CN109721733B - Preparation method of polysulfone resin - Google Patents
Preparation method of polysulfone resin Download PDFInfo
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- CN109721733B CN109721733B CN201910027089.3A CN201910027089A CN109721733B CN 109721733 B CN109721733 B CN 109721733B CN 201910027089 A CN201910027089 A CN 201910027089A CN 109721733 B CN109721733 B CN 109721733B
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- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 93
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 50
- 239000011347 resin Substances 0.000 title claims abstract description 50
- 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 84
- 229920000642 polymer Polymers 0.000 claims abstract description 84
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000002131 composite material Substances 0.000 claims abstract description 76
- 239000000178 monomer Substances 0.000 claims abstract description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 40
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 25
- 238000005406 washing Methods 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 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 15
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 6
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 5
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
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- 125000004122 cyclic group Chemical group 0.000 abstract description 51
- 239000003960 organic solvent Substances 0.000 abstract description 11
- 238000000746 purification Methods 0.000 abstract description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 3
- 238000003408 phase transfer catalysis Methods 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
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- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
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- 101001134861 Homo sapiens Pericentriolar material 1 protein Proteins 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 102100033422 Pericentriolar material 1 protein Human genes 0.000 description 6
- 102100036894 Protein patched homolog 2 Human genes 0.000 description 6
- 101710161395 Protein patched homolog 2 Proteins 0.000 description 6
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 102100022927 Nuclear receptor coactivator 4 Human genes 0.000 description 4
- 101100189632 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) PTC6 gene Proteins 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
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- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UWHSPZZUAYSGTB-UHFFFAOYSA-N 1,1,3,3-tetraethylurea Chemical compound CCN(CC)C(=O)N(CC)CC UWHSPZZUAYSGTB-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
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- RMNIZOOYFMNEJJ-UHFFFAOYSA-K tripotassium;phosphate;hydrate Chemical compound O.[K+].[K+].[K+].[O-]P([O-])([O-])=O RMNIZOOYFMNEJJ-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyethers (AREA)
Abstract
The invention provides a preparation method of polysulfone resin, which comprises the following steps: a) carrying out polymerization reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; the composite base catalyst contains a structure shown in a formula (I) or a formula (II); wherein, -R1Is selected from-CH3Or a phenyl group; -R2Is selected from-CH3、‑CH2CH3Or an isopropyl group; -R3Is selected from-CH3、‑CH2CH3(ii) a b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin. Compared with the prior art, the preparation method provided by the invention adopts the specific composite base catalyst to ensure that the polymerization reaction is carried out under a phase transfer catalysis system, thereby realizing the reduction (or partial inhibition) of the cyclic oligomerization in the reaction processThe content of the compound in the polymer solution is reduced, so that the obtained polymer solution can obtain the polysulfone resin with lower content of cyclic oligomer without additional purification of organic solvent.
Description
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a preparation method of polysulfone resin.
Background
Polysulfone-based resins (PSF) are a thermoplastic special engineering plastic, the main types of which include: polyphenylsulfone (PPSU), Polyethersulfone (PES) and Polysulfone (PSU). The polysulfone resin has the advantages of high strength, good toughness, high temperature resistance, chemical corrosion resistance, excellent film forming property and the like, can be processed into various devices such as flat sheet films, hollow fibers, ultrafiltration films and the like, and is widely applied to the industrial fields such as electronics, automobiles, airplanes and the like and the water treatment process. Moreover, the polysulfone resin also has the advantages of no toxicity, radiation resistance and hydrolysis resistance, especially can still keep good mechanical property and lower creep property under the condition of high-temperature continuous load or steam and disinfection environment, has long-term use temperature of more than 160 ℃, and is widely applied to the aspects of food sanitation, medical appliances and the like.
Taking polysulfone as an example, the global usage amount of the polysulfone has an increase rate of more than 10% per year (the annual production amount of the polysulfone resin in the world exceeds 4 ten thousand tons), and the annual demand increase rate of the polysulfone in China exceeds 20%. By 2017, the annual demand of domestic polysulfone is over 6000 tons, and especially in the field of medical application, the demand is increased year by year. However, the current domestic polysulfone production capacity is about 1500-2000 tons/year. Compared with the similar foreign polysulfone products, the domestic polysulfone has the problems of laggard production process, poor batch stability, high content of impurities such as oligomer, metal ions and the like, incapability of competing with imported products in variety or price and the like; in particular, medical grade polysulfone materials used for the preparation of high-end medical products such as hemodialysis membranes, membrane oxygenators, artificial heart valves, and the like, are almost entirely imported. In addition, because of the problems of high content of impurities such as cyclic oligomer, metal ions and the like, the domestic polysulfone resin is easy to cause the problems of low transmittance, uneven color, low processing yield and the like when being used for preparing a thin film device, and also limits the wide application of the domestic polysulfone resin in the field of high-end optical thin films. In conclusion, the purity problem of the polysulfone resin, especially the high content of the cyclic oligomer impurities, is a major bottleneck for restricting the extensive application of the polysulfone resin in high-end medical fields and high-end optical fields.
