CN118765299A - Functionalized poly (aryl ether sulfone) copolymers - Google Patents
Functionalized poly (aryl ether sulfone) copolymers Download PDFInfo
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- CN118765299A CN118765299A CN202280092420.XA CN202280092420A CN118765299A CN 118765299 A CN118765299 A CN 118765299A CN 202280092420 A CN202280092420 A CN 202280092420A CN 118765299 A CN118765299 A CN 118765299A
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- 229920000110 poly(aryl ether sulfone) Polymers 0.000 title claims abstract description 44
- 229920001577 copolymer Polymers 0.000 claims abstract description 143
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 31
- 239000000178 monomer Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 21
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 17
- 229920001519 homopolymer Polymers 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011541 reaction mixture Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- -1 alkaline earth metal sulfonate Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 230000009477 glass transition Effects 0.000 claims description 11
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003568 thioethers Chemical class 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- BNXZHVUCNYMNOS-UHFFFAOYSA-N 1-butylpyrrolidin-2-one Chemical compound CCCCN1CCCC1=O BNXZHVUCNYMNOS-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 229910003827 NRaRb Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 claims description 4
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005600 alkyl phosphonate group Chemical group 0.000 claims description 4
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 150000003949 imides Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 3
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000002432 hydroperoxides Chemical class 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- UBKQRASXZMLQRJ-UHFFFAOYSA-N 2-phenylsulfanylethanamine Chemical compound NCCSC1=CC=CC=C1 UBKQRASXZMLQRJ-UHFFFAOYSA-N 0.000 claims 2
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 claims 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229920002492 poly(sulfone) Polymers 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920006393 polyether sulfone Polymers 0.000 description 16
- 239000004695 Polyether sulfone Substances 0.000 description 15
- 229920000491 Polyphenylsulfone Polymers 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 150000003457 sulfones Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003880 polar aprotic solvent Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000007717 exclusion Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 2
- OGMADIBCHLQMIP-UHFFFAOYSA-N 2-aminoethanethiol;hydron;chloride Chemical compound Cl.NCCS OGMADIBCHLQMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000090 biomarker Substances 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- 229940097265 cysteamine hydrochloride Drugs 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001631 haemodialysis Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000000322 hemodialysis Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229960003151 mercaptamine Drugs 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 238000003303 reheating Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000013374 right angle light scattering Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 1
- IBSQPLPBRSHTTG-UHFFFAOYSA-N 1-chloro-2-methylbenzene Chemical compound CC1=CC=CC=C1Cl IBSQPLPBRSHTTG-UHFFFAOYSA-N 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 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 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000000746 allylic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229960002685 biotin Drugs 0.000 description 1
- 235000020958 biotin Nutrition 0.000 description 1
- 239000011616 biotin Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
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- FRTIVUOKBXDGPD-UHFFFAOYSA-M sodium;3-sulfanylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CCCS FRTIVUOKBXDGPD-UHFFFAOYSA-M 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
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- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention relates to side chain functionalized poly (aryl ether sulfone) (PAES) copolymers (P1), to a process for preparing such copolymers (P1), and to their use in the preparation of films, composites or coatings. The copolymer (P1) comprises PAES repeat units (RP 1) and PAES side chain functionalized repeat units (R P1).
Description
Cross Reference to Related Applications
The present application claims priority from U.S. provisional patent application No. 63/293106 filed on 12 months 23 and european patent application No. 22161495.1 filed on 3 months 11 of 2022, the entire contents of which are incorporated herein by reference for all purposes.
Technical Field
The present disclosure relates to a side chain functionalized copolymer (P1) and a method for preparing the side chain functionalized copolymer (P1). The invention also relates to the use of the copolymer (P1) for producing functional films (i.e. hydrophobic, hydrophilic, biomarker fluorescent tagged films), the use of the copolymer (P1) in composite materials, 3D printing applications, and the use of the copolymer (P1) in functional coatings.
Background
Poly (aryl ether sulfone) (PAES) polymers belong to the group of high performance thermoplastics and are characterized by high heat distortion resistance, good mechanical properties, excellent hydrolysis resistance, and inherent flame retardancy. General and useful PAES polymers have many applications in electronics, electrical industry, medicine, general engineering, food processing, and 3D printing. PAES polymers can be used in injection molded articles, composites and membranes (e.g., for water purification or hemodialysis).
PAES are typically made by polycondensation reactions using dihalodiphenylsulfones (sulfone monomers) and at least one aromatic diol monomer such as bisphenol a ("BPA"), biphenol ("BP"), or dihydroxydiphenyl sulfone (DHDPS) (also known as bisphenol S ("BPs")).
A commercially important group of PAES comprises polysulfone polymers, herein referred to as polysulfones, PSUs for short. PSU polymers contain repeat units derived from the condensation of BPA and dihalogen sulfone monomers, such as 4,4' -dichlorodiphenyl sulfone (DCDPS). Such PSU polymers are sold under the trademark Solvi specialty Polymer Co., ltd (Solvay Specialty Polymers USA, LLC)Are commercially available. The Tg of PSU is typically 185 ℃. The structure of the repeat unit of such PSU polymers is shown below:
another important group of PAES includes polyethersulfone polymers, abbreviated PES. PES polymers are derived from the condensation of BPS and dihalogen sulfone monomers (e.g., DCDPS). Such PES polymers are commercially available from Solvin specialty polymers, inc. of USA Are commercially available. The Tg of PES is typically 220 ℃. The structure of the repeating unit of such PES polymer is as follows:
another important group of PAES includes poly (biphenyl ether sulfone) polymers, abbreviated PPSU. PPSU is made by reacting 4,4' -Biphenol (BP) and a dihalosulfone monomer (e.g., DCDPS), and is notable for its trade name from the american sorv specialty polymer company, inc Are commercially available. The Tg of PPSU is typically 220 ℃. The structure of the repeat unit of such PPSU polymer is shown below:
while PAES polymers have many advantages and good physical properties, it is sometimes desirable to tailor these properties to improve performance in specific applications. For example, in membrane filtration, it is sometimes desirable to increase the hydrophilicity of PAES to improve key membrane performance attributes, such as flow rate. Modification of the basic properties, including but not limited to hydrophilicity, is often achieved by combining two homopolymers to prepare block copolymers having a combination of the inherent properties of each individual homopolymer. For example, in membrane applications, PAES homopolymers may be covalently linked to hydrophilic homopolymers to synthesize new PAES-hydrophilic block copolymers that have superior membrane properties due to enhanced flow induced by the hydrophilic component, while retaining the mechanically robust and amorphous pore structure of the PAES component.
The present invention provides a side chain functionalized copolymer and a process for preparing such a copolymer. These functionalized copolymers are complex polymer structures that can be used in potentially diverse applications, such as for the preparation of films, composites and coatings.
