CN117510854B - Polysulfone resin and preparation method thereof - Google Patents
Polysulfone resin and preparation method thereof Download PDFInfo
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- CN117510854B CN117510854B CN202410004454.XA CN202410004454A CN117510854B CN 117510854 B CN117510854 B CN 117510854B CN 202410004454 A CN202410004454 A CN 202410004454A CN 117510854 B CN117510854 B CN 117510854B
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 147
- 239000011347 resin Substances 0.000 title claims abstract description 113
- 229920005989 resin Polymers 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 69
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000001603 reducing effect Effects 0.000 claims abstract description 29
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 20
- 239000002516 radical scavenger Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 4
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 3
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 17
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical group [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 15
- 239000001110 calcium chloride Substances 0.000 claims description 15
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 15
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 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 claims description 9
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 235000011181 potassium carbonates Nutrition 0.000 claims description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 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 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical group [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000005469 granulation Methods 0.000 abstract description 5
- 230000003179 granulation Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 230000008859 change Effects 0.000 abstract description 4
- 239000012528 membrane Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000000843 powder Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- AOKCDAVWJLOAHG-UHFFFAOYSA-N 4-(methylamino)butyric acid Chemical compound C[NH2+]CCCC([O-])=O AOKCDAVWJLOAHG-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000009835 boiling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000001476 alcoholic effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000012038 nucleophile Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011361 granulated particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YXBZNMSPFZDRFZ-UHFFFAOYSA-M methanol;tetrabutylazanium;hydroxide Chemical compound [OH-].OC.CCCC[N+](CCCC)(CCCC)CCCC YXBZNMSPFZDRFZ-UHFFFAOYSA-M 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000012434 nucleophilic reagent Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses polysulfone resin and a preparation method thereof, and belongs to the technical field of polysulfone resin. The technical proposal is as follows: the method comprises the following steps: s1, adding bisphenol A, 4' -dichloro diphenyl sulfone, a salifying agent and a water diversion agent into N-methyl pyrrolidone, introducing protective gas, heating to 120-150 ℃, and preserving heat for 2-8 hours to perform salifying reaction; after the reaction is finished, adding a reducing agent-chloride reduction system, continuously heating to 170-210 ℃, and preserving heat to carry out nucleophilic polycondensation; cooling to 60-150 ℃ after the reaction is finished, adding a carboxyl end scavenger, and reacting for 0.5-2h to obtain polysulfone resin polymerization liquid; s2, capping the polysulfone resin polymerization liquid to obtain capped polysulfone resin polymerization liquid; s3, carrying out post-treatment on the end-capped polysulfone resin polymerization liquid to obtain polysulfone resin. The polysulfone resin has low carboxyl end content, and the molecular weight distribution and viscosity do not change obviously during granulation, thereby being beneficial to downstream membrane preparation.
Description
Technical Field
The invention relates to the technical field of polysulfone resin, in particular to polysulfone resin and a preparation method thereof.
Background
Polysulfone resin (PSU) is amorphous special engineering plastic, and has good oxidation resistance, mechanical property and thermal stability because of containing sulfonyl, isopropyl and benzene ring, and the existence of ether bond provides certain toughness for the PSU, so the PSU is widely applied to the fields of high-end medical treatment, electronic products, water treatment, aerospace and the like because of the excellent characteristics of the PSU.
The method for synthesizing polysulfone resin is a one-step method, namely, bisphenol A and 4, 4-dichloro diphenyl sulfone monomer are subjected to salification and nucleophilic substitution polycondensation in the presence of an alkaline nucleophile, wherein the alkaline nucleophile is usually potassium carbonate, and the solvent is N-methylpyrrolidone (NMP); after the polymerization is finished, a polymer solution is obtained, water, ethanol or methanol is used as a precipitator, and polysulfone is separated from the polymer solution in the precipitator; the polysulfone is purified, dried, granulated and packaged to obtain the product.