The polysulfone resin is usually prepared from bisphenol monomer (bisphenol A, bisphenol S, biphenol, etc.) and 4, 4' -dichlorodiphenyl sulfone in alkaline (NaOH, KOH, K)2CO3、K3PO4Etc.) under the condition of polycondensation reaction, and the common two-step synthesis method-farnesham (Farnham) nucleophilic substitution reaction and one-step synthesis method are adopted. Although the two preparation processes and procedures are different, the preparation of metal salts of phenol (NaOAr or KOAr) is the target, and the full polymerization is completed under proper temperature conditions. Synthesis of example with polysulfone: the two-step synthesis method is generally to react bisphenol A with sodium hydroxide (or potassium hydroxide) in a Dimethylsulfoxide (DMSO) solvent to produce a sodium salt (or potassium salt) of bisphenol A, and then to distill off a water-separating agent (toluene, xylene, cyclohexane, etc.); after the water separation is finished, 4' -dichlorodiphenyl sulfone is added into the mixture to carry out polycondensation reaction at the temperature of 140 ℃ and 160 ℃. This polycondensation process is described in detail in the U.S. Pat. No. 5,149,345. However, the production process is complex, especially has high control requirement on the water content of the system, and the condition control is strict during secondary feeding. The one-step synthesis method generally uses inorganic medium and strong alkali (potassium carbonate, sodium carbonate, cesium carbonate and the like) as a salifying reagent; the method can realize one-step feeding and greatly simplify the production process. However, the bicarbonate formed during the salt-forming reaction generates water upon heating, resulting in the necessity of an azeotropic water-splitting step. In recent years, Chinese patent CN200910069382.2 discloses a new method for preparing polysulfone resin by a water-separation-free process, and because stable potassium phosphate hydrate can be generated in the reaction process, the step of azeotropic water separation is omitted, and the reaction time is shortened; chinese patent CN201110286532.2 discloses a method for preparing polysulfone in a composite ionic liquid solvent, which shortens the time of salt formation and dehydration and realizes the green recovery of the solvent; chinese patents CN201410790045.3 and CN201510361661.1 disclose the use of high voltage (2.0-3.0M)Pa) synthesis process and a method for preparing polysulfone resin by taking microwaves as a heat source, greatly shorten the polymerization reaction time and save the energy consumption.
Through development of half a century, most of the developed production technologies of polysulfone resins have focused on the research on the adjustment of alkali species, the optimization of reaction solvent systems, the simplification of dehydration processes, and the like. But lack effective control of the cyclic oligomer content in the polymerization system. The chemical structure of the cyclic oligomer (taking polysulfone as an example) is shown in formula (III);
wherein n is 1 to 5. In the polycondensation reaction of the polysulfone resin, the resulting polymer is mainly a linear polymer and a small amount of cyclic oligomer is also present, wherein the cyclic oligomer is mainly cyclic dimer, trimer and tetramer. Different polymerized monomer structures and different polymerization processes finally result in larger content difference of cyclic oligomers of the polysulfone resin. The large difference between the solubility and rigidity of the cyclic oligomers and the main chain of the linear polymer and the high content of the cyclic oligomers are important reasons for the opaqueness (or turbidity of the solution) of the polysulfone resin. For the above reasons, the content of the cyclic oligomer must be controlled in the high-purity polysulfone-based resin. U.S. Pat. No. 2001/0056175A1 discloses a method for reducing cyclic oligomers in polysulfone resin by using chlorobenzene as a solvent and methanol as a precipitation solvent, but a large amount of organic solvent is needed in the post-treatment process, and the problem that the organic solvent of a ternary azeotropic system is difficult to recover is faced; chinese patent CN201210380356.3 discloses a method for preparing polysulfone resin by flash evaporation precipitation, which effectively reduces the content of inorganic salt particles wrapped by polysulfone resin, thereby improving the product purity and overcoming the problem of high energy consumption of solvent recovery after precipitation; chinese patent CN201710625749.9 discloses a method for preparing polysulfone resin with high purity by centrifugally separating and filtering the diluted polymer solution, concentrating, extruding and granulating.
However, most of the methods for preparing the high-purity polysulfone resin are to prepare the corresponding polysulfone resin, and then separate and purify the polysulfone resin to achieve the purpose of reducing the content of the cyclic oligomer; the purification process requires a large amount of organic solvent (such as methanol, ethanol, isopropanol, toluene, xylene, chlorobenzene, etc.), or the same solvent as the polymerization system as a diluent (such as DMSO, DMAc, NMP, sulfolane, etc.).
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a polysulfone resin, which can reduce (or partially inhibit) the generation of cyclic oligomers during the reaction process to reduce the content of cyclic oligomers in a polymer solution, so that the obtained polymer solution can be purified without an additional organic solvent to obtain a polysulfone resin with a lower content of cyclic oligomers.
The invention provides a preparation method of polysulfone resin, which comprises the following steps:
a) carrying out polymerization reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; the composite base catalyst contains a structure shown in a formula (I) or a formula (II);
wherein, -R1Is selected from-CH3Or
-R2Is selected from-CH3、-CH2CH3Or
-R3Is selected from-CH3、-CH2CH3；
b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin.
Preferably, the bisphenol monomer in step a) is selected from bisphenol a, bisphenol S or 4, 4' -biphenol.
Preferably, the salt forming agent in step a) is selected from NaOH, KOH, K2CO3And K3PO4One or more of (a).
Preferably, the amount of the composite base catalyst used in step a) is 0.1-3% of the molar amount of the bisphenol monomer.
Preferably, the dihalogen monomer in step a) is selected from 4,4 ' -dichlorodiphenyl sulfone, 4 ' -tetrafluorodiphenyl sulfone or 4,4 ' -difluorobenzophenone.
Preferably, the molar ratio of the bisphenol monomer, the salt-forming agent and the double-halogen monomer in step a) is 1: (2-3): (0.8 to 1.2).