Disclosure of Invention
One aspect of the present disclosure relates to a side chain functionalized poly (aryl ether sulfone) (PAES) copolymer (P1) as defined in claim 1. The copolymer (P1) comprises poly (aryl ether sulfone) (PAES) repeat units (R P1), and PAES repeat units having pendant groups (R x P1), more precisely PAES repeat units functionalized with pendant groups (R x P1).
The repeating unit (R P1) contains thioether functionalities which have several advantages. It is a stable but at the same time multifunctional functional group that can be easily modified to fine tune the properties of the PAES copolymer (P1).
The glass transition temperature Tg of the copolymer (P1) is equal to or greater than the Tg h of a homopolymer consisting essentially of identical repeating units (R P1), preferably measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418. The copolymer (P1) preferably has a Tg > Tg h, more preferably a Tg of > 5 ℃ plus Tg h, yet more preferably a Tg of > 7 ℃ plus Tg h, yet even more preferably a Tg of > 10 ℃ plus Tg h.
The invention also relates to a process for preparing the copolymer (P1) from the copolymer (P0) comprising allyl groups and/or functional groups containing carbon-carbon double bonds which are reactive and can therefore be used to effectively modify the copolymer. Thus, the present invention provides a method of introducing functionality into PAES polymers, and the resulting copolymers can then be further used in various applications, such as for preparing films.
The invention also relates to the use of the copolymer (P1) for producing films, composite materials or coatings.
Disclosure of the invention
In the present application:
even though any of the descriptions described with respect to specific embodiments are applicable to and interchangeable with other embodiments of the present disclosure;
When an element or component is said to be included in and/or selected from the list of enumerated elements or components, it is to be understood that in the relevant embodiments explicitly contemplated herein, the element or component may also be any one of these enumerated independent elements or components, or may also be selected from the group consisting of any two or more of the enumerated elements or components; any elements or components recited in a list of elements or components may be omitted from this list; and
Any recitation of numerical ranges herein by endpoints includes all numbers subsumed within that range, and the endpoints and equivalents of that range.
In the present application:
the term "comprising" includes "consisting essentially of … …" (consisting essentially of or consist essentially of) and "consisting of … …" (consisting of or consist of);
As used herein, the singular of 'a (a)' or 'a (one)' includes the plural unless specifically stated otherwise; and
It should be understood that elements, features and/or characteristics of a (co) polymer, product or article, method or use described in this specification may be combined in all possible ways with other elements, features and/or characteristics of the (co) polymer, product or article, method or use, either explicitly or implicitly, without departing from the scope of this specification.
The term "consisting essentially of … …" in relation to compositions, products, articles, polymers, processes, methods, and the like is intended to mean that any additional elements or features that may not be explicitly described herein and that do not materially affect the basic and novel characteristics of such compositions, products, articles, polymers, processes, methods, and the like may be included in such embodiments.
In the present disclosure, the term "repeating unit" refers to the smallest unit of the PAES polymer that repeats in the chain and consists of the condensation of a diol compound and a dihalo compound. The term "repeat unit" is synonymous with the terms "repeat unit (REPEATING UNIT)" and "structural unit".
As used herein, the term "homopolymer" encompasses polymers having only one type of repeating unit.
As used herein, the term "copolymer" encompasses polymers having two or more different types of repeating units.
Copolymer (P1)
The invention relates to a copolymer (P1) functionalized with side chains. The copolymer (P1) comprises at least two types of repeating units, namely a repeating unit (R P1) having formula (M) and a repeating unit (R x P1) having formula (N) described below. The repeating units (R P1) are functionalized with functional groups, which may be selected from the group consisting of:
- (CH 2)j-S-R2) wherein j is an integer of 3 to 7, and/or
- (CH 2)k-CH-CH2(CH3)-S-R2) wherein k is an integer of 0 to 4,
And R 2 is independently selected from the group consisting of:
- (CH 2)u -COOH, where u is an integer of 1 to 5, preferably u is 1 or 2,
- (CH 2)k -OH, where k is an integer from 1 to 5, preferably k is 1 or 2,
- (CH 2)p-NRaRb) wherein p is an integer from 1 to 5, and a and b are independently C1-C6 alkyl or H, provided that R a and R b cannot both be CH 3, -preferably-NR aRb is-NH 2, and preferably p is 1 or 2,
- (CH 2)q-SO3 Na in which q is an integer from 1 to 5, preferably q is 1,2 or 3,
- (CH 2)a-COCH3) wherein a is an integer of 0 to 10,
- (CH 2)r-Si(OCH3)3) wherein r is an integer from 1 to 5, preferably r is 1,2 or 3,
- (CH 2)s-(CF2)t-CF3) wherein s is an integer from 1 to 5, preferably 1 or 2, and t is an integer from 1 to 10, preferably between 5 and 9,
-C (O) -R c, wherein R c is C1-C6 alkyl or H, preferably H,
- (CH 2)v-CH3) wherein v is an integer of 5 to 30, preferably v is an integer of 8 to 20, and
- (CH 2) w-Ar, wherein w is an integer of 1 to 10, and Ar comprises one or two aromatic or heteroaromatic rings, for example one or two benzene rings.
The functional groups of the copolymer (P1) are internal functionalization within the copolymer backbone. Internal functionalization results from a stepwise polymerization in the presence of allyl-substituted monomers, which advantageously gives the system versatility since the content of functionality can be adjusted by varying the content of allyl-substituted monomers in the reaction mixture. The allyl-substituted monomer comprises two pendant allyl side chains, each side chain comprising 3 to 7 carbon atoms according to the invention.
The copolymer (P1) of the present invention comprises:
-a repeating unit (R P1) having formula (M):
-a repeating unit (R x P1) having formula (N):
Wherein the method comprises the steps of
-Each R 1 is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;
-each i is an integer independently selected from 0 to 4;
-T is selected from the group consisting of: bond 、-CH2-;-O-;-SO2-;-S-;-C(O)-;-C(CH3)2-;-C(CF3)2-;-C(＝CCl2)-;-C(CH3)(CH2CH2COOH)-;-N＝N-;-RaC＝CRb-, wherein R a and R b are each, independently of one another, hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; - (CH 2)m -and- (CF 2)m -, wherein m is an integer from 1 to 6), straight or branched aliphatic divalent radicals having up to 6 carbon atoms, and combinations thereof;
-G N is selected from the group consisting of at least one of the following formulae (G N1) to (G N6):
wherein, in the formulas (G N1) to (G N6),
-W is a bond or-SO 2 -, preferably-SO 2 -;
-each k is independently an integer from 0 to 4;
-each j is independently an integer from 3 to 7;
-each R 2 is independently selected from the group consisting of:
- (CH 2)u -COOH wherein u is an integer of 1 to 5, provided that when T and W are both-SO 2 -, then u is not 1 or 2,
- (CH 2)k -OH, wherein k is an integer of 1 to 5,
- (CH 2)p-NRaRb) wherein p is an integer from 1 to 5, and a and b are independently C1-C6 alkyl or H, provided that R a and R b cannot both be CH 3,
- (CH 2)q-SO3 Na in which q is an integer of 1 to 5,
- (CH 2)a-COCH3) wherein a is an integer of 0 to 10
- (CH 2)r-Si(OCH3)3) wherein r is an integer of 1 to 5,
- (CH 2)s-(CF2)t-CF3) wherein s is an integer of 1 to 5, and t is an integer of 1 to 10,
-C (O) -R c, wherein R c is C1-C6 alkyl or H, preferably H,
- (CH 2)v-CH3) wherein v is an integer of 5 to 30, and
- (CH 2)w -Ar, wherein w is an integer from 1 to 10, and Ar comprises one or two aromatic or heteroaromatic rings, for example one or two benzene rings, and wherein the glass transition temperature Tg of the copolymer (P1) is equal to or greater than Tg h, preferably Tg > Tg h, more preferably Tg > 5 ℃ + Tg h, still more preferably Tg > 7 ℃ + Tg h, still even more preferably Tg > 10 ℃ + Tg h of a homopolymer consisting essentially of the same repeat unit (R P1), preferably measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418.