In the salification stage, monomer bisphenol A reacts with an alkaline nucleophile to generate bisphenol A salt and water, and NMP is easily hydrolyzed by water generated in the salification stage under the reaction conditions of high temperature and strong alkali to generate N-methyl-4-aminobutyric acid (reaction formula I); further, N-methyl-4-aminobutyric acid reacts with 4, 4-dichlorodiphenyl sulfone, which is a raw material monomer of polysulfone, so that carboxyl groups appear at the end of a finally prepared polysulfone molecular chain (reaction formula II).
A formula I; Formula II.
The polysulfone molecular chain end synthesized by the traditional polymerization process contains a considerable amount of terminal carboxyl groups, and the thermal stability of the polysulfone molecular chain end is far lower than that of the chlorine end group and the methoxy group of the polysulfone end. At the granulating temperature of 320-360 ℃, crosslinking occurs between carboxyl-terminated active groups, so that the molecular weight of polysulfone is further improved, the molecular weight distribution is widened, and the viscosity is changed. Since the hydrolysis of NMP can not be inhibited during polymerization, the carboxyl end group content of polysulfone can not be controlled, so that the viscosity of polysulfone particles is often randomly fluctuated, and downstream membrane manufacturers need to frequently adjust the process, thereby greatly influencing the production efficiency.
Therefore, the reduction of the active carboxyl end groups of the polysulfone resin and the stabilization of the viscosity of the polysulfone are important directions for improving the polysulfone, and have important significance for promoting the application of the polysulfone.
Aiming at the problem of viscosity change during polysulfone resin granulation, it is generally considered that the crosslinking of the polysulfone resin is caused by phenolic hydroxyl groups of polysulfone, and the prior art is used for blocking the phenolic hydroxyl groups through blocking agents such as chloromethane and the like, so that only the polysulfone phenolic hydroxyl groups are eliminated, and the terminal carboxyl groups cannot be removed effectively in a targeted manner.
The Chinese patent No. 104530431A discloses an industrialized synthesis method of polysulfone resin with low color and high light transmittance, 3,4' -dihalogenophenone is selected as a blocking agent to block phenolic hydroxyl groups, and the blocked polysulfone resin with improved thermal stability is successfully obtained.
Chinese patent No. 115010926B discloses a polysulfone resin and a preparation method thereof, which adopts specific water-soluble end capping agent 1, 3-propane sultone, effectively reduces the content of hydroxyl groups, avoids oxidative discoloration of the resin during processing and granulation, and improves the thermal stability and transparency of the material.
Chinese patent No. 115216010A discloses a method for preparing polysulfone resin rapidly, which is to partially convert 4,4' -dichloro diphenyl sulfone into fluoro-compound under the combined action of salifying agent, a small amount of anhydrous potassium fluoride and phase transfer catalyst to carry out polymerization reaction, shorten polymerization time and reduce polymerization temperature, thus obtaining polysulfone resin with high thermal stability.
However, the above patent still cannot avoid hydrolysis of NMP as a solvent, and thus cannot reduce the active carboxyl end groups of polysulfone to stabilize the viscosity of polysulfone.
Disclosure of Invention
The invention aims to solve the technical problems that: the polysulfone resin and the preparation method thereof have the advantages that the defects of the prior art are overcome, the content of active carboxyl groups in the prepared polysulfone resin is low, the molecular weight distribution and viscosity do not change obviously during granulation, and the polysulfone resin is beneficial to the application in downstream membrane preparation.
The technical scheme of the invention is as follows:
in one aspect, the present invention provides a method for preparing polysulfone resin, comprising the steps of:
s1, adding bisphenol A (BPA), 4' -dichloro diphenyl sulfone (DCDPS), a salifying agent and a water diversion agent into N-methyl pyrrolidone (NMP), introducing protective gas, heating to 120-150 ℃, and preserving heat for 2-8 hours to perform salifying reaction; after the water yield reaches the theoretical water yield and the salification reaction is finished, adding a reducing agent-chloride reduction system in a low molecular weight stage before the viscosity of the reaction system is increased, continuously heating to 170-210 ℃, and preserving heat to perform nucleophilic polycondensation reaction; cooling to 60-150 ℃ after the reaction is finished, adding a carboxyl end scavenger, and reacting for 0.5-2h to obtain polysulfone resin polymerization liquid;
s2, carrying out end-capping treatment on the polysulfone resin polymerization liquid to obtain an end-capped polysulfone resin polymerization liquid;
S3, carrying out post-treatment on the end-capped polysulfone resin polymerization liquid to obtain polysulfone resin.
