2CO3And K3PO4One of or it is a variety of, it is more excellent
It is selected as KOH.In the preferred embodiment of the invention, the KOH is added in form of an aqueous solutions, and the present invention does not have special limit to this
System.The present invention is not particularly limited the source of the salt forming agent, using above-mentioned NaOH, KOH well known to those skilled in the art,
K2CO3And K3PO4Commercial goods.
In the present invention, the molar ratio of the salt forming agent and biphenol monomer is preferably (2~3): 1, more preferably (2~
2.4): 1.
In the present invention, the compound base catalyst contains structure shown in formula (I) or formula (II), preferably comprises formula (II) institute
Show structure；
Wherein ,-R1Selected from-CH3OrPreferably-R2Selected from-CH3、-CH2CH3Or
Preferably-R3Selected from-CH3、-CH2CH3, preferably-CH2CH3。
In the present invention, the compound base catalyst is preferably selected from It (is successively denoted as
The compound base catalyst in PTC1~6) one of or it is a variety of, more preferably It is more excellent
It is selected asThe present invention is not particularly limited the source of the compound base catalyst, using art technology
Preparation method known to personnel.
In the present invention, the dosage of the compound base catalyst is preferably the 0.1%~3% of biphenol monomer mole, more
Preferably the 0.2%~0.5% of biphenol monomer mole.
In the present invention, double halogen monomers are preferably selected from 4,4 '-dichloro diphenyl sulfones, 4,4 '-tetrafluoro diphenyl sulphone (DPS)s or 4, and 4 '-
Difluoro benzophenone, more preferably 4,4 '-dichloro diphenyl sulfones.The present invention is not particularly limited the source of double halogen monomers,
Using above-mentioned 4,4 '-dichloro diphenyl sulfone well known to those skilled in the art, 4,4 '-tetrafluoro diphenyl sulphone (DPS)s and 4,4 '-difluorodiphenyl first
The commercial goods of ketone or laboratory own product.
In the present invention, the molar ratio of double halogen monomers and biphenol monomer is preferably (0.8~1.2): 1, more preferably
1:1.
In the present invention, the solvent is preferably selected from one of DMAc, DMSO, NMP and sulfolane or a variety of, more preferably
For DMAc or DMSO.The present invention is not particularly limited the source of the solvent, using well known to those skilled in the art above-mentioned
The commercial goods of polar non-solute.In the present invention, the amount ratio of the solvent and biphenol monomer is preferably (1.5L
~5L): 1kg, more preferably (4L~5L): 1kg.
In the present invention, the temperature of the polymerization reaction is preferably 70 DEG C~220 DEG C, more preferably 80 DEG C~160 DEG C；Institute
The time for stating polymerization reaction is preferably 1h~15h, more preferably 3h~12h.
In the present invention, the process of the polymerization reaction is preferred specifically:
In a solvent by biphenol monomer dissolution, it after addition salt forming agent and compound base catalyst carry out point water reaction, adds
Double halogen monomer heatings, carry out first polycondensation reaction, obtain polymer solution；
Or biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst are sequentially added in a solvent carry out point water and react
Afterwards, it heats up, carries out the second polycondensation reaction, obtain polymer solution；
Or after sequentially adding biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst in a solvent, heat up, carries out
Third polycondensation reaction obtains polymer solution after dilution；
More preferably:
In a solvent by biphenol monomer dissolution, it after addition salt forming agent and compound base catalyst carry out point water reaction, adds
Double halogen monomer heatings, carry out first polycondensation reaction, obtain polymer solution.
In the present invention, the process of the polymerization reaction preferably carries out under nitrogen protection and stirring condition.
In a preferred embodiment of the invention, the process of the polymerization reaction specifically:
In a solvent by biphenol monomer dissolution, it after addition salt forming agent and compound base catalyst carry out point water reaction, adds
Double halogen monomer heatings, carry out first polycondensation reaction, obtain polymer solution.Biphenol monomer is dissolved in solvent first by the present invention
In；The biphenol monomer and solvent with it is as described in the above technical scheme identical, details are not described herein.
In the present invention, the temperature of the dissolution is preferably 70 DEG C~90 DEG C, more preferably 80 DEG C.
