CN118271618A - Method for preparing polyarylsulfone ether based on double-end capping method - Google Patents
Method for preparing polyarylsulfone ether based on double-end capping method Download PDFInfo
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 57
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000003518 caustics Substances 0.000 claims abstract description 18
- 238000012643 polycondensation polymerization Methods 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 16
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 125000005843 halogen group Chemical group 0.000 claims abstract description 9
- 125000005362 aryl sulfone group Chemical group 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 12
- 238000006068 polycondensation reaction Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- -1 alkali metal salt Chemical class 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000005755 formation reaction Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 150000003457 sulfones Chemical class 0.000 claims description 3
- 229910000025 caesium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000000243 solution Substances 0.000 description 49
- 229920000642 polymer Polymers 0.000 description 32
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 15
- 239000004033 plastic Substances 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 15
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 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 description 9
- 229920000491 Polyphenylsulfone Polymers 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 238000010998 test method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 230000000379 polymerizing effect Effects 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229940050176 methyl chloride Drugs 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- 238000004483 ATR-FTIR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- NYKRSGJRIJJRRK-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)sulfonylbenzene Chemical class ClC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1Cl NYKRSGJRIJJRRK-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- OUKZUIOFTUUCEN-UHFFFAOYSA-N 7$l^{6}-thiabicyclo[4.1.0]hepta-1,3,5-triene 7,7-dioxide Chemical class C1=CC=C2S(=O)(=O)C2=C1 OUKZUIOFTUUCEN-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002490 poly(thioether-sulfone) polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Abstract
The invention relates to a method for preparing polyarylsulfone ether based on a double-end capping method, which takes difunctional phenol and difunctional halogenated aryl sulfone as raw materials, and carries out condensation polymerization reaction in an organic solvent and in the presence of inorganic caustic alkali or inorganic caustic salt to prepare the polyarylsulfone ether. After the molecular weight of the polyarylsulfone ether reaches a preset value, adding a halogen-eliminating phenol metal end-capping agent into a polymerization system, removing the end group of halogen atoms on one hand, and controlling the distribution of the molecular weight of the polymerization on the other hand; after the condensation polymerization reaches the preset molecular weight, a high-activity phenol metal-removing aromatic end-capping agent is added into the polymerization system to remove the phenol metal end groups, terminate the condensation polymerization reaction, and not only lead the polyarylsulfone ether to have aromatic end groups but also contain necessary functional groups in the end capping process. The obtained polyarylsulfone ether has excellent comprehensive performance and also has the subsequent application field, and the requirements of different application scenes on the polyarylsulfone ether can be met through the end capping reaction by adopting the end capping agent containing corresponding functional groups.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a method for preparing polyarylsulfone ether based on a double-end capping method.
Background
The polyarylsulfone ether plastics are amorphous aromatic thermoplastic high molecular plastics which are formed by linking the 2 types of structures, wherein the aromatic sulfone bonds (-SO 2 -) and aromatic ether bonds are contained in the high molecular repeating unit structure. Commercially valuable polyarylsulfone ether plastics mainly include polysulfone (abbreviated PSF, PSU, PSO and the like hereinafter, PSU for polysulfone), polyethersulfone (abbreviated PES) polyphenylsulfone (abbreviated PPSF, PPSU, PPSO and the like hereinafter, PPSU for polyphenylsulfone), polythioether sulfone (abbreviated PTES) and the like.
The sulfone bond and the ether bond in the polyarylsulfone ether endow the polymer with toughness, transparency and high heat resistance. The sulfone bond on the main chain of the aromatic ring makes the polyarylsulfone ether possess rigidity and hardness, while the structure of the continuous aromatic ring makes them possess high-temperature oxidation resistance; on the other hand, the presence of flexible ether bonds in the main chain gives them toughness and impact resistance. The heat distortion temperature is 174-221 ℃, the continuous use temperature is 160-190 ℃, and the continuous use temperature of special varieties is up to 205 ℃ or more. This class of plastics also has intrinsic flame retardant properties and even when burned, gives up very little smoke. In addition, the plastics have high chemical resistance and can meet the severe safety requirements. The polyarylsulfone ether plastic is a special engineering plastic with high thermal stability, good transparency, excellent hydrolytic stability, low molding shrinkage, good biocompatibility, moderate electrical property and mechanical property and excellent resistance to acid, alkali, alcohol, aliphatic hydrocarbon and salt solution, and can be completely compared with high-quality engineering plastics such as polyether ether ketone (PEEK), polyether ketone (PEKK) and the like. Especially, the application of the polyarylsulfone ether plastic in the fields of sea water desalination, ultra-pure water filtration in the IC field, membrane separation of artificial kidneys and the like is unique, and the application value of the polyarylsulfone ether plastic is more remarkable.