In step S1, the calculation formula of the theoretical water yield is as follows: theoretical water yield = M x M 1/M2; wherein m is the mass of bisphenol A, g; m 1 is the relative molecular mass of water molecules, M 1=18;M2 is the relative molecular mass of bisphenol a, M 2 =228.3.
Preferably, in step S1, in the reducing agent-chloride reducing system, the reducing agent is sodium borohydride, and the chloride is calcium chloride.
Preferably, in the step S1, the addition amount of the reducing agent in the reducing agent-chloride reducing system is 0.05-2% of the mass of NMP, and the molar ratio of the reducing agent to the chloride is 1 (1-8).
Preferably, in step S1, the carboxyl end group scavenger is polycarbodiimide.
Preferably, in step S1, the addition amount of the terminal carboxyl group scavenger is 0.1 to 0.5% by mass of NMP.
Preferably, in the step S1, the mol ratio of bisphenol A, 4 '-dichlorodiphenyl sulfone and salifying agent is 1 (0.85-1): (1-3), the mass ratio of the total mass of bisphenol A and 4,4' -dichlorodiphenyl sulfone to NMP is 1 (2.5-5), and the mass of the water diversion agent is 20-40% of the mass of NMP.
Preferably, in step S1, the salt former is potassium bicarbonate, sodium bicarbonate, cesium carbonate, potassium carbonate or sodium carbonate; the water-splitting agent is toluene, dimethylbenzene, mesitylene, ethylbenzene or metaethylbenzene.
Preferably, in step S2, the capping treatment of the polysulfone resin polymer solution is: and (3) introducing chloromethane into the polysulfone resin polymerization liquid at 160-190 ℃ for reaction for 1-4h.
Preferably, in step S3, the post-treatment of the blocked polysulfone resin polymer solution is: the blocked polysulfone resin polymer solution is cooled, crushed, washed, filtered and dried.
On the other hand, the invention also provides polysulfone resin, which is prepared by the preparation method of the polysulfone resin.
According to the invention, a reducing system formed by a reducing agent and chloride is added after the salification reaction is completed, wherein the sodium borohydride reducing agent is used as a nucleophilic reagent to attack carbon-oxygen double bonds in the carboxyl of the N-methyl-4-aminobutyric acid to form an intermediate, and then proton transfer and charge rearrangement are carried out to generate alcoholic hydroxyl and borate. However, since sodium borohydride has weaker reducing power and slower reducing carboxyl rate, calcium chloride is added to form Ca (BH 4)2, which ensures the reducing rate of carboxyl) with stronger reducing power with sodium borohydride, and a terminal carboxyl scavenger is added before end capping after polymerization is finished to react with carboxyl which is difficult to be reduced by a reducing system due to the connection of polysulfone chain segments to form an amide bond with higher heat stability, wherein the reaction mechanism of reducing N-methyl-4-aminobutyric acid by the reducing agent is as follows:
。
compared with the prior art, the invention has the following beneficial effects:
1. The polysulfone resin prepared by the invention has low content of active carboxyl end groups, and the molecular weight distribution and viscosity do not change obviously during granulation, thereby being beneficial to the application of the polysulfone resin in downstream membrane preparation.
2. The reduction system adopted by the invention is used for reducing N-methyl-4-aminobutyric acid monomer, and the carboxyl end scavenger is used for reducing N-methyl-4-aminobutyric acid connected with polysulfone high molecular chain segment, so that the dosage of reagents is reduced while the carboxyl end content of polysulfone is reduced. Meanwhile, the invention uses sodium borohydride and calcium chloride which are mild in reduction as a reduction system, has no adverse effect on reaction raw materials and solvents, and uses polycarbodiimide as a carboxyl end scavenger, the boiling point is 154 ℃, and the sodium borohydride and the calcium chloride are easy to evaporate and remove in the subsequent end-capping treatment process.