After the biphenol monomer is completely dissolved, salt forming agent is added in the present invention and compound base catalyst carries out point water and reacts；
The salt forming agent and compound base catalyst with it is as described in the above technical scheme identical, details are not described herein.
In the present invention, the temperature for dividing water to react is preferably 110 DEG C~150 DEG C, more preferably 140 DEG C；Described point
The time of water reaction is preferably 5h~7h, more preferably 6h.
After dividing water, the present invention adds double halogen monomers heatings, carries out first polycondensation reaction, obtains polymer solution；
Double halogen monomers with it is as described in the above technical scheme identical, details are not described herein.
In the present invention, the temperature of the first polycondensation reaction is preferably 160 DEG C~220 DEG C, more preferably 160 DEG C；Institute
The time for stating first polycondensation reaction is preferably 1h~6h, more preferably 1h~3h.
In presently preferred embodiment, the process of the polymerization reaction specifically:
It is sequentially added after biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst carry out the reaction of point water in a solvent,
Heating carries out the second polycondensation reaction, obtains polymer solution.In the present invention, the solvent, biphenol monomer, double halogen monomers, at
Salt agent and compound base catalyst with it is as described in the above technical scheme identical, details are not described herein.
In the present invention, the temperature for dividing water to react is preferably 110 DEG C~150 DEG C, more preferably 140 DEG C；Described point
The time of water reaction is preferably 5h~7h, more preferably 6h.
In the present invention, the temperature of second polycondensation reaction is preferably 160 DEG C~220 DEG C, more preferably 160 DEG C；Institute
The time for stating the second polycondensation reaction is preferably 1h~6h, more preferably 3h~6h.
In presently preferred embodiment, the process of the polymerization reaction specifically:
After sequentially adding biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst in a solvent, heating carries out the
Three polycondensation reactions obtain polymer solution after dilution.In the present invention, the solvent, biphenol monomer, double halogen monomers, salt forming agent
With compound base catalyst with it is as described in the above technical scheme identical, details are not described herein.
In the present invention, the temperature of the third polycondensation reaction is preferably 160 DEG C~220 DEG C, more preferably 160 DEG C；Institute
The time for stating third polycondensation reaction is preferably 1h~6h, more preferably 3h~6h.
The present invention is not particularly limited the diluted process, using solvent identical with polymerization reaction solvent for use into
Row dilution.
In the present invention, the viscosity of the polymer solution is preferably 0.40~0.80dL g-1, more preferably 0.50dL
g-1。
Preparation method provided by the invention makes polymerization reaction in phase transfer catalysis system using specific compound base catalyst
Lower progress, so that the generation for reducing (or part inhibits) cyclic oligomer during the reaction is realized, to reduce it in polymer
Content in solution.
After obtaining the polymer solution, the present invention crushes after obtained polymer solution is entered water cure, then successively passes through
Washing, vacuum drying and granulation, obtain polysulfones resinoid.In the present invention, it is described enter water cure before it is also preferable to include:
The polymer solution is cooled down；The temperature of the cooling is preferably 20 DEG C~30 DEG C, more preferably 25 DEG C.
The present invention to it is described enter water cure and crushing process be not particularly limited, use is well known to those skilled in the art
Technical solution.In the present invention, the purpose of the washing is desalination, and it is not specifically limited to this by the present invention.
In the present invention, the vacuum drying temperature is preferably 100 DEG C~150 DEG C, more preferably 120 DEG C；It is described true
The sky dry time is preferably 20h~30h, more preferably for 24 hours.
The present invention is not particularly limited the process of the granulation, is using technical solution well known to those skilled in the art
It can.
The polymer solution that the present invention obtains is not necessarily to can be obtained lower cyclic oligomer through additional organic solvent purifying
The polysulfones resinoid of content；Meanwhile preparation method provided by the invention avoids complicated organic solvent purifying process, simplifies system
Standby technique.