However, the preparation of polyarylsulfone ether has a certain technical difficulty, which restricts the industrial application.
For example, when an ultrafiltration membrane is prepared using a polyarylsulfone ether, the most commonly used technique is a solution film-forming method, which requires dissolving a polyarylsulfone ether plastic in a solvent such as Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), etc., and then forming the membrane. This requires that the solution of the polyarylsulfone ether plastic be very clear, transparent, stable throughout the processing cycle. Unfortunately, in the prior art, a considerable number of products have failed to meet this requirement. In addition, since the synthesis of polyarylsulfone ether plastics basically adopts a condensation polymerization method that halogen is combined with phenol metal and removed, one end group of a molecular chain always retains halogen, which is extremely disadvantageous for the use of the plastics in a biological filtration membrane. In addition, the molecular weight distribution of the condensation polymerization process is also difficult to control, so that it is difficult to ensure both sufficient strength of the film and flowability during processing of the film and sufficient ductility of the resulting film. In addition, during the synthesis of the polyarylsulfone ether plastic, the phenol metal is also a main functional group of polycondensation, so that a large amount of phenol metal atoms are inevitably remained at the terminal of the molecular chain of the polyarylsulfone ether, which seriously hinders the application of the polyarylsulfone ether film in the field of ultra-pure water filtration of IC industry. In addition, some applications in the field of membrane separation, which require both maintaining the intrinsic properties of the polyarylsulfone ether and the stability in solution, and also require different permeabilities to certain substances for different applications, require some modification of the structure of the polyarylsulfone ether molecule, which have problems that are naturally also of interest to the scientific and industrial community and are in an effort to change this state of the art.
For example, chinese patent CN 116218220a discloses a polyphenylsulfone composition comprising, in parts by weight: 95-99 parts of polyphenylsulfone resin; 0.1-5 parts of polyaramide liquid crystal polymer; 0.05-0.3 part of acid absorber; wherein, the polyphenylsulfone resin comprises the following monomers and the derivatives of the same kind according to mole percent: 10-35mol% of 4,4' -biphenol; 15-40mol% of bisphenol monomer containing amide groups; 45-55mol% of 4,4' -dichloro diphenyl sulfone. The main innovation of the scheme is that 0.1-5 parts of polyaramid liquid crystal polymer is added into polymerized monomer to carry out copolymerization so as to increase the hydrophilic property of polyphenylsulfone, and 0.15% parts of acid absorber is added so as to simplify the polycondensation process. However, there is no clear contribution to the formation of clear, transparent, stable polyarylsulfone ether plastic solutions, as well as to the control of molecular weight distribution and elimination of phenolic metal residues.
Chinese patent CN 116589680A discloses a method for preparing an aromatic polymer, which comprises performing polycondensation reaction of halogenated monomer and second monomer in the presence of alkali, solvent and water absorbent, wherein the second monomer comprises phenol monomer, thiophenol monomer or amine monomer, the main innovation of the scheme is that the monomer is not limited to phenol group only, and thiophenol group or amine group can be adopted at the same time; also, not limited to the use of dichlorobenzene sulfone, various types of chlorophenyl sulfones may be used, and even fluorinated phenylene sulfones may be used. In addition, a water absorbing agent is added during the reaction. The water absorbent is considered to be cheap and easy to obtain, is used for absorbing water generated in the polymerization reaction process, does not need to add a water diversion agent or a water diversion process, and reduces insoluble solid content, so that the synthesis of the series of aromatic polymers with low cost and high efficiency can be realized. However, this approach also does not clearly contribute to the formation of clear, transparent, stable polyarylsulfone ether plastic solutions, and to how to control the molecular weight distribution and eliminate the phenol metal residue.
In addition, in terms of the end capping technique, li Shengzhu and Wu Cunlei are disclosed in the description of sulfone polymers and their applications, which uses methyl chloride to cap the end groups. However, since the boiling point of chloromethane is far lower than the temperature of polycondensation reaction, most chloromethane is inevitably emitted into the gas phase in the polymerization process, and the chloromethane has no end-sealing effect and can cause environmental pollution due to escaping into the air.
Disclosure of Invention
The invention aims to overcome the defects of the prior polyarylsulfone ether preparation technology and provides a method for preparing the polyarylsulfone ether based on a double-end capping method.