Preferably, the temperature of the polymerization reaction in the step a) is 70-220 ℃ and the time is 1-15 h.
Preferably, the polymerization reaction in step a) is specifically carried out by:
dissolving a bisphenol monomer in a solvent, adding a salt forming agent and a composite base catalyst to carry out a water-splitting reaction, then adding a double-halogen monomer to heat, and carrying out a first polycondensation reaction to obtain a polymer solution;
or sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent for carrying out a water-splitting reaction, heating, and carrying out a second polycondensation reaction to obtain a polymer solution;
or sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent, heating, carrying out a third polycondensation reaction, and diluting to obtain a polymer solution.
Preferably, the temperature of the water diversion reaction is 110-150 ℃, and the time is 5-7 h.
Preferably, the temperature of the vacuum drying in the step b) is 100-150 ℃, and the time is 20-30 h.
The invention provides a preparation method of polysulfone resin, which comprises the following steps: a) carrying out polymerization reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; said compoundingThe alkali catalyst contains a structure shown in a formula (I) or a formula (II); wherein, -R1Is selected from-CH3Or a phenyl group; -R2Is selected from-CH3、-CH2CH3Or an isopropyl group; -R3Is selected from-CH3、-CH2CH3(ii) a b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin. Compared with the prior art, the preparation method provided by the invention adopts the specific composite base catalyst, so that the polymerization reaction is carried out under a phase transfer catalysis system, thereby reducing (or partially inhibiting) the generation of the cyclic oligomer in the reaction process, so as to reduce the content of the cyclic oligomer in the polymer solution, and further, the polysulfone resin with lower content of the cyclic oligomer can be obtained without purifying the obtained polymer solution by an additional organic solvent; meanwhile, the preparation method provided by the invention avoids a complex organic solvent purification process and simplifies the preparation process. Experimental results show that the content of the bicyclic oligomer in the polysulfone resin prepared by the preparation method provided by the invention can be reduced to 1.06%, and the total content of the cyclic oligomer can be reduced to 3.51%.
In addition, the preparation method provided by the invention has wide adaptability, and can be combined with the processes of one-step synthesis, two-step synthesis, no water separation and the like to prepare different types of polysulfone resins such as PPSU, PES, PSU and the like.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a PTC1 composite base catalyst used in an example of the present invention;
FIG. 2 is a NMR carbon spectrum of a PTC1 composite base catalyst used in an example of the present invention;
FIG. 3 is a NMR spectrum of a PTC2 composite base catalyst used in an example of the present invention;
FIG. 4 is a NMR carbon spectrum of a PTC2 composite base catalyst used in an example of the present invention;
FIG. 5 is a NMR spectrum of a PTC3 composite base catalyst used in an example of the present invention;
FIG. 6 is a NMR carbon spectrum of a PTC3 composite base catalyst used in an example of the present invention;
FIG. 7 is a NMR chart of a PTC4 composite base catalyst used in an example of the invention;
FIG. 8 is a NMR carbon spectrum of a PTC4 composite base catalyst used in an example of the present invention;
FIG. 9 is a NMR spectrum of a PTC5 composite base catalyst used in an example of the present invention;
FIG. 10 is a NMR carbon spectrum of a PTC5 composite base catalyst used in an example of the present invention;
FIG. 11 is a NMR spectrum of a PTC6 composite base catalyst used in an example of the present invention;
FIG. 12 is a NMR carbon spectrum of a PTC6 composite base catalyst used in an example of the present invention;
FIG. 13 is an infrared spectrum of polysulfone prepared by the preparation process provided in example 5 of the present invention;
FIG. 14 is a NMR chart of polysulfone prepared by the preparation method provided in example 5 of the present invention;
FIG. 15 is a gel chromatogram of polysulfone prepared by the preparation method provided in example 5 of the present invention;
FIG. 16 is a gel chromatogram of polysulfone prepared by the preparation method provided in comparative example 1.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of polysulfone resin, which comprises the following steps:
a) carrying out polymerization reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; the composite base catalyst contains a structure shown in a formula (I) or a formula (II);
wherein, -R1Is selected from-CH3Or
-R2Is selected from-CH3、-CH2CH3Or
-R3Is selected from-CH3、-CH2CH3；
b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin.
The invention firstly carries out polymerization reaction on bisphenol monomer, salt forming agent, composite base catalyst and double-halogen monomer in solvent to obtain polymer solution. In the present invention, the bisphenol monomer is preferably selected from bisphenol a, bisphenol S or 4, 4' -biphenol; wherein bisphenol A is used for preparing PSU, and bisphenol S is used for preparing PES, 4, 4' -biphenol is used for preparing PPSU. In a preferred embodiment of the invention, the bisphenol monomer is bisphenol a. The source of the bisphenol monomer is not particularly limited in the present invention, and commercially available products or laboratory products of bisphenol A, bisphenol S and 4, 4' -biphenol as described above, which are well known to those skilled in the art, may be used.
In the present invention, the salt forming agent is preferably selected from NaOH, KOH, K2CO3And K3PO4More preferably KOH. In a preferred embodiment of the present invention, the KOH is added in the form of an aqueous solution, and the present invention is not particularly limited thereto. The source of the salt forming agent is not particularly limited in the present invention, and NaOH, KOH, K and the like as described above, which are well known to those skilled in the art, are used2CO3And K3PO4The product of (4) is a commercially available product.