The present invention provides a kind of preparation methods of polysulfones resinoid, comprising the following steps: a) by biphenol monomer, at salt
Agent, compound base catalyst and double halogen monomers carry out polycondensation reaction in a solvent, obtain polymer solution；The compound base catalyst
Contain structure shown in formula (I) or formula (II)；Wherein ,-R1Selected from-CH3Or phenyl；-R2Selected from-CH3、-CH2CH3Or isopropyl；-
R3Selected from-CH3、-CH2CH3；B) it is crushed after the obtained polymer solution of step a) being entered water cure, then successively through washing, vacuum
Dry and granulation, obtains polysulfones resinoid.Compared with prior art, preparation method provided by the invention is using specific compound alkali
Catalyst carries out polymerization reaction under phase transfer catalysis system, reduces (or part inhibits) during the reaction to realize
The generation of cyclic oligomer, to reduce its content in a polymer solution, so that the polymer solution made is not necessarily to through volume
Outer organic solvent purifying can be obtained the polysulfones resinoid of lower cyclic oligomer levels；Meanwhile preparation provided by the invention
Method avoids complicated organic solvent purifying process, simplifies preparation process.The experimental results showed that preparation side provided by the invention
Two cyclic oligomer contents of the polysulfones resinoid that method is prepared can reduce to 1.06%, and cyclic oligomer total content can drop
Down to 3.51%.
In addition, preparation method provided by the invention have extensive adaptability, can in conjunction with one-step synthesis, two steps synthesis and
Nothing divides the different types of polysulfones resinoids such as the preparation of the techniques such as water PPSU, PES and PSU.
In order to further illustrate the present invention, it is described in detail below by following embodiment.Following embodiment of the present invention
The structural formula of the compound base catalyst of PTC1 used is referring to shown in formula (I-1)；
Preparation method specifically:
Under ice bath, to bromoethane is added in 1,8- diazabicylo, 11 carbon -7- alkene (DBU), it is stirred to react at room temperature
Then 5h is filtered；It is washed for several times with ethyl acetate and ether respectively, obtains white solid, then exchanged and set through alkali ion again
Rouge obtains corresponding hydroxyl form, and yield is greater than 95%；Through nuclear magnetic resonance spectroscopy, to turn out to be target product PTC1 compound for carbon spectrum
Base catalyst, nuclear magnetic resonance spectroscopy, carbon spectrum are referring to shown in Fig. 1~2.
The structural formula of the compound base catalyst of PTC2 used in following embodiment of the present invention is referring to shown in formula (I-2)；
Preparation method specifically:
Under ice bath, to cylite is added in 1,8- diazabicylo, 11 carbon -7- alkene (DBU), it is stirred to react at room temperature
Then 5h is filtered；It is washed for several times with ethyl acetate and ether respectively, obtains white solid, then exchanged and set through alkali ion again
Rouge obtains corresponding hydroxyl form, and yield is greater than 95%；Through nuclear magnetic resonance spectroscopy, to turn out to be target product PTC2 compound for carbon spectrum
Base catalyst, nuclear magnetic resonance spectroscopy, carbon spectrum are referring to shown in Fig. 3~4.
The reaction equation of the compound base catalyst of the PTC1 and the compound base catalyst of PTC2 is referring to shown in formula (IV)；
The structural formula of the compound base catalyst of PTC3 used in following embodiment of the present invention is referring to shown in formula (II-1)；
The structural formula of the compound base catalyst of PTC4 used is referring to shown in formula (II-2)；
The structural formula of the compound base catalyst of PTC5 used is referring to shown in formula (II-3)；
The structural formula of the compound base catalyst of PTC6 used is referring to shown in formula (II-4)；
The preparation method of the above-mentioned compound base catalyst in PTC3~6 is referring to document TetrahedronLett., and 1989,30,
1927；J.Org.Chem.,2007,72,4067；J.Membr.Sci., 2017,537,151, using tetraethyl urea or five alkyl
The preparation of the raw materials such as guanidine；The compound base catalyst in target product PTC3~6 is turned out to be through nuclear magnetic resonance spectroscopy, carbon spectrum, referring to Fig. 5~12
It is shown.
Quaternary ammonium salt catalyst used in comparative example of the present invention is commercially available.