3. According to the invention, a reduction system is added at the stage that most N-methyl-4 aminobutyric acid is not connected into a polysulfone chain segment and has low molecular weight and is easy to reduce, so that reduction of carboxyl is carried out, and the conversion rate of carboxyl is ensured.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention.
Example 1
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
S1 polymerization reaction: adding 60.48kg of N-methylpyrrolidone into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 7278.89g of 4,4' -dichloro diphenyl sulfone, 3866.67g of potassium carbonate and 12.16kg of dimethylbenzene, replacing with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 145 ℃ for reaction with water for 4 hours; after reaching the theoretical water yield, all the dimethylbenzene is distilled out, 30.07g of sodium borohydride and 88.21g of calcium chloride are added, the temperature is raised to 185 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 150 ℃, 60.15g of polycarbodiimide is added, and the reaction is continued for 0.5h, thus obtaining polysulfone resin polymer;
s2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 2 hours at 170 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Example 2
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
S1 polymerization reaction: adding 31.474kg of N-methylpyrrolidone into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 6505.34g of 4,4' -dichlorodiphenyl sulfone, 2966.07g of sodium carbonate and 6.3kg of toluene, replacing with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 120 ℃ for 8h with water; after reaching the theoretical water yield, all toluene is distilled out, 157.37g of sodium borohydride and 3693.5g of calcium chloride are added, the temperature is raised to 190 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 110 ℃, 157.37g of polycarbodiimide is added, and the reaction is continued for 1h, thus obtaining polysulfone resin polymer liquid;
s2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 2.5 hours at 160 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Example 3
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
s1 polymerization reaction: adding 64.479kg of N-methylpyrrolidone into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 6811.47g of 4,4' -dichlorodiphenyl sulfone, 26051.08g of cesium carbonate and 19.343kg of ethylbenzene into the kettle, replacing the mixture with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 140 ℃ for reaction with water for 2 hours; after reaching the theoretical water yield, all ethylbenzene is distilled out, 32.25g of sodium borohydride and 425.6g of calcium chloride are added, the temperature is raised to 210 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 60 ℃, 193.4g of polycarbodiimide is added, and the reaction is continued for 1h, thus obtaining polysulfone resin polymer solution;
S2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 3 hours at 165 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Example 4
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
S1 polymerization reaction: adding 45.938kg of N-methylpyrrolidone into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 7041.07g of 4,4' -dichlorodiphenyl sulfone, 6404.11g of potassium bicarbonate and 13.781kg of mesitylene, replacing with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 150 ℃ for reaction with water for 4 hours; after reaching the theoretical water yield, all mesitylene is distilled out, 229.69g of sodium borohydride and 673.88g of calcium chloride are added, the temperature is raised to 170 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 100 ℃, 64.48g of polycarbodiimide is added, and the reaction is continued for 1h, thus obtaining polysulfone resin polymer solution;
S2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 1h at 190 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Example 5
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
S1 polymerization reaction: adding 46.742kg of N-methylpyrrolidone into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 7270.67g of 4,4' -dichlorodiphenyl sulfone, 5373.64g of sodium bicarbonate and 18.695kg of xylene, replacing with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 145 ℃ to carry out water reaction for 4 hours; after reaching the theoretical water yield, all the meta-ethylbenzene is distilled out, 476.7g of sodium borohydride and 1398.77g of calcium chloride are added, the temperature is raised to 170 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 90 ℃, 140.22g of polycarbodiimide is added, and the reaction is continued for 1h, thus obtaining polysulfone resin polymer solution;
S2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 4 hours at 160 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Example 6