In the invention, the molar ratio of the salt forming agent to the bisphenol monomer is preferably (2-3): 1, more preferably (2 to 2.4): 1.
in the invention, the composite base catalyst contains a structure shown in a formula (I) or a formula (II), preferably contains a structure shown in a formula (II);
wherein, -R1Is selected from-CH3Or
Preferably, it is
-R2Is selected from-CH3、-CH2CH3Or
Preferably, it is
-R3Is selected from-CH3、-CH2CH3Is preferably-CH2CH3。
In the present invention, the complex base catalyst is preferably selected from
(as PTC 1-6 composite base catalyst in sequence), and more preferably
More preferably
The invention is a source of the composite base catalystThe method is not particularly limited, and a method known to those skilled in the art can be used.
In the present invention, the amount of the composite base catalyst used is preferably 0.1 to 3% by mole of the bisphenol monomer, and more preferably 0.2 to 0.5% by mole of the bisphenol monomer.
In the present invention, the dihalogen monomer is preferably selected from 4,4 '-dichlorodiphenyl sulfone, 4' -tetrafluorodiphenyl sulfone or 4,4 '-difluorobenzophenone, more preferably 4, 4' -dichlorodiphenyl sulfone. The present invention is not particularly limited in terms of the source of the dihalogeno monomer, and commercially available products or laboratory-derived products of the above-mentioned 4,4 ' -dichlorodiphenyl sulfone, 4 ' -tetrafluorodiphenyl sulfone and 4,4 ' -difluorobenzophenone, which are well known to those skilled in the art, can be used.
In the present invention, the molar ratio of the dihalogen monomer to the bisphenol monomer is preferably (0.8 to 1.2): 1, more preferably 1: 1.
in the present invention, the solvent is preferably selected from one or more of DMAc, DMSO, NMP, and sulfolane, and more preferably DMAc or DMSO. The source of the solvent is not particularly limited in the present invention, and a commercially available product of the above-mentioned polar aprotic solvent, which is well known to those skilled in the art, may be used. In the present invention, the ratio of the amount of the solvent to the bisphenol monomer is preferably (1.5L to 5L): 1kg, more preferably (4L to 5L): 1 kg.
In the present invention, the polymerization temperature is preferably 70 ℃ to 220 ℃, more preferably 80 ℃ to 160 ℃; the time for the polymerization reaction is preferably 1 to 15 hours, and more preferably 3 to 12 hours.
In the present invention, the polymerization reaction is preferably carried out by:
dissolving a bisphenol monomer in a solvent, adding a salt forming agent and a composite base catalyst to carry out a water-splitting reaction, then adding a double-halogen monomer to heat, and carrying out a first polycondensation reaction to obtain a polymer solution;
or sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent for carrying out a water-splitting reaction, heating, and carrying out a second polycondensation reaction to obtain a polymer solution;
or after sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent, heating, carrying out a third polycondensation reaction, and diluting to obtain a polymer solution;
more preferably:
dissolving a bisphenol monomer in a solvent, adding a salt forming agent and a composite base catalyst to carry out a water diversion reaction, then adding a double-halogen monomer to heat, and carrying out a first polycondensation reaction to obtain a polymer solution.
In the present invention, the polymerization process is preferably carried out under nitrogen protection and stirring conditions.
In a preferred embodiment of the present invention, the polymerization process is specifically:
dissolving a bisphenol monomer in a solvent, adding a salt forming agent and a composite base catalyst to carry out a water diversion reaction, then adding a double-halogen monomer to heat, and carrying out a first polycondensation reaction to obtain a polymer solution. Firstly, dissolving a bisphenol monomer in a solvent; the bisphenol monomer and the solvent are the same as those described in the above technical scheme, and are not described again here.
In the present invention, the temperature of the dissolution is preferably 70 to 90 ℃, more preferably 80 ℃.
After the bisphenol monomer is completely dissolved, adding a salt forming agent and a composite base catalyst to carry out a water diversion reaction; the salt forming agent and the composite base catalyst are the same as those in the technical scheme, and are not described again.
In the invention, the temperature of the water diversion reaction is preferably 110-150 ℃, and more preferably 140 ℃; the time of the water diversion reaction is preferably 5 to 7 hours, and more preferably 6 hours.
After water distribution is finished, adding a double-halogen monomer, heating, and carrying out a first polycondensation reaction to obtain a polymer solution; the double-halogen monomer is the same as that described in the above technical scheme, and is not described again here.
In the present invention, the temperature of the first polycondensation reaction is preferably 160 to 220 ℃, more preferably 160 ℃; the time of the first polycondensation reaction is preferably 1 to 6 hours, and more preferably 1 to 3 hours.
In another preferred embodiment of the present invention, the polymerization process is specifically:
and (2) sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent to carry out a water-splitting reaction, heating, and carrying out a second polycondensation reaction to obtain a polymer solution. In the present invention, the solvent, the bisphenol monomer, the double-halogen monomer, the salt forming agent and the composite base catalyst are the same as those described in the above technical solution, and are not described herein again.
In the invention, the temperature of the water diversion reaction is preferably 110-150 ℃, and more preferably 140 ℃; the time of the water diversion reaction is preferably 5 to 7 hours, and more preferably 6 hours.
In the present invention, the temperature of the second polycondensation reaction is preferably 160 to 220 ℃, more preferably 160 ℃; the time of the second polycondensation reaction is preferably 1 to 6 hours, and more preferably 3 to 6 hours.