The scheme of the application adopts the halogen-eliminating phenol metal end-capping agent to be added into the system when the polycondensation reaction reaches a preset stage, so that not only can the end groups of halogen atoms which are not suitable for some application occasions be eliminated, but also the molecular weight distribution of the polyarylsulfone ether can be controlled according to the needs, so that the polyarylsulfone ether not only meets the requirements on strength, but also can ensure the fluidity in the processing process and the requirement on sufficient ductility after being made into a film.
In addition, after the condensation polymerization reaches the preset molecular weight, the scheme of the application adopts the high-activity phenol metal-removing aromatic end-capping agent to terminate the polymerization reaction, so that the polymerization reaction can be quickly terminated, the pollution caused by the fact that the low-boiling end-capping agent is discharged into the air is avoided, the heat resistance of the polyarylsulfone ether is not influenced by the end capping of the aryl, and the phenol metal end group with an undesirable metal atom is removed. More prominently, the stability of the solution can be further improved according to different solvents used when the ultrafiltration membrane is prepared from the polyarylsulfone ether, and the selective permeability of certain substances is realized through the functional groups contained in the high-activity dephenolization metal aromatic end-capping agent according to different application fields, so that the application range of the ultrafiltration membrane prepared from the polyarylsulfone ether is wider.
The aim of the invention can be achieved by the following technical scheme:
The invention provides a method for preparing polyarylsulfone ether based on a double-end capping method, which comprises the following steps:
s1, salifying and polycondensing: taking difunctional phenol and difunctional halogenated aryl sulfone as raw materials, carrying out condensation polymerization reaction in an organic solvent in the presence of inorganic caustic alkali or inorganic caustic salt, wherein the inorganic caustic alkali or inorganic caustic salt firstly reacts with the difunctional phenol to generate phenolate, then reacts with halogen atoms to remove halogenated alkali metal salt, and forming polycondensation product polyarylsulfone ether;
S2, controlling the molecular weight distribution of the polyarylsulfone ether: after the molecular weight of the polyarylsulfone ether reaches a preset value, adding a halogen-eliminating phenol metal end-capping agent into a polymerization system, gradually removing the end group of halogen atoms through reaction, so that the only remaining end of the end-capped molecular chain can carry out chain growth reaction, and the two ends of the molecular chain which is not end-capped can still bidirectionally continue the chain growth reaction, thereby realizing control on the distribution of the molecular weight of the polymerization through the sequence before and after end capping;
S3, terminating condensation polymerization reaction: after the condensation polymerization reaches the preset molecular weight, a high-activity phenol-removing metal aromatic end-capping agent is added into the polymerization system to remove the phenol metal end groups, and the condensation polymerization reaction is terminated, so that the polyarylsulfone ether has aromatic end groups and contains necessary functional groups, namely, the high-activity phenol-removing metal aromatic end-capping agent is adopted, and the polyarylsulfone ether has corresponding functional groups through a simple end-capping reaction.
In one embodiment of the invention, the amount of difunctional phenol used in relation to difunctional haloaryl sulfone is: the molar ratio of phenol to halogen is (0.8-1.1): 1, preferably, the molar ratio of phenol to halogen is 1:1.
In one embodiment of the invention, the difunctional phenol is selected from the group consisting of one or more of the following structural formulas:
In one embodiment of the invention, the difunctional haloaryl sulfone is selected from the group consisting of one or more of the following structural formulas:
in one embodiment of the invention, the number of equivalents of inorganic caustic or inorganic caustic salt is 1 to 1.5 times the number of phenol equivalents.
In one embodiment of the invention, the inorganic caustic or inorganic caustic salt is selected from one or a combination of several of the following:
LiOH、NaOH、KOH、CsOH、Na2O、Na2CO3、K2CO3、Cs2CO3、NaHCO3、KHCO3、CsHCO3、Li3PO4、Na3PO4、K3PO4、Cs3PO4、Na2HPO4、Cs2HPO4 Or K 2HPO4.
In one embodiment of the invention, the organic solvent is selected from one or a combination of several of the following: dimethylformamide, dimethylacetamide, dimethylsulfoxide, sulfolane, N-methylpyrrolidone, cyclohexanone.
In one embodiment of the invention, the theoretical amount of the halogen-removing phenol metal type end-capping agent and the high-activity phenol-removing metal aromatic end-capping agent are shown as the formula (1)
Wherein: w is the dosage of the end-capping agent, and the unit is weight unit, and can be one of gram, kilogram, ton and the like; m is the molecular weight of the polyarylsulfone ether; v is the mass of the theoretical repeating unit of the polyarylsulfone ether; n is the number of theoretical repeating unit structures converted from the raw materials of the difunctional phenol and the difunctional sulfone; q is the sum of the masses of the added functional groups after the two ends of the polyarylsulfone ether are completely blocked; c is the molar mass of the end-capping agent. M, V, Q, C must all be the same as W, which means that when W is in grams, the molecular weight of the polyarylsulfone ether must be in grams, and so on.