The test method of cyclic oligomer in following embodiment of the present invention specifically:
Experiment carries out in Waters-GPC volume exclusion (SEC) chromatographic column, is first dissolved in the polysulfones resinoid of preparation
In the THF of chromatographically pure, 20 μ L (concentration 0.4wt%) is taken to inject chromatographic column；Flow rate of mobile phase: 1.0mL/min；Detector: UV
254；Column temperature: 30 DEG C；The calculation method of cyclic oligomer content use method for normalizing: the corresponding peak area of two cyclic oligomers with
Polymer and the ratio of cyclic oligomer peak area summation are the percentage composition of two cyclic oligomers；Similarly, cyclic oligomer peak
Area and polymer and the ratio of cyclic oligomer peak area summation are the percentage composition of cyclic oligomer.
Embodiment 1
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.25mol PTC1, are warming up to 140 DEG C, and water is divided to react 6h；Water is divided to terminate
Afterwards, the 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until poly-
It closes viscosity and reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 1 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.31%, cyclic oligomer total content is 3.65%.
Embodiment 2
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.25mol PTC2, are warming up to 140 DEG C, and water is divided to react 6h；Water is divided to terminate
Afterwards, the 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until poly-
It closes viscosity and reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 2 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.25%, cyclic oligomer total content is 3.68%.
Embodiment 3
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, adding 11.222kg mass fraction is 50%
KOH (100mol) aqueous solution and the compound base catalyst of 0.25mol PTC3, are warming up to 140 DEG C, and water is divided to react 6h；Water is divided to terminate
Afterwards, the 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until poly-
It closes viscosity and reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 3 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.31%, cyclic oligomer total content is 4.41%.
Embodiment 4
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.25molPTC4, are warming up to 140 DEG C, and water is divided to react 6h；After dividing water,
The 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until polymerization
Viscosity reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 4 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.13%, cyclic oligomer total content is 3.70%.
Embodiment 5
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.25molPTC5, are warming up to 140 DEG C, and water is divided to react 6h；After dividing water,
The 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until polymerization
Viscosity reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 5 provides obtains polysulfones, infrared spectrogram and hydrogen nuclear magnetic resonance
Spectrogram is referring to shown in Figure 13~14；The gel chromatography figure ginseng for the polysulfones that the preparation method that the embodiment of the present invention 5 provides is prepared
As shown in Figure 15, peak comprehensive statistics is referring to table 1~2；It follows that two cyclic oligomer contents of polymer are 1.06%, it is cyclic annular
Oligomer total content is 3.51%.
1 comprehensive statistics of peak in the gel chromatography figure for the polysulfones that the preparation method that 1 embodiment of the present invention 5 of table provides is prepared
| Title | Retention time (minute) | Area (microvolt * seconds) | % area | Highly (microvolt) | |
| 1 | Peak 1 | 12.579 | 61670561 | 98.94 | 330517 |
| Mean | 12.579 | 61670561.467 | 330516.821 |
2 comprehensive statistics of peak in the gel chromatography figure for the polysulfones that the preparation method that 2 embodiment of the present invention 5 of table provides is prepared
| Title | Retention time (minute) | Area (microvolt * seconds) | % area | Highly (microvolt) | |
| 1 | Peak 2 | 19.865 | 660921 | 1.06 | 24430 |
| Mean | 19.865 | 660921.144 | 24429.666 |
Embodiment 6
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.25molPTC6, are warming up to 140 DEG C, and water is divided to react 6h；After dividing water,
The 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until polymerization
Viscosity reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 6 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.24%, cyclic oligomer total content is 4.43%.
Embodiment 7
(1) 50L DMSO is injected in 100L reaction kettle, then under nitrogen protection and stirring condition, is added into reaction kettle
Enter 11.451kg bisphenol-A (50mol), be warming up to 80 DEG C, after it is completely dissolved, it is 50% that 11.222kg mass fraction, which is added,
KOH (100mol) aqueous solution and the compound base catalyst of 0.1molPTC5, are warming up to 140 DEG C, and water is divided to react 6h；After dividing water,
The 14.358kg4 being dissolved in toluene is added, 4 '-dichloro diphenyl sulfones (50mol) are warming up to 160 DEG C of 1~3h of reaction, until polymerization
Viscosity reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 7 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.19%, cyclic oligomer total content is 3.96%.