In another preferred embodiment of the present invention, the polymerization process is specifically:
and (2) adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent in sequence, heating, carrying out a third polycondensation reaction, and diluting to obtain a polymer solution. In the present invention, the solvent, the bisphenol monomer, the double-halogen monomer, the salt forming agent and the composite base catalyst are the same as those described in the above technical solution, and are not described herein again.
In the present invention, the temperature of the third polycondensation reaction is preferably 160 to 220 ℃, more preferably 160 ℃; the time of the third polycondensation reaction is preferably 1 to 6 hours, and more preferably 3 to 6 hours.
The dilution process is not particularly limited in the present invention, and the dilution is carried out using the same solvent as that used in the polymerization reaction.
In the present invention, the viscosity of the polymer solution is preferably 0.40 to 0.80dL g-1More preferably 0.50dL g-1。
The preparation method provided by the invention adopts a specific composite base catalyst, so that the polymerization reaction is carried out under a phase transfer catalysis system, thereby reducing (or partially inhibiting) the generation of cyclic oligomer in the reaction process so as to reduce the content of the cyclic oligomer in a polymer solution.
After the polymer solution is obtained, the obtained polymer solution is put into water for solidification and then crushed, and then the polysulfone resin is obtained after washing, vacuum drying and granulation in sequence. In the present invention, it is preferable that the water-in curing further includes:
cooling the polymer solution; the cooling temperature is preferably 20 ℃ to 30 ℃, more preferably 25 ℃.
The process of the water-entering solidification and pulverization is not particularly limited by the invention, and the technical scheme familiar to the technical personnel in the field can be adopted. In the present invention, the purpose of the water washing is to remove salt, and the present invention is not particularly limited thereto.
In the present invention, the temperature of the vacuum drying is preferably 100 to 150 ℃, more preferably 120 ℃; the time for vacuum drying is preferably 20 to 30 hours, and more preferably 24 hours.
The granulation process is not particularly limited in the present invention, and may be performed by a method known to those skilled in the art.
The polymer solution obtained by the invention can be used for obtaining the polysulfone resin with lower cyclic oligomer content without additional purification of organic solvent; meanwhile, the preparation method provided by the invention avoids a complex organic solvent purification process and simplifies the preparation process.
The invention provides a preparation method of polysulfone resin, which comprises the following steps: a) carrying out polycondensation reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; the composite base catalyst contains a structure shown in a formula (I) or a formula (II); wherein, -R1Is selected from-CH3Or phenyl; -R2Is selected from-CH3、-CH2CH3Or an isopropyl group; -R3Is selected from-CH3、-CH2CH3(ii) a b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin. Compared with the prior art, the preparation method provided by the invention adopts the specific composite base catalyst to catalyze the polymerization reaction in a phase transfer mannerThe method is carried out under a system, so that the generation of cyclic oligomer is reduced (or partially inhibited) in the reaction process, the content of the cyclic oligomer in a polymer solution is reduced, and the polysulfone resin with lower cyclic oligomer content can be obtained from the obtained polymer solution without additional purification of an organic solvent; meanwhile, the preparation method provided by the invention avoids a complex organic solvent purification process and simplifies the preparation process. Experimental results show that the content of the bicyclic oligomer in the polysulfone resin prepared by the preparation method provided by the invention can be reduced to 1.06%, and the total content of the cyclic oligomer can be reduced to 3.51%.
In addition, the preparation method provided by the invention has wide adaptability, and can be combined with processes such as one-step synthesis, two-step synthesis and no water separation to prepare different types of polysulfone resins such as PPSU, PES, PSU and the like.
To further illustrate the present invention, the following examples are provided for illustration. The structural formula of the PTC1 composite base catalyst used in the following examples of the invention is shown in formula (I-1);
the preparation method specifically comprises the following steps:
adding bromoethane into 1, 8-diazabicycloundecen-7-ene (DBU) in an ice bath, stirring and reacting for 5 hours at room temperature, and then filtering; washing with ethyl acetate and diethyl ether for several times to obtain white solid, and treating with alkaline ion exchange resin to obtain corresponding hydroxyl form with yield higher than 95%; the hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance prove that the target product PTC1 composite base catalyst is shown in figures 1-2.
The structural formula of the PTC2 composite base catalyst used in the following examples of the invention is shown in formula (I-2);
the preparation method specifically comprises the following steps:
adding benzyl bromide into 1, 8-diazabicycloundecen-7-ene (DBU) in an ice bath, stirring and reacting for 5 hours at room temperature, and then filtering; washing with ethyl acetate and diethyl ether for several times to obtain white solid, and treating with alkaline ion exchange resin to obtain corresponding hydroxyl form with yield higher than 95%; the hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance prove that the target product PTC2 composite base catalyst is shown in figures 3-4.
The reaction formula of the PTC1 composite base catalyst and the reaction formula of the PTC2 composite base catalyst are shown in a formula (IV);
the structural formula of the PTC3 composite base catalyst used in the following examples of the invention is shown in formula (II-1);
the structural formula of the PTC4 composite base catalyst is shown in formula (II-2);
the structural formula of the PTC5 composite base catalyst is shown in formula (II-3);
the structural formula of the PTC6 composite base catalyst is shown in formula (II-4);
the preparation method of the PTC 3-6 composite base catalyst is disclosed in tetrahedron Lett.,1989,30, 1927; chem, 2007,72, 4067; J.Membr.Sci.,2017,537,151, prepared from tetraethyl urea or pentaalkylguanidine; the hydrogen spectrum and the carbon spectrum of the nuclear magnetic resonance prove that the target product PTC 3-6 composite base catalyst is shown in figures 5-12.