In one embodiment of the present invention, the halogen-eliminating phenol metal blocking agent is selected from one or more of the following structural formulas:
In one embodiment of the present invention, the highly reactive dephenolization metal aromatic endcapping agent is selected from one or more of the following structural formulas: wherein n is a natural number from 0 to 16:
In one embodiment of the present invention, during the salt formation and polycondensation reaction in step S1, gas phase protection is performed by using inert gases such as Ar and N 2.
In one embodiment of the present invention, during the salt formation and polycondensation reaction of step S1, water, a reaction byproduct, and an alkali metal halide salt are simultaneously removed to gradually increase the molecular weight of the polyarylsulfone ether. In the salt forming and polycondensation reaction process of the step S1, water and halogenated alkali metal salt are formed through the end groups of 2 molecules, and after the reaction byproducts are removed, the rest parts are bonded with each other to form macromolecules.
In one embodiment of the present invention, in step S2 and step S3, the method for determining whether the molecular weight of the polyarylsulfone ether reaches a predetermined value is as follows: and continuously sampling in the polymerization process, testing the viscosity of the obtained sample in a fixed solvent and concentration, and determining the molecular weight of the polyarylsulfone ether according to the viscosity.
Compared with the prior art, the invention has the advantages and beneficial effects that:
1) Since the synthesis of polyarylsulfone ethers is basically a condensation polymerization method in which one halogen atom of a bifunctional halogen-containing aryl sulfone is bonded to one phenol metal atom of a bifunctional phenol metal and removed, and the removed molecular chains are bonded to each other, one end group of the molecular chain still retains one halogen atom, which is extremely disadvantageous for use as a biological filtration membrane. In addition, the molecular weight distribution of the condensation polymerization process is difficult to control, so that it is difficult to ensure both sufficient strength and process flowability and sufficient ductility of the article or film. The classical synthesis method is left at the discretion of the halogen atoms left at one end of the polyarylsulfone ether chain and is also uncontrollable with respect to the molecular weight distribution during the condensation polymerization. When the polymerization reaches the preset molecular weight, the halogen-eliminating phenol metal end-capping agent for removing the end groups of the aryl halogen is added, so that the end groups of the halogen are gradually removed; on the other hand, the molecular chain losing the halogen end group only leaves the other end to carry out chain growth reaction, and the molecular chain which is not blocked can still carry out bidirectional continuous chain growth reaction at the two ends, so that the requirement of expanding molecular weight distribution is realized;
2) In the synthesis process of the polyarylsulfone ether, besides eliminating and blocking the halogen, the other end group is the functional group of the phenol metal, so that a great amount of phenol metal is inevitably remained at the molecular chain terminal of the polyarylsulfone ether. This severely hampers the use of polyarylsulfone ether membranes in the field of ultra-pure water filtration in the IC field and can lead to the occurrence of solution instability in the film making process. In the classical synthesis method, methyl chloride is used for end capping, but the boiling point of methyl chloride is far lower than the polymerization temperature, so that the methyl chloride inevitably escapes into the weather, the utilization rate is very low, the metering is impossible, and the toxic gases pollute the environment. The technical scheme provided by the application adopts the high-activity dephenolization metal aromatic end-capping agent with the boiling point higher than the polymerization temperature, so that the utilization rate is high, the metering can be precisely carried out, and the environmental pollution is avoided. On the one hand, the aromatic end group is beneficial to improving the heat-resistant stability of the polyarylsulfone ether, and on the other hand, the corresponding functional group can be bonded according to the requirement of an application scene;
3) In the application field of the polyarylsulfone ether membrane separation, firstly, the film preparation solution is required to be stable, secondly, not only the intrinsic performance of the polyarylsulfone ether is required to be ensured, but also the permeability with different selectivity to certain substances is required to be aimed at different application occasions, and then the molecular structure of the polyarylsulfone ether is required to be modified. For example, for certain applications, it is desirable to increase hydrophilicity, carbophilicity, amidphilicity, etc. In the classical polymerization technique, the copolymerization is usually carried out by adding other monomers, which often changes the intrinsic properties of the polyarylsulfone ether and does not have the effect of activating the higher end groups. The scheme of the application is as described in the above 2, and the high-activity phenol metal-removing aromatic end-capping agent containing corresponding functional groups is adopted, so that the required preset target can be achieved through a simple end-capping reaction while the phenol metal is removed.