The copolymer (P1) of the present invention is in the form of a racemate product. Due to the presence of base and the high temperature during polymerization, allylic substituted monomers are typically racemized during polymerization in such a way that the position of the double bond may vary along the side chain. This results in the formation of molecules that differ from each other in that the double bond may be at the end of the side chain or at one carbon before the end of the side chain. The amount of racemization depends on the reaction time and temperature.
In some embodiments, copolymer (P1) is such that in the repeating unit (R P1), T is selected from the group consisting of a bond, -SO 2-、-C(CH3)2 -, and mixtures thereof. The copolymers (P1) according to the invention may, for example, comprise recurring units (R P1) in which T is-C (CH 3)2 -and recurring units (R P1) in which T is-SO 2 -.
T in the repeating unit (R P1) is preferably-C (CH 3)2 -.
In some embodiments, copolymer (P1) is such that each R 1 is independently selected from the group consisting of: a C1-C12 moiety optionally comprising one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.
In some embodiments, the copolymer (P1) is such that for each R 1 of the repeating unit (R P1) and the repeating unit (R x P1), i is zero.
In some embodiments, copolymer (P1) is such that the repeating unit (R P1) is according to formula (M1), (M2), or (M3):
in some embodiments, copolymer (P1) is such that it comprises:
-wherein the group G N is a repeating unit (R x P1) according to formula (G N1), preferably at least 25mol.%, more preferably at least 30mol.%, even more preferably 35mol.% of repeating units (R x P1) are such that the group G N is according to formula (G N1);
-wherein the group G N is a repeating unit (R x P1) according to formulae (G N1) and (G N6), preferably at least 35mol.%, more preferably at least 40mol.%, even more preferably 45mol.% of repeating units (R x P1) are such that the group G N is according to formulae (G N1) and (G N6); or (b)
-Wherein the group G N is at least a repeating unit (R x P1) according to formulae (G N1)、(GN4) and (G N6), preferably at least 50mol.%, more preferably at least 60mol.%, even more preferably 70mol.%, 80mol.% or 90mol.% of repeating units (R x P1) is such that the group G N is according to formulae (G N1) and (G N6).
In some embodiments, copolymer (P1) is such that in repeating unit (R P1), k is zero and j is 3.
In some embodiments, copolymer (P1) is such that in the repeating unit (R P1), W is-SO 2 -.
In some embodiments, the copolymer (P1) is such that the molar ratio of repeating units (R P1)/repeating units (R P1) varies between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1, more preferably between 1/1 and 12/1, even more preferably between 4/1 and 10/1.
In some embodiments, copolymer (P1) is such that R 2 in the repeating unit (R P1) is independently selected from the group consisting of:
-CH2-COOH，
-(CH2)2-OH，
-(CH2)2-NH2，
-(CH2)3-SO3Na，
-(CH2)3-Si(OCH3)3，
-(CH2)2-(CF2)7-CF3，
-CHO，
- (CH 2)9-CH3, and
-CH 2 -Ph, wherein Ph is benzene.
In some embodiments, copolymer (P1) comprises at least 50mol.% total of repeating units (R P1) and (R x P1) based on the total moles in copolymer (P1). The copolymer (P1) may for example comprise at least 60mol.%, at least 70mol.%, at least 80mol.%, at least 90mol.%, at least 95mol.%, at least 99mol.% of recurring units (R P1) and (R x P1) in total based on the total moles of the copolymer (P1). The copolymer (P1) may preferably consist essentially of recurring units (R P1) and (R x P1).
The glass transition temperature Tg of the PAES copolymer (P1) is preferably greater than Tg h of a homopolymer consisting essentially of identical PAES repeat units (R P1), more preferably Tg.gtoreq.5deg.C+Tg h, still more preferably Tg.gtoreq.7deg.C+Tgh, yet even more preferably Tg.gtoreq.10deg.C+Tg h.
When PAES repeat unit (R P1) has formula (M1) and the corresponding homopolymer is PSU having Tg h of about 185 ℃, PAES copolymer (P1) comprising the same PAES repeat unit (R P1) having formula (M1) and functionalized repeat unit (R P1) having formula (N) (wherein in formulae (G N1) to (G N6) W is a bond or-SO 2 -, preferably-SO 2 -) Tg > Tg PSU, preferably Tg > 3 ℃ + Tg PSU, more preferably Tg > 5 ℃ + Tg PSU, still more preferably Tg > 7 ℃ + Tg PSU, yet even more preferably Tg > 10 ℃ + Tg PSU.
When PAES repeat unit (R P1) has formula (M2) and the homopolymer corresponds to PPSU having a Tg h of about 220 ℃, PAES copolymer (P1) comprising the same PAES repeat unit (R P1) having formula (M2) and a functionalized repeat unit (R P1) having formula (N) (wherein in formulae (G N1) to (G N6) W is a bond or a glass transition temperature Tg of-SO 2 -, preferably-SO 2 -) > Tg PPSU, preferably Tg > 3 ℃ + Tg PPSU, more preferably Tg > 5 ℃ + Tg PPSU, still more preferably Tg > 7 ℃ + Tg PPSU, yet even more preferably Tg > 10 ℃ + Tg PPSU.
When PAES repeat unit (R P1) has formula (M3) and the homopolymer corresponds to PES having a Tg h of about 220 ℃, PAES copolymer (P1) comprising the same PAES repeat unit (R P1) having formula (M3) and a functionalized PAES repeat unit (R P1) having formula (N) (wherein in formulae (G N1) to (G N6) W is a bond or-SO 2 -, preferably-SO 2 -) Tg > Tg PES, preferably Tg > 3 ℃ + Tg PES, more preferably Tg > 5 ℃ + Tg PES, still more preferably Tg > 7 ℃ + Tg PES, yet even more preferably Tg > 10 ℃ + Tg PES.