The preparation method of the polysulfone resin of the embodiment comprises the following steps:
S1 polymerization reaction: adding 53.42kg of NMP (N-methyl pyrrolidone) into a 100L polymerization reaction kettle, adding 6084.34g of bisphenol A, 7270.67g of 4,4' -dichloro diphenyl sulfone, 7367.09g of potassium carbonate and 21.368kg of dimethylbenzene, replacing the mixture with nitrogen for three times, introducing nitrogen to perform normal pressure reaction, performing nitrogen protection in the whole polymerization reaction, and heating to 145 ℃ for 4 hours with water; after reaching the theoretical water yield, all the dimethylbenzene is distilled out, 1068.4g of sodium borohydride and 3135g of calcium chloride are added, the temperature is raised to 170 ℃, and the heat preservation is continued; the reaction is carried out until the stirring torque is not increased any more, the temperature is reduced to 105 ℃, 160.26g of polycarbodiimide is added, and the reaction is continued for 2 hours, thus obtaining polysulfone resin polymer liquid;
S2 end capping: introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, and end-capping for 4 hours at 170 ℃ to obtain an end-capped polysulfone resin polymerization liquid;
S3, post-treatment: pouring the blocked polysulfone resin polymerization liquid into cold water for cooling and precipitation, mechanically crushing the blocked polysulfone resin polymerization liquid into powder, boiling the powder for a plurality of times with high temperature, filtering and drying the powder to obtain polysulfone resin white powder.
Comparative example 1
The difference from example 1 is that: in step S1, no reducing agent-chloride reducing system and no carboxyl end scavenger are added.
Comparative example 2
The difference from example 1 is that: in step S1, no calcium chloride is added to the reducing agent-chloride reduction system.
Comparative example 3
The difference from example 1 is that: in step S1, zirconium tetrachloride is used to replace calcium chloride in the reducing agent-chloride reduction system.
Comparative example 4
The difference from example 1 is that: in step S1, no sodium borohydride reducing agent is added to the reducing agent-chloride reduction system.
Comparative example 5
The difference from example 1 is that: in step S1, sodium hydrosulfite is used to replace sodium borohydride in a reducing agent-chloride reduction system.
Comparative example 6
The difference from example 1 is that: in step S1, a reducing agent-chloride reducing system is added when the polysulfone molecular weight reaches 80% of the target molecular weight.
Comparative example 7
The difference from example 1 is that: the polycarbodiimide is added in step S2, specifically: and (3) introducing a chloromethane end-capping agent into the polysulfone resin polymerization liquid, capping at 170 ℃ for 1h, adding polycarbodiimide, and continuing to react for 1h to obtain the capped polysulfone resin polymerization liquid.
Comparative example 8
The difference from example 1 is that: in step S1, polycarbodiimide is not added.
The polysulfone resin powders obtained in examples 1to 6 and comparative examples 1to 8 were pelletized to obtain polysulfone resin particles: the drying temperature was 145℃and the drying time was 3.5 hours, the solution temperature was 350 ℃.
The polysulfone resin powder and the granulated particles were subjected to the following tests, and the test results are shown in table 1.
1. Gel Permeation Chromatography (GPC) test molecular weight
Test instrument: volter E2695 gel chromatograph, equipped with ultraviolet detector (wavelength 254 nm).
Test conditions: the flow rate was 1mL/min and the column temperature was 40 ℃.
Sample preparation: the sample to be tested was dissolved in THF to make a 1wt.% solution, which was filtered through a filter.
The integration method comprises the following steps: the relative molecular weight was determined using polystyrene standards as standard curves, and the cyclic dimer content was determined using an area normalization method.
2. Terminal carboxyl group content test
Dissolving a polysulfone resin sample to be detected in N, N-Dimethylacetamide (DMAC), preparing 1wt.% of liquid to be detected, adding hydrochloric acid and an internal standard of p-hydroxybenzoic acid (PHBA), titrating with 0.1M tetrabutylammonium hydroxide methanol solution, and determining the end point by potential to obtain the total quantity M of carboxyl groups at the end of the polysulfone solution; weighing the same hydrochloric acid and PHBA, dissolving in DMAC to prepare a blank solution, and performing potentiometric titration to test the blank carboxyl end group amount M, wherein the difference (M-M) between the two is the carboxyl end group content of the polysulfone resin.