Drawings
FIG. 1 is an FTIR ATR infrared spectrum of the polyarylsulfone ether pellets of comparative example 2;
FIG. 2 is a GPC curve of the molecular weight and distribution of polyarylsulfone ether pellets in comparative example 2.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Comparative example 1:
20 mol of biphenol, 24 mol of sodium carbonate, 20.05 mol of dichlorodiphenyl sulfone and 27.5L of N-methylpyrrolidone as a solvent were added one by one into a 50L pilot reactor equipped with a rectifying device, while a stirrer was turned on, the rotation speed was set to 100r/min, and pure nitrogen was introduced for gas phase protection. Then, a heater for circulating heat conducting oil in the jacket of the reaction kettle is started to gradually increase the temperature. And when the temperature reaches 180 ℃, maintaining for 2 hours, and completing the salification reaction. Then heating to 203 ℃, maintaining the reflux ratio R=1.1 of the rectifying device, and polymerizing while removing the water of the byproducts, and continuously reacting for 5-6h. Until the rotational viscosity of the melt in 25% (mass percent, the same applies below) dimethylacetamide solution at 40 ℃ reaches 3100 mPa.s (measured by a rotational viscosimeter, the same applies below), namely the molecular weight of the polyarylsulfone ether is controlled to reach a preset value, heating and stirring are stopped, and the polymerization system is allowed to stand and precipitate while naturally cooling down. After the system had been cooled to 120℃the temperature was maintained until the polymer solution precipitated out of the by-product salt, sodium chloride and the upper layer exhibited a clear solution, after which the upper clear polymer solution was separated off.
Concentrating the upper clear polymer solution, extracting part of solvent, circularly grinding the concentrated solution in deionized water to obtain a mixed solution of fine powder and water, centrifugally separating and filtering out water, and drying under reduced pressure at 170 ℃ by using a spiral-belt drier to obtain the polymer dry powder of the polyarylsulfone ether. Then atUnder the protection of an antioxidant, granulating by adopting a equidirectional parallel double-screw extruder with phi 35 and L/D=40 at the temperature of 150 ℃,200 ℃,225 ℃,250 ℃,260 ℃,270 ℃,280 ℃,290 ℃,300 ℃ and 300 ℃ to obtain the granules of the polyarylsulfone ether. The performance measurements are shown in Table 1.
Comparative example 2:
Similarly to comparative example 1, 20 moles of bisphenol A, 24 moles of potassium carbonate, 20.05 moles of dichlorodiphenyl sulfone, and 27.5L of N-dimethylacetamide as a solvent were added one by one to a 50L pilot reactor equipped with a rectifying apparatus while turning on a stirrer at a rotation speed set to 100r/min, and pure nitrogen was introduced for gas phase protection. Then, a heater for circulating heat conducting oil in the jacket of the reaction kettle is started to gradually increase the temperature. And when the temperature reaches 140 ℃, maintaining for 3 hours, and completing the salification reaction. Then heating to 165 ℃, maintaining the reflux ratio R=1.1 of the rectification device, and polymerizing while removing the water of the byproducts, and continuously reacting for 5-6h. Stopping heating and stirring until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40 ℃ reaches 2800 mPa.s, and allowing the polymer solution to stand and precipitate while naturally cooling the polymerization system. After the system had been cooled to 120℃the temperature was maintained until the polymer solution precipitated out of the by-product salt, potassium chloride and the upper layer exhibited a clear solution, after which the upper clear polymer solution was separated off.
And (3) pumping out part of solvent from the clear polymer solution at the upper layer, circularly grinding the concentrated solution in deionized water into a mixed solution of fine powder and water, centrifugally separating and filtering out water, and drying under reduced pressure at 170 ℃ by using a spiral-belt drier to obtain polymer dry powder of the polyarylsulfone ether. Then atUnder the protection of an antioxidant, granulating by adopting a equidirectional parallel double-screw extruder with phi 35 and L/D=40 at the temperature of 150 ℃,200 ℃,225 ℃,250 ℃,260 ℃,270 ℃,280 ℃,290 ℃,300 ℃ and 300 ℃ to obtain the granules of the polyarylsulfone ether. The performance measurements are shown in Table 1, and the FTIR ATR infrared spectra and GPC curves of the molecular weights and distributions are shown in FIGS. 1 and 2, respectively.