The quaternary ammonium salt type catalysts used in the comparative examples of the present invention are all commercially available.
The test method of the cyclic oligomer in the following embodiment of the invention specifically comprises the following steps:
the experiment was performed on a Waters-GPC Size Exclusion (SEC) column, first dissolving the prepared polysulfone resin in chromatographically pure THF, and injecting 20. mu.L (concentration 0.4 wt%) into the column; flow rate of mobile phase: 1.0 mL/min; a detector: UV 254; column temperature: 30 ℃; the calculation method of the content of the cyclic oligomer adopts a normalization method: the ratio of the peak area corresponding to the bicyclic oligomer to the sum of the peak areas of the polymer and the cyclic oligomer is the percentage content of the bicyclic oligomer; similarly, the ratio of cyclic oligomer peak area to the sum of polymer and cyclic oligomer peak areas is the percent cyclic oligomer content.
Example 1
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg of bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg of KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol of PTC1 composite alkali catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 1 of the invention, and the content of the bicyclic oligomer in the polymer is 1.31%, and the total content of the cyclic oligomer is 3.65%.
Example 2
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg of bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg of KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol of PTC2 composite alkali catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 2 of the invention, and the content of the bicyclic oligomer in the polymer is 1.25%, and the total content of the cyclic oligomer is 3.68%.
Example 3
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol PTC3 composite alkali catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 3 of the invention, and the content of the bicyclic oligomer in the polymer is 1.31%, and the total content of the cyclic oligomer is 4.41%.
Example 4
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg of bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg of KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol of PTC4 composite base catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 4 of the invention, and the content of the bicyclic oligomer in the polymer is 1.13%, and the total content of the cyclic oligomer is 3.70%.
Example 5
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg of bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg of KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol of PTC5 composite base catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 5 of the invention, and an infrared spectrogram and a nuclear magnetic resonance spectrogram of the polysulfone are shown in figures 13-14; the gel chromatogram of the polysulfone prepared by the preparation method provided by the embodiment 5 of the invention is shown in FIG. 15, and the comprehensive statistics of peaks are shown in tables 1-2; it can be seen that the polymer had a bicyclic oligomer content of 1.06% and a total cyclic oligomer content of 3.51%.
TABLE 1 comprehensive statistics of Peak 1 in the gel chromatogram of polysulfone prepared by the preparation method provided in example 5 of the present invention
| Name (R) | Retention time (minutes) | Area (microvolt seconds) | % area | Height (microvolt) | |
| 1 | |
12.579 | 61670561 | 98.94 | 330517 |
| Mean | 12.579 | 61670561.467 | 330516.821 |
TABLE 2 Peak 2 comprehensive statistics of the gel chromatogram of polysulfone prepared by the preparation method provided in example 5 of the present invention
| Name (R) | Retention time (minutes) | Area (microvolt seconds) | % area | Height (microvolt) | |
| 1 | |
19.865 | 660921 | 1.06 | 24430 |
| Mean | 19.865 | 660921.144 | 24429.666 |
Example 6
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg of bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg of KOH (100mol) aqueous solution with the mass fraction of 50% and 0.25mol of PTC6 composite base catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 6 of the invention, and the polymer has the bicyclic oligomer content of 1.24% and the cyclic oligomer content of 4.43%.
Example 7
(1) Injecting 50L DMSO into a 100L reaction kettle, then adding 11.451kg bisphenol A (50mol) into the reaction kettle under the conditions of nitrogen protection and stirring, heating to 80 ℃, adding 11.222kg KOH (100mol) aqueous solution with the mass fraction of 50% and 0.1mol of PTC5 composite base catalyst after the bisphenol A is completely dissolved, heating to 140 ℃, and carrying out water diversion reaction for 6 hours; after the water diversion is finished, 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) dissolved in toluene is added, the temperature is raised to 160 ℃, the reaction is carried out for 1 to 3 hours, and the polymerization viscosity reaches 0.40 to 0.80dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 7 of the invention, and the content of the bicyclic oligomer in the polymer is 1.19%, and the total content of the cyclic oligomer is 3.96%.
Example 8
(1) 50L DMAc was charged into a 100L reactor, and then 11.451kg bisphenol A (50mol), 14.358kg4, 4' -dichlorodiphenyl sulfone (50mol) and 14.51kg anhydrous K were added to the reactor in this order under nitrogen protection and stirring2CO3(105mol) and 0.25mol of PTC5 composite base catalyst, heating to 140 ℃, and carrying out water division reaction for 6 h; after the water diversion is finished, the temperature is raised to 160 ℃ for reaction for 3-6 h until the polymerization viscosity reaches 0.40-0.80 dL g-1The reaction was stopped to obtain a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 8 of the invention, and the polymer has the bicyclic oligomer content of 1.34% and the cyclic oligomer content of 3.97%.
Example 9
(1) 50L DMAc was charged into a 100L reactor, and 11.451kg of bisphenol A (50mol), 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) and 25.472kg of anhydrous K were added to the reactor in this order under nitrogen protection and stirring3PO4(120mol) and 0.25mol of PTC4 composite base catalyst, directly heating to 160 ℃ for reaction for 3-6 h until the polymerization viscosity reaches 0.40-0.80 dL g-1The reaction was stopped and diluted with DMAc to give a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the preparation method provided by the embodiment 9 of the invention obtains polysulfone, and the content of the bicyclic oligomer in the polymer is 1.63%, and the total content of the cyclic oligomer is 4.31%.