This is in contrast to what is described for the functionalized PAES copolymers in WO 2020/187684 A1 and WO 2021/123405 A1, in which cysteamine is used during the synthesis, wherein the copolymers described in the examples have a glass transition temperature Tg which is less than the Tg of their corresponding homopolymers. The functionalized PSU copolymer (P1-C) of WO'684 prepared with cysteamine hydrochloride had a Tg of 175 ℃ (< Tg PSU). The functionalized PSU copolymers (P1-A), (P1-B) and (P1-E) of WO'405 have Tg (< Tg PSU) at 150 ℃, 143 ℃ and 162 ℃. These functionalized PSU polymers were prepared from copolymer precursors made using DCDPS, diallyl bisphenol a, and bisphenol a. The functionalized PPSU copolymer (P1-C) of WO '405 has a Tg (< Tg PPSU) of 170 ℃ and the functionalized PPSU copolymer (P1-C) is prepared from a copolymerization precursor made using DCDPS, diallyl bisphenol a and 4,4' -biphenol. The functionalized PES copolymer of WO'405 (P1-D) has a Tg of 190 ℃ (< Tg PES) and is prepared from copolymer precursors made using DCDPS, diallyl bisphenol a and bisphenol S.
The copolymer (P1) of the present invention may have a glass transition temperature Tg ranging from 170℃to 240℃or 185℃to 240℃and preferably from 190℃to 240℃and more preferably from 195℃to 240℃or from 200℃to 235 ℃.
The glass transition temperature is preferably measured according to ASTM D3418, preferably by Differential Scanning Calorimetry (DSC). For example, DSC measurements can be performed using Q100 from TA instruments (TA instruments) and under a nitrogen purge. The DSC profile was recorded by heating, cooling, reheating and then cooling the sample between 25 ℃ and 320 ℃ at a heating and cooling rate of 20 ℃/min. The second heating curve was used to provide reported Tg values unless indicated otherwise.
The thioether bond-S-R 2 contained in the repeating unit (R P1) has several advantages. First, the thioether linkage is a stable, non-hydrolyzable linkage, which is important for applications in membranes, especially for medical applications. Moreover, the thioether bond is a highly biocompatible and biostable bond, and thus can be used in hemodialysis applications; many bioactive molecules contain thioether moieties, such as biotin. However, after treatment with a suitable oxidizing agent (like hydrogen peroxide), this bond can be oxidized to form a sulfoxide and sulfone linkage. In addition, the thioether can be easily alkylated with an alkyl halide to form a sulfonium salt; the polymeric sulfonium salt can then be used in chemical conversions, such as epoxidation. In addition, thioethers can coordinate or bind to heavy metals, and thus the copolymers of the present invention can be used as polymeric ligands for metal removal.
The copolymers (P1) according to the invention can also be characterized by their end groups. The polymer end groups are part of the respective ends of the PAES copolymer (P1) chain.
Depending on the monomers used to prepare the copolymer (P0), from which the copolymer (P1) is prepared, and the additional end-capping agent possibly used during the polycondensation process, or the protonating agent possibly added after polymerization (in order to obtain phenolic-OH end groups), the copolymer (P1) may, for example, have end groups derived from the monomers and/or end groups derived from the end-capping agent. Since the copolymers (P0) are generally produced by polycondensation between at least two dihydroxy components and dihalogenated components and without end-capping agents, the end groups of the copolymers (P1) generally comprise, or preferably consist of, hydroxy end groups and halogenated end groups, such as chlorinated end groups. The production of the copolymer (P0) from which the copolymer (P1) is derived preferably excludes the use of aminophenols as end-capping agents, which at least partially convert some of the halogenated end groups into amine end groups. The concentration of hydroxyl end groups can be determined by titration. The concentration of halogen groups can be determined with a halogen analyzer. However, any suitable method may be used to determine the concentration of end groups. For example, titration, NMR, FTIR, or halogen analyzers may be used.
Process for preparing copolymer (P1)
The copolymer (P1) may be prepared by various chemical methods, for example, by a radical thermal reaction, a radical UV reaction, a base catalytic reaction or a nucleophilic catalytic reaction.
The process for preparing the copolymer (P1) comprises reacting an allyl/vinylidene-functionalized copolymer (P0) with a compound having formula (I):
R2-SH，(I)
wherein R 2 is independently selected from the group consisting of:
- (CH 2)u -COOH, where u is an integer of 1 to 5, preferably u is 1 or 2,
- (CH 2)k -OH, where k is an integer from 1 to 5, preferably k is 1 or 2,
- (CH 2)p-NRaRb) wherein p is an integer from 1 to 5, and a and b are independently C1-C6 alkyl or H, provided that R a and R b cannot both be CH 3, p is preferably 1 or 2, and R a and R b are preferably CH 3 or H,
- (CH 2)q-SO3 Na in which q is an integer from 1 to 5, preferably q is 1,2 or 3,
- (CH 2)a-COCH3) wherein a is an integer of 0 to 10,
- (CH 2)r-Si(OCH3)3) wherein r is an integer from 1 to 5, preferably r is 1,2 or 3,
- (CH 2)s-(CF2)t-CF3) wherein s is an integer of 1 to 5, preferably 1 or 2, and t is an integer of 1 to 10, preferably 5 to 9, and
-C (O) -R c, wherein R c is C1-C6 alkyl or H, preferably H,
- (CH 2)v-CH3) wherein v is an integer from 5 to 30, preferably v is selected from 8 to 20, and
- (CH 2)w -Ar) wherein w is an integer of 1 to 10, and Ar comprises one or two aromatic or heteroaromatic rings, for example one or two benzene rings.
The copolymer (P0) used in the process of the present invention comprises recurring units (R P0) with 2 pendant allyl/vinylidene side chains, which recurring units are reactive with the compounds R 2 -SH. The copolymer (P0) more precisely comprises:
-a repeating unit (R P0) having formula (M):
-a repeating unit (R x P0) having formula (P):
Wherein the method comprises the steps of
-Each R 1 is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;
-each i is independently selected from 0 to 4;
-T is selected from the group consisting of: bond 、-CH2-;-O-;-SO2-;-S-;-C(O)-;-C(CH3)2-;-C(CF3)2-;-C(＝CCl2)-;-C(CH3)(CH2CH2COOH)-;-N＝N-;-RaC＝CRb-, wherein R a and R b are each, independently of one another, hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; - (CH 2)m -and- (CF 2)m -, wherein m is an integer from 1 to 6), a straight or branched aliphatic divalent group having up to 6 carbon atoms, and combinations thereof,
-G p is selected from the group consisting of at least one of the following formulae (G P1) to (G P3):
Wherein:
-W is a bond or-SO 2 -, preferably-SO 2 -;
-each k is independently an integer from 0 to 4.