Embodiment 8
(1) by 50L DMAc inject 100L reaction kettle in, then under nitrogen protection and stirring condition, into reaction kettle according to
Secondary addition 11.451kg bisphenol-A (50mol), 14.358kg 4,4 '-dichloro diphenyl sulfone (50mol), 14.51kg anhydrous K2CO3
(105mol) and the compound base catalyst of 0.25molPTC5, is warming up to 140 DEG C, and water is divided to react 6h；After dividing water, it is warming up to 160
DEG C reaction 3~6h, until polymeric viscosity reaches 0.40~0.80dL g-1Stop reaction, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 8 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.34%, cyclic oligomer total content is 3.97%.
Embodiment 9
(1) by 50L DMAc inject 100L reaction kettle in, then under nitrogen protection and stirring condition, into reaction kettle according to
Secondary addition 11.451kg bisphenol-A (50mol), 14.358kg 4,4 '-dichloro diphenyl sulfone (50mol), 25.472kg anhydrous K3PO4
(120mol) and the compound base catalyst of 0.25molPTC4 is directly warming up to 160 DEG C of 3~6h of reaction, until polymeric viscosity reaches 0.40
~0.80dL g-1Stop reaction, is diluted using DMAc, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 9 provides obtains polysulfones, and two cyclic oligomer contents of polymer
It is 1.63%, cyclic oligomer total content is 4.31%.
Embodiment 10
(1) by 50L DMAc inject 100L reaction kettle in, then under nitrogen protection and stirring condition, into reaction kettle according to
Secondary addition 11.451kg bisphenol-A (50mol), 14.358kg 4,4 '-dichloro diphenyl sulfone (50mol), 25.472kg anhydrous K3PO4
(120mol) and the compound base catalyst of 0.25molPTC5 is directly warming up to 160 DEG C of 3~6h of reaction, until polymeric viscosity reaches 0.40
~0.80dL g-1Stop reaction, is diluted using DMAc, obtains polymer solution.
(2) reaction system is cooled to room temperature, and the polymer solution that step (1) obtains is entered into water cure, is crushed, obtained
The fluoropolymer resin of white powder；Again through water-washing desalting, vacuum drying (120 DEG C, for 24 hours), finally it is granulated, obtains target
Product.
Through detecting, the preparation method that the embodiment of the present invention 10 provides obtains polysulfones, and two cyclic oligomers of polymer contain
Amount is 1.55%, and cyclic oligomer total content is 4.29%.
Comparative example 1
The preparation method provided using embodiment 1, difference are: the compound base catalyst of PTC1 is not added.
Through detecting, the preparation method that comparative example 1 provides obtains polysulfones, and gel chromatography figure is shown in Figure 16, and peak is comprehensive
Statistics is closed referring to table 3~4；It follows that two cyclic oligomer contents of polymer are 1.32%, cyclic oligomer total content is
4.58%.
1 comprehensive statistics of peak in the gel chromatography figure for the polysulfones that the preparation method that 3 comparative example 1 of table provides is prepared
| Title | Retention time (minute) | Area (microvolt * seconds) | % area | Highly (microvolt) | |
| 1 | Peak 1 | 12.054 | 61752463 | 98.68 | 350115 |
| Mean | 12.054 | 61752463.425 | 350114.674 |
2 comprehensive statistics of peak in the gel chromatography figure for the polysulfones that the preparation method that 4 comparative example 1 of table provides is prepared
| Title | Retention time (minute) | Area (microvolt * seconds) | % area | Highly (microvolt) | |
| 1 | Peak 2 | 19.992 | 825130 | 1.32 | 29502 |
| Mean | 19.992 | 825129.575 | 29502.496 |
Comparative example 2
The preparation method provided using embodiment 1, difference are: being replaced using 0.25mol benzyltrimethylammonium chloride
The compound base catalyst of 0.25molPTC1.
Through detecting, the preparation method that comparative example 2 provides obtains polysulfones, and two cyclic oligomer contents of polymer are
1.49%, cyclic oligomer total content is 5.32%.