Example 10
(1) 50L DMAc was charged into a 100L reactor, and 11.451kg of bisphenol A (50mol), 14.358kg of 4, 4' -dichlorodiphenyl sulfone (50mol) and 25.472kg of anhydrous K were added to the reactor in this order under nitrogen protection and stirring3PO4(120mol) and 0.25mol of PTC5 composite base catalyst, directly heating to 160 ℃ for reaction for 3-6 h until the polymerization viscosity reaches 0.40-0.80 dL g-1The reaction was stopped and diluted with DMAc to give a polymer solution.
(2) Cooling the reaction system to room temperature, adding the polymer solution obtained in the step (1) into water for solidification, and crushing to obtain white powdery polymer resin; and then washing with water to remove salt, drying in vacuum (120 ℃, 24h), and finally granulating to obtain the target product.
Through detection, the polysulfone is obtained by the preparation method provided by the embodiment 10 of the invention, and the polymer has the bicyclic oligomer content of 1.55% and the cyclic oligomer content of 4.29%.
Comparative example 1
The preparation process provided in example 1 was used with the difference that: no PTC1 complex base catalyst was added.
Through detection, the polysulfone is obtained by the preparation method provided by the comparative example 1, the gel chromatogram of the polysulfone is shown in FIG. 16, and the comprehensive statistics of peaks are shown in tables 3-4; from this, it was found that the polymer had a bicyclic oligomer content of 1.32% and a total cyclic oligomer content of 4.58%.
TABLE 3 comprehensive statistics of Peak 1 in the gel chromatogram of polysulfone prepared by the preparation method provided in comparative example 1
| Name (R) | Retention time (minutes) | Area (microvolt seconds) | % area | Height (microvolt) | |
| 1 | |
12.054 | 61752463 | 98.68 | 350115 |
| Mean | 12.054 | 61752463.425 | 350114.674 |
TABLE 4 comprehensive statistics of Peak 2 in the gel chromatogram of polysulfone prepared by the preparation method provided in comparative example 1
| Name (R) | Retention time (minutes) | Area (microvolt seconds) | % area | Height (microvolt) | |
| 1 | |
19.992 | 825130 | 1.32 | 29502 |
| Mean | 19.992 | 825129.575 | 29502.496 |
Comparative example 2
The preparation process provided in example 1 was used with the difference that: 0.25mol of benzyltrimethylammonium chloride was used instead of 0.25mol of PTC1 composite base catalyst.
Through detection, the preparation method provided by the comparative example 2 obtains the polysulfone, and the content of the bicyclic oligomer in the polymer is 1.49%, and the total content of the cyclic oligomer is 5.32%.
Comparative example 3
The preparation process provided in example 1 was used with the difference that: 0.25mol of dodecyltrimethylammonium chloride was used instead of 0.25mol of PTC1 composite base catalyst.
Through detection, the preparation method provided by the comparative example 3 obtains the polysulfone, and the content of the bicyclic oligomer in the polymer is 1.59%, and the total content of the cyclic oligomer is 4.69%.
Comparative example 4
The preparation process provided in example 1 was used with the difference that: 0.25mol of tetrabutylammonium bromide was used instead of 0.25mol of PTC1 complex base catalyst.
Through detection, the preparation method provided by the comparative example 4 obtains the polysulfone, and the content of the bicyclic oligomer in the polymer is 1.46%, and the total content of the cyclic oligomer is 4.86%.
Comparative example 5
The preparation process provided in example 8 was used, with the difference that: no PTC5 complex base catalyst was added.
Through detection, the preparation method provided by the comparative example 5 obtains polysulfone, and the polymer has the content of the bicyclic oligomer of 1.57% and the total content of the cyclic oligomer of 4.71%.
Comparative example 6
The preparation process provided in example 9 was used with the difference that: no PTC4 complex base catalyst was added.
Through detection, the polysulfone is obtained by the preparation method provided by the comparative example 6, and the content of the bicyclic oligomer in the polymer is 1.98%, and the total content of the cyclic oligomer is 5.09%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of polysulfone resin comprises the following steps:
a) carrying out polymerization reaction on a bisphenol monomer, a salt forming agent, a composite base catalyst and a double-halogen monomer in a solvent to obtain a polymer solution; the composite base catalyst contains a structure shown in a formula (I) or a formula (II);
wherein, -R1Is selected from-CH3Or
；-R2Is selected from-CH3、-CH2CH3Or
；-R3Is selected from-CH3、-CH2CH3；
b) And b) solidifying the polymer solution obtained in the step a) in water, crushing, and then sequentially washing, vacuum drying and granulating to obtain the polysulfone resin.
2. The method of claim 1, wherein the bisphenol monomer in step a) is selected from bisphenol a, bisphenol S, and 4, 4' -biphenol.
3. The method of claim 1, wherein the salt forming agent in step a) is selected from NaOH, KOH, K2CO3And K3PO4One or more of (a).
4. The preparation method of claim 1, wherein the amount of the composite base catalyst used in step a) is 0.1 to 3% of the molar amount of the bisphenol monomer.
5. The method of claim 1, wherein the dihalogen monomer in step a) is selected from 4,4 ' -dichlorodiphenyl sulfone, 4 ' -difluorodiphenyl sulfone or 4,4 ' -difluorobenzophenone.
6. The method of claim 1, wherein the molar ratio of bisphenol monomer, salt former, and bishaloid monomer in step a) is 1: (2-3): (0.8 to 1.2).