Example 1:
Similarly to comparative example 2, 20 moles of bisphenol A, 24 moles of potassium carbonate, 20.05 moles of dichlorodiphenyl sulfone, and 27.5L of N-dimethylacetamide as a solvent were added one by one to a 50L pilot reactor equipped with a rectifying apparatus while turning on a stirrer at a rotation speed set to 100r/min, and pure nitrogen was introduced for gas phase protection. Then, a heater for circulating heat conducting oil in the jacket of the reaction kettle is started to gradually increase the temperature. And when the temperature reaches 140 ℃, maintaining for 3 hours, and completing the salification reaction. Then heating to 165 ℃, maintaining the reflux ratio R=1.1 of the rectification device, and polymerizing while removing the water of the byproducts, and continuously reacting for 5-6h. Until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40℃reaches 2400 mPa.s, 25.31g of potassium phenoxide are added according to formula (1) and the reaction is continued for 2-3h. When the rotational viscosity of the melt in 25% dimethylacetamide solution at 40 ℃ reaches 2800 mPa.s, heating and stirring are stopped, and the polymer solution is allowed to stand and precipitate while the polymerization system is naturally cooled. After the system had been cooled to 120℃the temperature was maintained until the polymer solution precipitated out of the by-product salt, potassium chloride and the upper layer exhibited a clear solution, after which the upper clear polymer solution was separated off.
Concentrating the upper clear polymer solution, extracting part of solvent, circularly grinding the concentrated solution in deionized water to obtain a mixed solution of fine powder and water, centrifugally separating and filtering out water, and drying under reduced pressure at 170 ℃ by using a spiral-belt drier to obtain the polymer dry powder of the polyarylsulfone ether. Then atUnder the protection of an antioxidant, granulating by adopting a equidirectional parallel double-screw extruder with phi 35 and L/D=40 at the temperature of 150 ℃,200 ℃,225 ℃,250 ℃,260 ℃,270 ℃,280 ℃,290 ℃,300 ℃ and 300 ℃ to obtain the granules of the polyarylsulfone ether. The performance measurements are shown in Table 1.
Example 2:
Similarly to example 1, 20 moles of bisphenol A, 24 moles of potassium carbonate, 20.05 moles of dichlorodiphenyl sulfone, and 27.5L of N-dimethylacetamide as a solvent were added one by one to a 50L pilot reactor equipped with a rectifying apparatus while turning on a stirrer at a rotation speed of 100r/min, and pure nitrogen was introduced for gas phase protection. Then, a heater for circulating heat conducting oil in the jacket of the reaction kettle is started to gradually increase the temperature. And when the temperature reaches 140 ℃, maintaining for 3 hours, and completing the salification reaction. Then heating to 165 ℃, maintaining the reflux ratio R=1.1 of the rectification device, and polymerizing while removing the water of the byproducts, and continuously reacting for 4-6 hours. Until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40 ℃ reaches 2400, 25.31g of potassium phenoxide is added according to formula (1), and the reaction is continued for 2-3 hours. Until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40℃reaches 2800 mPa.s, 38.81g of biphenylbenzyl chloride was added to the reaction vessel in accordance with formula (1), and the reaction was continued for 2 hours. Then stopping heating and stirring, and allowing the polymer solution to stand and precipitate while naturally cooling the polymerization system. After the system had been cooled to 120℃the temperature was maintained until the polymer solution precipitated out of the by-product salt, potassium chloride and the upper layer exhibited a clear solution, after which the upper clear polymer solution was separated off.
Concentrating the upper clear polymer solution, extracting the solvent, circularly grinding the concentrated solution in deionized water into a mixed solution of fine powder and water, centrifugally separating and filtering out water, and drying under reduced pressure at 170 ℃ by using a spiral-link drier to obtain the polymer dry powder of the polyarylsulfone ether. Then at1790/Under the protection of 168 antioxidant, granulating by adopting a equidirectional parallel double-screw extruder with phi 35 and L/D=40 at the temperature of 150 ℃,200 ℃,225 ℃,250 ℃,260 ℃,270 ℃,280 ℃,290 ℃,300 ℃ and 300 ℃ to obtain the granules of the polyarylsulfone ether. The performance measurements are shown in Table 1.