When T and W are both-SO 2 -, then u is not equal to 1 or 2.
In some embodiments, copolymer (P0) is such that in the repeating unit (R P0), k is zero.
The reaction for preparing the copolymer (P1) is preferably carried out in a solvent. When the reaction for producing the copolymer (P1) is carried out in a solvent, for example, a polar aprotic solvent selected from the group consisting of: n-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), 1, 3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), chlorobenzene, anisole and sulfolane. The solvent may also be chloroform or Dichloromethane (DCM). The reaction for preparing the copolymer (P1) is preferably carried out in sulfolane or NMP.
The molar ratio of compound/polymer (P0) having formula (I) may vary between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1, more preferably between 1/1 and 10/1.
The temperature of the reaction used to prepare the copolymer (P1) varies between 10℃and 300℃and preferably between room temperature and 200℃or more preferably between 35℃and 100 ℃.
In some embodiments, copolymer (P0) is such that T in repeating unit (R P0) is selected from the group consisting of a bond, -SO 2-、-C(CH3)2 -, and any mixtures thereof. The copolymer (P0) may, for example, comprise repeat units (R P0) in which T is-C (CH 3)2 -and repeat units (R P1) in which T is-SO 2 -.
T in the repeating unit (R P0) is preferably-C (CH 3)2 -.
In some embodiments, the copolymer (P0) is such that each R 1 is independently selected from the group consisting of: a C1-C12 moiety optionally comprising one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.
In some embodiments, the copolymer (P0) is such that for each R 1 of the repeating unit (R P0) and the repeating unit (R x P0), i is zero.
In some embodiments, copolymer (P0) is such that in repeating unit (R P0), j is 2.
In some embodiments, the copolymer (P0) is such that the molar ratio of repeating units (R P0)/repeating units (R x P0) varies between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1.
In some embodiments, copolymer (P0) is such that repeat unit (R P0) is according to formula (M1), (M2), or (M3):
In some embodiments, copolymer (P0) comprises at least 50mol.% total of repeating units (R P0) and (R x P0) based on the total moles in copolymer (P0). The copolymer (P0) may for example comprise at least 60mol.%, at least 70mol.%, at least 80mol.%, at least 90mol.%, at least 95mol.%, at least 99mol.% of recurring units (R P0) and (R x P0) in total based on the total moles of the copolymer (P0). The copolymer (P0) preferably consists essentially of recurring units (R P0) and (R x P0).
The glass transition temperature Tg of the copolymer (P0) is equal to or greater than Tg h of a homopolymer consisting essentially of the same repeating units (R P0), preferably having a Tg > Tgh, more preferably having a Tg of > 5 ℃ plus Tgh, still more preferably having a Tg of > 7 ℃ plus Tgh, still more preferably having a Tg of > 10 ℃ plus Tgh, preferably as measured by Differential Scanning Calorimetry (DSC) according to ASTM D3418.
This is in contrast to what is described for the functionalized PAES copolymers in WO 2020/187684 A1 and WO 2021/123405 A1, in which cysteamine is used during the synthesis, in which the Tg of the copolymer (P0) described in its examples is smaller than that of its corresponding homopolymer. The allyl/vinylidene modified PSU copolymer (P0-a) of WO'684 has a Tg (< TgPSU) of 175 ℃. The allyl/vinylidene modified PSU copolymers (P0-a) and (P0-B) of WO'405 have Tg (< TgPSU) of 160.5 ℃ and 154 ℃ and these copolymer precursors were made using DCDPS, diallyl bisphenol a and bisphenol a. The allyl/vinylidene modified PPSU copolymer (P0-C) of WO '405 has a Tg (< TgPPSU) of 179 ℃ and the copolymer precursor (P0-C) is made using DCDPS, diallyl bisphenol a and 4,4' -biphenol. The allyl/vinylidene modified PES copolymer of WO'405 (P0-D) has a Tg of 187 ℃ (< Tg PES) and the copolymer precursor (P0-D) is made using DCDPS, diallyl bisphenol a and bisphenol S.
According to embodiments, the copolymer (P0) of the present invention may have a Tg ranging from 170 ℃ to 240 ℃, preferably 180 ℃ to 240 ℃ or 185 ℃ to 240 ℃, more preferably 190 ℃ to 240 ℃, still more preferably 195 ℃ to 240 ℃ or 195 ℃ to 235 ℃, as measured by DSC as described herein.
In some embodiments, the compounds R 2 -SH for reaction with copolymer (P0) are such that R 2 in the repeating unit (R x P1) is independently selected from the group consisting of:
-CH2-COOH，
-(CH2)2-OH，
-(CH2)2-NH2，
-(CH2)3-SO3Na，
-(CH2)3-Si(OCH3)3，
-(CH2)2-(CF2)7-CF3，
-CHO，
- (CH 2)9-CH3, and
-CH 2 -Ph, wherein Ph is benzene.
In some embodiments, the reaction used to prepare copolymer (P1) may be performed in the presence of a base, for example selected from the group consisting of: potassium carbonate (K 2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2CO3), cesium carbonate (Cs 2CO3) and sodium tert-butoxide. The base may also be selected from the group consisting of N-ethyl-N- (prop-2-yl) prop-2-amine (henigy (huntg) base), triethylamine (TEA) and pyridine.
In some embodiments, the reaction used to prepare copolymer (P1) may be performed in the presence of:
at least one radical initiator, preferably 2,2' -azobis (2-methylpropanenitrile) (AIBN), and/or
At least one catalyst, preferably chosen from peroxides and hydroperoxides.
According to embodiments, the amount of copolymer (P1) at the end of the reaction is at least 10wt.%, e.g., at least 15wt.%, at least 20wt.%, or at least 30wt.%, based on the total weight of copolymer (P0) and solvent.
At the end of the reaction, the copolymer (P1) is separated from the other components (salt, base, … …) to obtain a solution. Filtration may be used, for example, to separate the copolymer (P1) from the other components. The solution may then be used as is to react the copolymer (P1) with other compounds, or alternatively the copolymer (P1) may be recovered from the solvent, for example by coagulation or devolatilization of the solvent.
Process for preparing copolymer (P0)
In some embodiments, the allyl/vinylidene-functionalized copolymer (P0) used in the process of the present invention is prepared by condensation of at least one aromatic dihydroxy monomer (a 1) with at least one aromatic sulfone monomer (a 2) comprising at least two halogen substituents and at least one allyl-substituted aromatic dihydroxy monomer (a 3).
The condensation for preparing the copolymer (P0) is preferably carried out in a solvent. When the condensation used to prepare the copolymer (P0) is carried out in a solvent, for example, a polar aprotic solvent selected from the group consisting of: n-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N Dimethylformamide (DMF), N Dimethylacetamide (DMAC), 1, 3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), chlorobenzene and sulfolane. The condensation used to prepare the copolymer (P0) is preferably carried out in sulfolane or NMP.