7. The preparation method of claim 1, wherein the polymerization reaction in step a) is carried out at a temperature of 70 ℃ to 220 ℃ for 1h to 15 h.
8. The method according to claim 1, wherein the polymerization reaction in step a) is carried out by:
dissolving a bisphenol monomer in a solvent, adding a salt forming agent and a composite base catalyst to carry out a water diversion reaction, then adding a double-halogen monomer to heat up, and carrying out a first polycondensation reaction to obtain a polymer solution;
or sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent for carrying out a water-splitting reaction, heating, and carrying out a second polycondensation reaction to obtain a polymer solution;
or sequentially adding a bisphenol monomer, a double-halogen monomer, a salt forming agent and a composite base catalyst into a solvent, heating, carrying out a third polycondensation reaction, and diluting to obtain a polymer solution.
9. The preparation method of claim 8, wherein the temperature of the water diversion reaction is 110-150 ℃ and the time is 5-7 h.
10. The preparation method of claim 1, wherein the temperature of the vacuum drying in the step b) is 100 ℃ to 150 ℃ and the time is 20h to 30 h.
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| WO2021031531A1 (en) * | 2019-08-22 | 2021-02-25 | 南京清研高分子新材料有限公司 | Polysulfone resin polymer material and preparation method therefor |
| CN116284763B (en) * | 2023-02-23 | 2024-06-04 | 华南理工大学 | Polyalkenamine compound containing cyclic/linear structure, and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050305A (en) * | 2006-04-07 | 2007-10-10 | Ht材料有限公司 | High temperature poly(aryl ether)s containing a phthalazinone moiety |
| CN105504284A (en) * | 2016-01-04 | 2016-04-20 | 中国科学院长春应用化学研究所 | Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof |
| CN105555819A (en) * | 2013-08-13 | 2016-05-04 | 费森尤斯医疗保健集团 | Process for making polyarylethers and use in membrane preparation |
| CN110527094A (en) * | 2019-08-22 | 2019-12-03 | 南京清研高分子新材料有限公司 | Reduce the preparation method of cyclic dimer in polysulfones resinous polymeric material |
| CN111072965A (en) * | 2019-08-22 | 2020-04-28 | 南京清研高分子新材料有限公司 | Polysulfone resin polymer material and preparation method thereof |
| WO2021099297A1 (en) * | 2019-11-19 | 2021-05-27 | Solvay Specialty Polymers Usa, Llc | Process for preparing a polysulfone (psu) polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010056175A1 (en) * | 1999-06-28 | 2001-12-27 | Selvaraj Savariar | Polysulfone films |
| EP3235854B1 (en) * | 2013-09-09 | 2023-06-28 | Basf Se | Polyarylene ether sulfone polymers for membrane applications |
| US9534086B2 (en) * | 2014-05-07 | 2017-01-03 | International Business Machines Corporation | Methods of forming poly(aryl ether sulfone)s and articles therefrom |
-
2019
- 2019-01-11 CN CN201910027089.3A patent/CN109721733B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050305A (en) * | 2006-04-07 | 2007-10-10 | Ht材料有限公司 | High temperature poly(aryl ether)s containing a phthalazinone moiety |
| CN105555819A (en) * | 2013-08-13 | 2016-05-04 | 费森尤斯医疗保健集团 | Process for making polyarylethers and use in membrane preparation |
| CN105504284A (en) * | 2016-01-04 | 2016-04-20 | 中国科学院长春应用化学研究所 | Polymer containing quaternary ammonium group, anion exchange membrane and preparation method thereof |
| CN110527094A (en) * | 2019-08-22 | 2019-12-03 | 南京清研高分子新材料有限公司 | Reduce the preparation method of cyclic dimer in polysulfones resinous polymeric material |
| CN111072965A (en) * | 2019-08-22 | 2020-04-28 | 南京清研高分子新材料有限公司 | Polysulfone resin polymer material and preparation method thereof |
| WO2021099297A1 (en) * | 2019-11-19 | 2021-05-27 | Solvay Specialty Polymers Usa, Llc | Process for preparing a polysulfone (psu) polymer |
Non-Patent Citations (5)
| Title |
|---|
| Polyphenylsulfone (PPSU) for baby bottles: a comprehensive assessment on polymer-related non-intentionally added substances (NIAS);Martin Eckardt，等;《FOOD ADDITIVES AND CONTAMINANTS PART A-CHEMISTRY ANALYSIS CONTROL EXPOSURE & RISK ASSESSMENT》;20171215;第35卷(第7期);第1421-1437页 * |
| Synthesis of Soluble Poly(arylene ether sulfone) Ionomers with Pendant Quaternary Ammonium Groups for Anion Exchange Membranes;Wang, Junhua，等;《MACROMOLECULES》;20090910;第42卷(第22期);第8711-8717页 * |
| Universal response quantification approach using a Corona Charged Aerosol Detector (CAD) - Application on linear and cyclic oligomers extractable from polycondensate plastics polyesters, polyamides and polyarylsulfones;Martin Eckardt，等;《JOURNAL OF CHROMATOGRAPHY A》;20181019;第1572卷;第187-202页 * |
| 官能化酚酞聚芳醚砜分离膜材料的制备与性能;张所波，等;《2015年全国高分子学术论文报告会论文摘要集——主题J 高性能高分子》;20151031;第13页 * |
| 新型共聚醚砜的合成及性能研究;张源;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080215(第2期);B016-24 * |
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