Example 3:
Similarly to example 2, 18.4 mol of bisphenol A, 1.6 mol of N, 1-di-p-phenolformamide, 24 mol of potassium carbonate, 20.05 mol of dichlorodiphenyl sulfone, and 27.5L of N-dimethylacetamide as a solvent were added one by one to a 50L pilot reactor equipped with a rectifying apparatus while turning on a stirrer at a rotation speed of 100r/min and gas phase protection was performed by introducing pure nitrogen. Then, a heater for circulating heat conducting oil in the jacket of the reaction kettle is started to gradually increase the temperature. And when the temperature reaches 140 ℃, maintaining for 3 hours, and completing the salification reaction. Then heating to 165 ℃, maintaining the reflux ratio R=1.1 of the rectification device, and polymerizing while removing the water of the byproducts, and continuously reacting for 3-6h. Until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40℃reaches 2600 mPa.s, 25.31g of potassium phenoxide are added according to formula (1) and the reaction is continued for 2-3h. Until the rotational viscosity of the melt in 25% dimethylacetamide solution at 40 ℃ reaches 3000 mPa.s, 47.05g N-p-benzyl chloride, 1-phenylformamide are added into the reaction kettle according to formula (1), and the reaction is continued for 2h. Then stopping heating and stirring, and allowing the polymer solution to stand and precipitate while naturally cooling the polymerization system. After the system had been cooled to 120℃the temperature was maintained until the polymer solution precipitated out of the by-product salt, potassium chloride and the upper layer exhibited a clear solution, after which the upper clear polymer solution was separated off.
Concentrating the upper clear polymer solution, extracting the solvent, circularly grinding the concentrated solution in deionized water into a mixed solution of fine powder and water, centrifugally separating and filtering out water, and drying under reduced pressure at 170 ℃ by using a spiral-link drier to obtain the polymer dry powder of the polyarylsulfone ether. Then at1790/Under the protection of 168 antioxidant, granulating by adopting a equidirectional parallel double-screw extruder with phi 35 and L/D=40 at the temperature of 150 ℃,200 ℃,225 ℃,250 ℃,260 ℃,270 ℃,280 ℃,290 ℃,300 ℃ and 300 ℃ to obtain the granules of the polyarylsulfone ether. The performance measurements are shown in Table 1.
TABLE 1 Properties of pellets of the polyarylsulfone ethers of comparative examples, examples
In table 1, wherein: tensile properties: test methods refer to GB/T1040.2-2006 (type 1A); bending properties: the test method refers to GB/T9341-2008; impact strength: the test method refers to GB/T9341-2008; glass transition temperature: test methods refer to ASTM D3418-15; dielectric constant: test methods refer to ASTM D150-18; dielectric strength: test methods refer to ASTM D150-18; contact angle: test methods refer to GB/T30047-2013; metal content: atomic spectrometry; chlorine content: elemental analysis.
As can be seen from fig. 1,2 and table 1, the predetermined polyarylsulfone ether polymer can be obtained according to the method of the present invention, whether comparative or example. In particular, in the examples, not only the halogen content was reduced by several tens times after elimination and blocking of the halogen end groups, but also the molecular weight distribution was fully effectively enlarged by conducting the end-capping reaction at a predetermined degree of polymerization. Thereby greatly improving the breaking elongation of the resin and the ductility of the product. This is extremely advantageous for the use of polyarylsulfone ether polymers in the field of membrane filtration.
Secondly, the elimination and end capping of the phenolic metal end groups reduce the content of alkali metal by more than ten times, which is very favorable for the application of the polyarylsulfone ether membrane in the field of IC industry ultrapure water filtration.
Furthermore, by eliminating and blocking the phenolic metal end group, functional groups such as amido, hydroxyl or carbonyl are introduced, so that the polyarylsulfone ether membrane meets the requirement of filtering different compounds in various application fields. For example, in example 3, the reaction of eliminating the phenol metal caused by bonding the aromatic end group containing the amide group significantly improved the hydrophilicity, particularly the hydrophilicity, as compared with example 2. Therefore, the transmissivity of wastes such as urea and the like can be greatly improved in the application of the polyarylsulfone ether membrane in the renal dialysis membrane separation.
In addition, the pellets of the above examples and comparative examples were prepared as a relatively general 18% concentrated solution using dimethylformamide, which is most widely used in the film-forming process, and the time for which they remained clear, transparent and stable solutions was observed, and the results are shown in table 2.