The condensation used to prepare the copolymer (P0) may be carried out in the presence of a base, for example selected from the group consisting of: potassium carbonate (K 2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na 2CO3), cesium carbonate (Cs 2CO3) and sodium tert-butoxide. The base is used to deprotonate components (a 1) and (a 3) during the condensation reaction.
The molar ratio (a 1) + (a 3)/(a 2) may be 0.9 to 1.1, for example 0.92 to 1.08, or 0.95 to 1.05.
In some embodiments, monomer (a 2) is a 4, 4-dihalogenated sulfone comprising at least one of 4,4 '-dichlorodiphenyl sulfone (DCDPS) or 4,4' difluorodiphenyl sulfone (DFDPS), preferably DCDPS.
In some embodiments, monomer (a 1) comprises at least 50wt.% 4,4 'dihydroxybiphenyl (bisphenol), at least 50wt.% 2, 2-bis (4-hydroxyphenyl) propane (bisphenol a), or at least 50wt.% 4,4' dihydroxydiphenyl sulfone (bisphenol S), based on the total weight of monomer (a 1).
In some embodiments, monomer (a 3) comprises at least 50wt.% 2,2' -diallyl bisphenol a (DABA) based on the total weight of monomer (a 1).
Depending on the condensation used to prepare the copolymer (P0), the monomers of the reaction mixture are generally reacted simultaneously. The reaction is preferably carried out in one stage. This means that the deprotonation of the monomers (a 1) and (a 3) and the condensation reaction between the monomers (a 1)/(a 3) and (a 2) take place in a single reaction stage without isolation of the intermediates.
According to an embodiment, the condensation is carried out in a mixture of a polar aprotic solvent and a solvent forming an azeotrope with water. Solvents that form azeotropes with water include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene, and the like. It is preferably toluene or chlorobenzene. The azeotrope-forming solvent and the polar aprotic solvent are typically used in a weight ratio of about 1:10 to about 1:1, preferably about 1:5 to about 1:1. Water is continuously removed from the reaction mass as an azeotrope with the solvent that forms the azeotrope so that substantially anhydrous conditions are maintained during polymerization. After removal of the water formed in the reaction, the solvent forming the azeotropic mixture (e.g. chlorobenzene) is removed from the reaction mixture, typically by distillation, to dissolve the copolymer (P0) in the polar aprotic solvent.
The temperature of the reaction mixture used to prepare copolymer (P0) is maintained at about 150℃to about 350℃and preferably about 210℃to about 300℃for about 1 hour to 15 hours.
The inorganic component (e.g., sodium chloride or potassium chloride or an excess of alkali) may be removed by a suitable method (e.g., dissolution and filtration, sieving or extraction) before or after the separation of the copolymer (P0).
According to embodiments, the amount of copolymer (P0) at the end of condensation is at least 30wt.%, e.g., at least 35wt.%, or at least 37wt.%, or at least 40wt.%, based on the total weight of copolymer (P0) and polar aprotic solvent.
At the end of the reaction, the copolymer (P0) is separated from the other components (salt, base, … …) to obtain a solution. Filtration may be used, for example, to separate the copolymer (P0) from the other components. The solution may then be used as such in the process of the invention to react the copolymer (P0) with the compounds R 2 -SH, or alternatively the copolymer (P0) may be recovered from the solvent, for example by coagulation or devolatilization of the solvent.
Application of
The copolymer (P1) of the present invention can be used for producing a functional film. For example, these membranes may be hydrophobic, hydrophilic, biomarker, such as a membrane with a fluorescent label.
The copolymers (P1) according to the invention can also be used for preparing composite materials. In this application, the functionality improves the adhesion of the resin to the reinforcing fibers, thereby improving performance.
The copolymers (P1) according to the invention can also be used for the preparation of functional coatings. The chemical moieties on the surface of the coating may be selected to render the coating hydrophobic, hydrophilic, biomarker-able, antimicrobial, stain-resistant, and/or UV curable.
The disclosure of any patent, patent application, or publication that incorporates the application by reference should be given priority if it conflicts with the description of the present application to the extent that the term "does not become clear".
The invention will now be described in more detail with reference to the following examples, which are intended to be illustrative only and do not limit the scope of the invention.
Examples
Raw materials
DCDPS (4, 4' -dichlorodiphenyl sulfone) available from Sorvy specialty Polymer Co
BPA (bisphenol A), available from Korschner Inc. (Covestro)
BP (biphenol), polymer grade, available from Nippon Chemie Co., ltd. (Honshu Chemicals)
DaBPA-S (2, 2' -diallyl bisphenol S) is available from Toronto research chemical Co (Toronto RESEARCH CHEMICALS).
K 2CO3 (Potassium carbonate) obtainable from Armand Products
NMP (2-methylpyrrolidone), available from Sigma Aldrich, USA
MCB (methyl chlorobenzene), available from sigma Aldrich, USA
ADVN (2, 2' -azobis (2, 4-dimethylvaleronitrile)), available from Miller-stevenson chemical company, usa (Miller-Stephenson Chemical co., inc)
AIBN (2, 2-azobis (2-methylpropanenitrile)), available from sigma Aldrich, USA
Test method
GPC-molecular weight (Mn, mw)
Method 1: molecular weight was measured by Gel Permeation Chromatography (GPC) using methylene chloride as the mobile phase. The separation was performed using two 5 μmixed D columns with guard columns from agilent technologies company (Agilent Technologies). A chromatogram was obtained using a 254nm uv detector. A flow rate of 1.5mL/min and an injection volume of 20 μl of 0.2w/v% solution in the mobile phase were selected. Calibration was performed with 12 narrow molecular weight polystyrene standards (peak molecular weight range: 371,000 to 580 g/mol). The number average molecular weight Mn, the weight average molecular weight Mw and the higher average molecular weight Mz are reported.
Method 2: viscotek GPC Max (autosampler, pump and degasser) with TDA302 triplex detector array consisting of RALS (right angle light scattering), RI and viscosity detector was used. Samples were run through a set of 3 columns at 65℃in NMP containing 0.2w/w% LiBr at 1.0 mL/min: guard columns (CLM 1019-with 20k Da exclusion limit), high Mw columns (CLM 1013, 10MM daltons against polystyrene exclusion), and low Mw columns (CLM 1011-20 k daltons against PS exclusion limit). Calibration was accomplished using a single monodisperse polystyrene standard of about 100k Da. The light scattering, RI and viscosity detectors are calibrated based on a set of input data provided according to the standard. Samples were prepared at about 2mg/mL in NMP/LiBr.
The Viscotek's OMNISec v4.6.1 software was used for data analysis. The number average molecular weight Mn, the weight average molecular weight Mw and the higher average molecular weight Mz are reported.