Comparative example 3
The preparation method provided using embodiment 1, difference are: using 0.25mol dodecyl trimethyl ammonium chloride generation
For the compound base catalyst of 0.25molPTC1.
Through detecting, the preparation method that comparative example 3 provides obtains polysulfones, and two cyclic oligomer contents of polymer are
1.59%, cyclic oligomer total content is 4.69%.
Comparative example 4
The preparation method provided using embodiment 1, difference are: being replaced using 0.25mol tetrabutylammonium bromide
The compound base catalyst of 0.25molPTC1.
Through detecting, the preparation method that comparative example 4 provides obtains polysulfones, and two cyclic oligomer contents of polymer are
1.46%, cyclic oligomer total content is 4.86%.
Comparative example 5
The preparation method provided using embodiment 8, difference are: the compound base catalyst of PTC5 is not added.
Through detecting, the preparation method that comparative example 5 provides obtains polysulfones, and two cyclic oligomer contents of polymer are
1.57%, cyclic oligomer total content is 4.71%.
Comparative example 6
The preparation method provided using embodiment 9, difference are: the compound base catalyst of PTC4 is not added.
Through detecting, the preparation method that comparative example 6 provides obtains polysulfones, and two cyclic oligomer contents of polymer are
1.98%, cyclic oligomer total content is 5.09%.
The above description of the disclosed embodiments, enables those skilled in the art to implement or use the present invention.It is right
A variety of modifications of these embodiments will be readily apparent to those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with the principles and novel features disclosed herein
Widest scope.
Claims (10)
1. a kind of preparation method of polysulfones resinoid, comprising the following steps:
A) biphenol monomer, salt forming agent, compound base catalyst and double halogen monomers are subjected to polymerization reaction in a solvent, obtain polymer
Solution；The compound base catalyst contains structure shown in formula (I) or formula (II)；
Wherein ,-R1Selected from-CH3Or-R2Selected from-CH3、-CH2CH3Or-R3Selected from-CH3、-
CH2CH3；
B) it crushes after the obtained polymer solution of step a) being entered water cure, then is successively obtained through washing, vacuum drying and granulation
Polysulfones resinoid.
2. preparation method according to claim 1, which is characterized in that biphenol monomer described in step a) is selected from bisphenol-A, double
Phenol S or 4,4 '-'-biphenyl diphenol.
3. preparation method according to claim 1, which is characterized in that salt forming agent described in step a) be selected from NaOH, KOH,
K2CO3And K3PO4One of or it is a variety of.
4. preparation method according to claim 1, which is characterized in that the dosage of compound base catalyst described in step a) is
The 0.1%~3% of biphenol monomer mole.
5. preparation method according to claim 1, which is characterized in that double halogen monomers described in step a) are selected from 4,4 '-two
Chloro-diphenyl sulfone, 4,4 '-tetrafluoro diphenyl sulphone (DPS)s or 4,4 '-difluoro benzophenones.
6. preparation method according to claim 1, which is characterized in that biphenol monomer described in step a), salt forming agent and double
The molar ratio of halogen monomer is 1:(2~3): (0.8~1.2).
7. preparation method according to claim 1, which is characterized in that the temperature of polymerization reaction described in step a) is 70 DEG C
~220 DEG C, the time is 1h~15h.
8. preparation method according to claim 1, which is characterized in that the process of polymerization reaction described in step a) is specific
Are as follows:
In a solvent by biphenol monomer dissolution, after addition salt forming agent and compound base catalyst carry out point water reaction, double halogen are added
Monomer heating, carries out first polycondensation reaction, obtains polymer solution；
Or sequentially added after biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst carry out the reaction of point water in a solvent, it rises
Temperature carries out the second polycondensation reaction, obtains polymer solution；
Or after sequentially adding biphenol monomer, double halogen monomers, salt forming agent and compound base catalyst in a solvent, heating carries out third
Polycondensation reaction obtains polymer solution after dilution.
9. preparation method according to claim 8, which is characterized in that the temperature for dividing water to react is 110 DEG C~150
DEG C, the time is 5h~7h.
10. preparation method according to claim 1, which is characterized in that vacuum drying temperature described in step b) is 100
DEG C~150 DEG C, the time is 20h~30h.
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