Table 2 observations of stability after the pellets in examples and comparative examples were formulated into solutions
It can be clearly seen that the polyarylsulfone ether polymer with molecular weight and mechanical property meeting application requirements can be obtained by adopting the conventional synthesis method, but the requirements of the film making process are difficult to meet. However, by adopting the double-end capping technology in the invention, the requirement of the film preparation process on the standing period of the stable solution (see the example 3) can be met, the content of halogen and alkali metal in the polyarylsulfone ether can be greatly reduced, and the requirement of the application field on the molecular weight distribution of the polyarylsulfone ether polymer can be met according to different application occasions.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The method for preparing the polyarylsulfone ether based on the double-end capping method is characterized by comprising the following steps of:
S1, salifying and polycondensing: taking difunctional phenol and difunctional halogenated aryl sulfone as raw materials, carrying out condensation polymerization reaction in an organic solvent in the presence of inorganic caustic alkali or inorganic caustic salt, wherein the inorganic caustic alkali or inorganic caustic salt firstly reacts with the difunctional phenol to generate phenol metal salt, then reacts with halogen atoms to remove halogenated alkali metal salt, and forming polycondensation product polyarylsulfone ether;
S2, controlling the molecular weight distribution of the polyarylsulfone ether: after the molecular weight of the polyarylsulfone ether reaches a preset value, adding a halogen-eliminating phenol metal end-capping agent into a polymerization system, gradually removing the end group of halogen atoms through reaction, so that only the other end of the end-capped molecular chain can carry out chain growth reaction, and the two ends of the non-end-capped molecular chain can still bidirectionally continue the chain growth reaction, thereby realizing control on the distribution of the molecular weight of the polymerization through the sequence of end capping;
s3, terminating condensation polymerization reaction: after the condensation polymerization reaches the preset molecular weight, a high-activity phenol metal-removing aromatic end-capping agent is added into the polymerization system to remove the phenol metal end groups, terminate the condensation polymerization reaction, and not only can the polyarylsulfone ether have aromatic end groups in the end capping process, but also contain necessary functional groups.
2. The method for preparing polyarylsulfone ether based on the double-end-capping method according to claim 1, wherein the dosage relationship of the difunctional phenol and the difunctional halogenated aryl sulfone is as follows: the molar ratio of phenol to halogen is (0.8-1.1): 1.
3. The method for preparing polyarylsulfone ether based on the double-end-capping process according to claim 1, wherein the difunctional phenol is selected from one or more of the following structural formulas:
4. The method of preparing polyarylsulfone ether based on the double-ended process according to claim 1, wherein the difunctional halogenated aryl sulfone is selected from the group consisting of one or more of the following structural formulas:
5. The method for preparing polyarylsulfone ether based on the double-ended process according to claim 1, wherein the number of equivalents of inorganic caustic alkali or inorganic caustic salt is 1 to 1.5 times the number of phenol equivalents;
The inorganic caustic alkali or inorganic caustic salt is selected from one or a combination of several of the following substances:
LiOH、NaOH、KOH、CsOH、Na2CO3、K2CO3、Cs2CO3、NaHCO3、KHCO3、CsHCO3、Li3PO4、Na3PO4、K3PO4、Cs3PO4、Na2HPO4、Cs2HPO4 Or K 2HPO4.
6. The method for preparing polyarylsulfone ether based on the double-end capping method as claimed in claim 1, wherein the theoretical amounts of the halogen-removing phenol metal type end capping agent and the high-activity phenol-removing metal aromatic type end capping agent are shown as formula (1)
Wherein: w is the dosage of the end capping agent, and is the weight unit; m is the molecular weight of the polyarylsulfone ether; v is the mass of the theoretical repeating unit of the polyarylsulfone ether; n is the number of theoretical repeating unit structures converted from the raw materials of the difunctional phenol and the difunctional sulfone; q is the sum of the masses of the added functional groups after the two ends of the polyarylsulfone ether are completely blocked; c is the molar mass of the end-capping agent.
7. The method for preparing polyarylsulfone ether based on the double-end capping method according to claim 1, wherein the dehalogenated phenol metal end capping agent is selected from one or more of the following structural formulas:
8. the method for preparing polyarylsulfone ether based on the double-end capping method according to claim 1, wherein the highly reactive dephenolizing metal aromatic end capping agent is selected from one or more of the following structural formulas: wherein n is a natural number from 0 to 16:
9. The method for preparing polyarylsulfone ether based on the double-end capping method according to claim 1, wherein the water and the halogenated alkali metal salt which are by-products of the reaction are simultaneously removed during the salt formation and polycondensation reaction in the step S1, so that the molecular weight of the polyarylsulfone ether is gradually increased.
10. The method for preparing polyarylsulfone ether based on the double-end-capping process according to claim 1, wherein inert gas is used for gas phase protection in the salt forming and polycondensation reaction process of step S1;
In the step S2 and the step S3, the method for judging whether the molecular weight of the polyarylsulfone ether reaches a preset value is as follows: and continuously sampling in the polymerization process, testing the viscosity of the obtained sample in a fixed solvent and concentration, and determining the molecular weight of the polyarylsulfone ether according to the viscosity.
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