3. Viscosity test
Polysulfone resin was dissolved in N, N-Dimethylacetamide (DMAC) to prepare a 25wt.% polymer solution, which was tested for rotational viscosity using a rotational viscometer at 40 ℃ and shear rate of 30s -1.
TABLE 1 test results of Performance of polysulfone resin powder obtained in examples 1-6 and comparative examples 1-8 and granulated particles
As can be seen from the results of examples 1-6 and comparative examples 1-8 in Table 1, the data of comparative example 1 and example 1 show that the reduction system and the carboxyl end scavenger are not added during the polymerization process, and the carboxyl end content in the product is obviously improved from 10mmol/kg to a high level of 97 mmol/kg. This is because N-methyl-4-aminobutyric acid generated by hydrolysis of NMP causes high content of carboxyl end groups of the prepared polysulfone resin in normal polymerization process, and the active carboxyl end groups trigger high-temperature crosslinking when polysulfone is granulated, so that polysulfone molecular weight distribution is increased and viscosity is increased. The carboxyl in the N-methyl-4-aminobutyric acid can be reduced into alcoholic hydroxyl by adding a reducing agent, and then the alcoholic hydroxyl reacts with the raw materials to be connected into a polysulfone molecular chain, so that the carboxyl is converted into ether bonds in chain segments; for N-methyl-4-aminobutyric acid which has reacted with polysulfone raw material, the carboxyl end group is difficult to be reduced by a reducing agent, but the reaction activity of the N-methyl-4-aminobutyric acid with a carboxyl end group scavenger is high, the N-methyl-4-aminobutyric acid is easy to react, and finally the purpose of removing the carboxyl end group is achieved.
In comparative example 2, the reduction system used was free of calcium chloride, and the content of terminal carboxyl groups in the polysulfone resin product was less decreased than in comparative example 1, indicating that sodium borohydride alone was too low in the reduction, and insufficient in the reduction of carboxyl groups of N-methyl-4-aminobutyric acid, resulting in a larger molecular weight distribution and an increased viscosity of the pelletized polysulfone resin as compared with example 1.
Comparative example 3 shows that the sodium borohydride-zirconium tetrachloride is inferior in reducibility and hardly plays a role in converting carboxyl groups when the sodium borohydride-zirconium tetrachloride is used as a reduction system, as compared with example 1, since the content of carboxyl groups at the terminal ends in the polysulfone resin product is high after the calcium chloride is replaced with zirconium tetrachloride.
In comparative example 4, no reducing agent was added and only the terminal carboxyl scavenger was added, resulting in a large amount of N-methyl-4-aminobutyric acid monomer remaining in the reaction process, and the carboxyl content in the polysulfone resin was increased.
In comparative example 5, sodium hydrosulfite was used instead of sodium borohydride, and decomposition occurs under the reaction conditions for preparing polysulfone resin due to its low thermal stability, which does not exert a reducing effect, resulting in an increase in the carboxyl content of polysulfone.
In comparative example 6, the reduction system was added at the latter stage of polysulfone polymerization when the polymer molecular weight was high, and the terminal carboxyl group content was less decreased than that of comparative example 1. This is because N-methyl-4-aminobutyric acid is incorporated into the polysulfone polymer chain end in the latter stage of polymerization, and is difficult to be reduced by a reduction system, so that the polysulfone resin after pelletization has a larger molecular weight distribution and a higher viscosity than in example 1.
Comparative example 7 a carboxyl end scavenger was added during the end capping process, and the polysulfone end capping temperature was higher than the boiling point of the carboxyl end scavenger, allowing it to evaporate rapidly and not function, resulting in a substantial increase in carboxyl end content.
Comparative example 8 was free of added carboxyl end scavenger, which also resulted in a significant increase in carboxyl end content.