Thermogravimetric analysis (TGA)
TGA experiments were performed using TGA Q500 of TA instruments. TGA measurements were obtained by heating the samples from 20 ℃ to 800 ℃ under nitrogen at a heating rate of 10 ℃/min.
1H NMR
1 H NMR spectra were measured using a 400MHz Brookfield (Bruker) spectrometer with TCE or DMSO as deuterated solvent. All spectra are referenced to residual protons in the solvent.
DSC
DSC is used to determine the glass transition temperature (Tg) and melting point (Tm), if any. DSC experiments were performed using Q100 from TA instruments. The DSC profile was recorded by heating, cooling, reheating and then cooling the sample between 25 ℃ and 320 ℃ at a heating and cooling rate of 20 ℃/min. All DSC measurements were taken under a nitrogen purge. The second heating curve is used to provide reported Tg (and Tm, if any) values unless otherwise indicated.
I. preparation of copolymer (P0-A)
The copolymer (P0-A) was prepared according to scheme 1.
The polymerization was carried out in a glass reactor vessel (1L) equipped with an overhead stirrer, nitrogen inlet and overhead distillation apparatus. The monomers 4,4 '-dichlorodiphenyl sulfone (143.58 g), bisphenol A (102.73 g) and 2,2' diallyl bisphenol S (16.52 g) were first added to the vessel followed by potassium carbonate (78.29 g) and NMP (690 g) and chlorobenzene (170 g). The reaction mixture was heated from room temperature to 190 ℃ using a heating ramp of 150 ℃/min and chlorobenzene was continuously removed using a Dean-Stark apparatus. The temperature of the reaction mixture was maintained for about eight hours depending on the viscosity of the solution. The reaction was stopped by turning off the heat source and diluting the reaction mixture with cold solvent. The reaction mixture was filtered, coagulated in methanol and dried at 110 ℃.
Characterization of copolymer (P0-A)
GPC (method 1): mn=12743 g/mol, mw= 58832g/mol, PDI=4.61
TGA：477℃；DSC：Tg＝195℃
1 H NMR: the presence of unsaturated groups was confirmed by the appearance of multiple peaks at 6.1-6.4ppm, indicating the incorporation of 2,2' -diallyl BPS monomer in the polymer.
II preparation of copolymer (P0-B)
The copolymer (P0-B) was prepared according to scheme 2.
The polymerization was carried out in a glass reactor vessel (1L) equipped with an overhead stirrer, nitrogen inlet and overhead distillation apparatus. The monomers 4,4' -dichlorodiphenyl sulfone (172.29 g), 4' -biphenol (106.13 g) and 2,2' -diallylbisphenol S (9.91 g) were first added to the vessel followed by potassium carbonate (93.69 g) and sulfolane (570 g). The reaction mixture was heated from room temperature to 210 ℃ using a heating ramp of 150 ℃/min. The temperature of the reaction mixture was maintained for about five hours depending on the viscosity of the solution. The reaction was stopped by removing the heat source and diluting with more solvent. The reaction mixture was filtered, coagulated in methanol and dried at 110 ℃.
Characterization of copolymer (P0-B)
GPC (method 1): mn=19251 g/mol, mw= 71960g/mol, pdi=3.70.
TGA：505℃；DSC：Tg＝235℃
1 H NMR: no spectrum was obtained due to poor solubility in NMR solvents.
Preparation of functionalized copolymers (P1-A) by radical reaction
The copolymer (P1-A) according to the invention is prepared according to scheme 3.
31.2G of the copolymer (P0-A) prepared according to the above section I (scheme 1) was dissolved in 89g of NMP and 3.2g of cysteamine hydrochloride was added in a 250mL three-necked flask equipped with a nitrogen inlet, a thermocouple and an overhead stirrer. The reaction mixture was heated to 50 ℃ under nitrogen, then 0.8g of ADVN was added in one portion. The reaction was continued for 24 hours, after which the reaction mass was coagulated in methanol, the precipitated polymer was then washed with methanol, water and then finally with methanol and dried under reduced pressure at 110 ℃.
Characterization of
GPC (method 2): mw= 152023g/mol, mn=50044 g/mol, pdi=3.30
DSC：Tg＝206℃；TGA：411℃
Quantitative estimates of amine functionalization were analyzed by titrating amine groups. Amine content: 295 microequivalents/g.
Preparation of functionalized copolymers (P1-B) by free radical reaction
The copolymer (P1-B) according to the invention is prepared according to scheme 4.
In a 250mL three-necked flask equipped with a nitrogen inlet, thermocouple and overhead stirrer, 30g of copolymer (P0-B) prepared according to section II (scheme 2) above was dissolved in 110g of NMP and 3.9g of sodium 3-mercapto-1-propanesulfonate was added. The reaction mixture was heated to 75 ℃ under nitrogen, then 0.59g of AIBN was added in one portion. The reaction was continued for 24 hours, after which the reaction mass was coagulated in methanol, the precipitated polymer was then washed with methanol, water and then finally with methanol and dried under reduced pressure at 110 ℃.
Characterization of
GPC (method 2): mw= 342287g/mol, mn=75154 g/mol, pdi=4.50
DSC：Tg＝234℃；TGA：517℃
Sodium content: 1337ppm
Claims (15)
1. A copolymer (P1) comprising:
-a repeating unit (R P1) having formula (M):
-a repeating unit (R x P1) having formula (N):
Wherein the method comprises the steps of
-Each R 1 is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;
-each i is independently an integer from 0 to 4;
-T is selected from the group consisting of: bond 、-CH2-;-O-;-SO2-;-S-;-C(O)-;-C(CH3)2-;-C(CF3)2-;-C(＝CCl2)-;-C(CH3)(CH2CH2COOH)-;-N＝N-;-RaC＝CRb-, wherein R a and R b are each, independently of one another, hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; - (CH 2)m -and- (CF 2)m -, wherein m is an integer from 1 to 6), straight or branched aliphatic divalent radicals having up to 6 carbon atoms, and combinations thereof;
-G N is selected from the group consisting of at least one of the following formulae (G N1) to (G N6):
Wherein the method comprises the steps of
-W is a bond or-SO 2 -, preferably-SO 2 -;
-each k is independently an integer from 0 to 4;
-each j is independently an integer from 3 to 7;
-each R 2 is independently selected from the group consisting of:
- (CH 2)u -COOH wherein u is an integer of 1 to 5, provided that when T and W are both-SO 2 -, then u is not 1 or 2,
- (CH 2)k -OH, wherein k is an integer of 1 to 5,
- (CH 2)p-NRaRb) wherein p is an integer from 1 to 5, and a and b are independently C1-C6 alkyl or H, provided that R a and R b cannot both be CH 3,
- (CH 2)q-SO3 Na in which q is an integer of 1 to 5,
- (CH 2)a-COCH3) wherein a is an integer of 0 to 10
- (CH 2)r-Si(OCH3)3) wherein r is an integer of 1 to 5,
- (CH 2)s-(CF2)t-CF3) wherein s is an integer of 1 to 5, and t is an integer of 1 to 10,
-C (O) -R c, wherein R c is C1-C6 alkyl or H, preferably H,
- (CH 2)v-CH3) wherein v is an integer of 5 to 30, and
- (CH 2)w -Ar wherein w is an integer of 1 to 10 and Ar comprises one or two aromatic or heteroaromatic rings, for example one or two benzene rings, and
Wherein the copolymer (P1) has a glass transition temperature Tg equal to or greater than Tg h of a homopolymer consisting essentially of the same repeating unit (R P1), as measured by Differential Scanning Calorimetry (DSC).