Claims (6)
1. A method for preparing polysulfone resin, comprising the steps of:
S1, adding bisphenol A, 4' -dichloro diphenyl sulfone, a salifying agent and a water diversion agent into N-methyl pyrrolidone, introducing protective gas, heating to 120-150 ℃, and preserving heat for 2-8 hours to perform salifying reaction; after the water yield reaches the theoretical water yield and the salification reaction is finished, adding a reducing agent-chloride reduction system, continuously heating to 170-210 ℃, and preserving heat to carry out nucleophilic polycondensation reaction; cooling to 60-150 ℃ after the reaction is finished, adding a carboxyl end scavenger, and reacting for 0.5-2h to obtain polysulfone resin polymerization liquid;
s2, carrying out end-capping treatment on the polysulfone resin polymerization liquid to obtain an end-capped polysulfone resin polymerization liquid;
S3, carrying out post-treatment on the end-capped polysulfone resin polymerization liquid to obtain polysulfone resin;
in the step S1, in a reducing agent-chloride reducing system, the reducing agent is sodium borohydride, and the chloride is calcium chloride;
in the step S1, in a reducing agent-chloride reducing system, the adding amount of the reducing agent is 0.05-2% of the mass of N-methyl pyrrolidone, and the mol ratio of the reducing agent to the chloride is 1 (1-8);
In the step S1, the carboxyl end scavenger is polycarbodiimide;
in the step S1, the addition amount of the terminal carboxyl scavenger is 0.1-0.5% of the mass of the N-methylpyrrolidone.
2. The method for producing polysulfone resin according to claim 1, wherein in step S1, the molar ratio of bisphenol A, 4 '-dichlorodiphenyl sulfone and salifying agent is 1 (0.85-1): (1-3), the mass ratio of the total mass of bisphenol A and 4,4' -dichlorodiphenyl sulfone to N-methylpyrrolidone is 1 (2.5-5), and the mass of the water-separating agent is 20-40% of the mass of N-methylpyrrolidone.
3. The method for producing polysulfone resin according to claim 1, wherein in step S1, the salt former is potassium bicarbonate, sodium bicarbonate, cesium carbonate, potassium carbonate or sodium carbonate; the water-splitting agent is toluene, dimethylbenzene, mesitylene, ethylbenzene or metaethylbenzene.
4. The method for producing polysulfone resin according to claim 1, wherein in step S2, the capping treatment of the polysulfone resin polymer solution is: and (3) introducing chloromethane into the polysulfone resin polymerization liquid at 160-190 ℃ for reaction for 1-4h.
5. The method for producing polysulfone resin according to claim 1, wherein in step S3, the post-treatment of the blocked polysulfone resin polymer solution is: the blocked polysulfone resin polymer solution is cooled, crushed, washed, filtered and dried.
6. A polysulfone resin prepared by the method of any one of claims 1 to 5.
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| US5462867A (en) * | 1988-10-17 | 1995-10-31 | Hemasure, Inc. | Covalent attachment of macromolecules to polysulfones or polyethersulfones modified to contain functionalizable chain ends |
| CN101531758A (en) * | 2008-03-14 | 2009-09-16 | 中国科学院宁波材料技术与工程研究所 | Polythioetherimide and preparation method thereof |
| CN105330842A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Synthesis method of high-transparency polysulfone resin containing cycloalkyl group substituted phenol |
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| JP2011506691A (en) * | 2007-12-19 | 2011-03-03 | 中国科学院▲寧▼波材料技▲術▼▲与▼工程研究所 | Polythioetherimide and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5462867A (en) * | 1988-10-17 | 1995-10-31 | Hemasure, Inc. | Covalent attachment of macromolecules to polysulfones or polyethersulfones modified to contain functionalizable chain ends |
| CN101531758A (en) * | 2008-03-14 | 2009-09-16 | 中国科学院宁波材料技术与工程研究所 | Polythioetherimide and preparation method thereof |
| CN105330842A (en) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | Synthesis method of high-transparency polysulfone resin containing cycloalkyl group substituted phenol |
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