2. The copolymer (P1) according to claim 1, wherein T in the repeating unit (R P1) is selected from the group consisting of a bond, -SO 2 -, and-C (CH 3)2 -.
3. The copolymer (P1) according to any one of claims 1 to 2, wherein i is zero for each R 1 of the repeating unit (R P1) and the repeating unit (R x P1).
4. A copolymer (P1) according to any one of claims 1 to 3, wherein in the repeating unit (R x P1), k is 0 and j is 3.
5. The copolymer (P1) according to any one of claims 1 to 4, wherein the molar ratio of repeating units (R P1)/repeating units (R x P1) varies between 0.01/100 and 100/0.01, preferably between 1/100 and 100/1, more preferably between 1/1 and 10/1.
6. The copolymer (P1) according to any one of claims 1 to 5, wherein the repeating unit (R P1) is according to formula (M1), (M2) or (M3):
7. The copolymer (P1) according to any one of claims 1 to 6, wherein R 2 in formula (G N1)、(GN2)、(GN3)、(GN4)、(GN5) or (G N6) is independently selected from the group consisting of:
-CH2-COOH，
-(CH2)2-OH，
-(CH2)2-NH2，
-(CH2)3-SO3Na，
-(CH2)3-Si(OCH3)3，
-(CH2)2-(CF2)7-CF3，
-CHO，
-(CH2)9-CH3，
-CH 2 -Ph, wherein Ph is benzene.
8. The copolymer (P1) of any one of claims 1 to 7, comprising a total of at least 50mol.% of repeat units (R P1) and (R x P1), based on the total moles in the copolymer (P1).
9. A process for preparing the copolymer (P1) according to any one of claims 1 to 8, which comprises reacting, in a solvent: copolymer (P0) comprising
-A repeating unit (R P0) having formula (M):
-a repeating unit (R x P0) having formula (P):
Wherein the method comprises the steps of
-Each R 1 is independently selected from the group consisting of: halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali metal or alkaline earth metal sulfonate, alkyl sulfonate, alkali metal or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium;
-each i is independently an integer from 0 to 4;
-T is selected from the group consisting of: bond 、-CH2-;-O-;-SO2-;-S-;-C(O)-;-C(CH3)2-;-C(CF3)2-;-C(＝CCl2)-;-C(CH3)(CH2CH2COOH)-;-N＝N-;-RaC＝CRb-, wherein R a and R b are each, independently of one another, hydrogen or C1-C12-alkyl, C1-C12-alkoxy or C6-C18-aryl; - (CH 2)m -and- (CF 2)m -, wherein m is an integer from 1 to 6), a straight or branched aliphatic divalent group having up to 6 carbon atoms, and combinations thereof,
-G p is selected from the group consisting of at least one of the following formulae (G p1) to (G p3):
Wherein:
-W is a bond or-SO 2 -, preferably-SO 2 -;
each k is independently selected from 0 to 4,
Wherein the copolymer (P0) has a glass transition temperature Tg equal to or greater than Tg h, preferably a Tg > Tg h, more preferably a Tg of > 5 ℃ C.+Tg h, still more preferably a Tg of > 7 ℃ C.+Tg h, still more preferably a Tg of > 10 ℃ C.+Tg h, of a homopolymer consisting essentially of the same repeating units (R P0), as measured by Differential Scanning Calorimetry (DSC),
A compound having the formula (I):
R2-SH(I)
Wherein R 2 is selected from the group consisting of:
- (CH 2)u -COOH wherein u is an integer of 1 to 5, provided that when T and W are both-SO 2 -, then u is not 1 or 2,
- (CH 2)k -OH, wherein k is an integer of 1 to 5,
- (CH 2)p-NRaRb) wherein p is an integer from 1 to 5, and a and b are independently C1-C6 alkyl or H, provided that R a and R b cannot both be CH 3,
- (CH 2)q-SO3 Na in which q is an integer of 1 to 5,
- (CH 2)a-COCH3) wherein a is an integer of 0 to 10
- (CH 2)r-Si(OCH3)3) wherein r is an integer of 1 to 5,
- (CH 2)s-(CF2)t-CF3) wherein s is an integer of 1 to 5, and t is an integer of 1 to 10,
-C (O) -R c, wherein R c is C1-C6 alkyl or H,
- (CH 2)v-CH3) wherein v is an integer of 5 to 30, and
- (CH 2)w -Ar wherein w is an integer of 1 to 10, and Ar comprises one or two aromatic or heteroaromatic rings,
Wherein the molar ratio of compound (I)/polymer (P0) varies between 0.01/100 and 100/0.01, the reaction being carried out at a temperature ranging from 10℃to 300 ℃.
10. The method of claim 9, which is performed in a solvent selected from the group consisting of: n-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), 1, 3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), chlorobenzene, anisole, chloroform, dichloromethane (DCM), and sulfolane.
11. The method of any one of claims 9-10, which is carried out in the presence of:
at least one radical initiator, preferably 2,2' -azobis (2-methylpropanenitrile) (AIBN), and/or
At least one catalyst, preferably chosen from peroxides and hydroperoxides, and/or
-In the presence of a base, preferably selected from the group consisting of N-ethyl-N- (prop-2-yl) prop-2-amine (henigine), triethylamine (TEA) and pyridine.
12. The process of any one of claims 9-10, which is carried out by exposing the reaction mixture to UV light at a wavelength in the range 300nm to 600nm, preferably 350nm to 450nm, more preferably 365 nm.
13. The method of any of claims 9-12, wherein the functionalized PAES copolymer (P0) comprises a total of at least 50mol.% of repeating units (R P0) and (R x P0) based on the total moles in the copolymer (P0).
14. The method of any of claims 9-13, wherein the functionalized PAES copolymer (P0) is prepared by condensation of at least one aromatic dihydroxy monomer (a 1) with at least one aromatic sulfone monomer (a 2) comprising at least two halogen substituents and at least one allyl-substituted aromatic dihydroxy monomer (a 3).
15. Use of a copolymer (P1) according to any one of claims 1 to 8 for the preparation of films, composites or coatings.
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| PCT/EP2022/087247 WO2023118302A1 (en) | 2021-12-23 | 2022-12-21 | Functionalized poly(aryl ether sulfone) copolymers |
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