WO2010057822A1 - Reaktive polyarylenether und verfahren zu deren herstellung - Google Patents
Reaktive polyarylenether und verfahren zu deren herstellung Download PDFInfo
- Publication number
- WO2010057822A1 WO2010057822A1 PCT/EP2009/065035 EP2009065035W WO2010057822A1 WO 2010057822 A1 WO2010057822 A1 WO 2010057822A1 EP 2009065035 W EP2009065035 W EP 2009065035W WO 2010057822 A1 WO2010057822 A1 WO 2010057822A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer composition
- end groups
- polyarylene ether
- solvent
- polyarylene
- Prior art date
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 229920000642 polymer Polymers 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 49
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical group OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 150000002170 ethers Chemical class 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 88
- 239000007858 starting material Substances 0.000 claims description 31
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001556 precipitation Methods 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 125000005843 halogen group Chemical group 0.000 claims description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
- 239000011591 potassium Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 5
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 4
- 239000001384 succinic acid Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims 1
- 239000000047 product Substances 0.000 description 27
- 238000006068 polycondensation reaction Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 11
- IBRQUKZZBXZOBA-UHFFFAOYSA-N 1-chloro-3-(3-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC(S(=O)(=O)C=2C=C(Cl)C=CC=2)=C1 IBRQUKZZBXZOBA-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000269 nucleophilic effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- 238000007792 addition Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- -1 cyclopropylethyl Chemical group 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000559 atomic spectroscopy Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 4
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 4
- 229940031826 phenolate Drugs 0.000 description 4
- 238000003918 potentiometric titration Methods 0.000 description 4
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
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- 229920005989 resin Polymers 0.000 description 3
- 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 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 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 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Chemical class 0.000 description 2
- 239000011707 mineral Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 125000004957 naphthylene group Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000007339 nucleophilic aromatic substitution reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920000090 poly(aryl ether) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 2
- CFTSORNHIUMCGF-UHFFFAOYSA-N (1,1,1,3,3,3-hexafluoro-2-phenylpropan-2-yl)benzene Chemical class C=1C=CC=CC=1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1 CFTSORNHIUMCGF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-dioxonaphthalene Natural products C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- BOKGTLAJQHTOKE-UHFFFAOYSA-N 1,5-dihydroxynaphthalene Chemical compound C1=CC=C2C(O)=CC=CC2=C1O BOKGTLAJQHTOKE-UHFFFAOYSA-N 0.000 description 1
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 description 1
- NYKRSGJRIJJRRK-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)sulfonylbenzene Chemical class ClC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1Cl NYKRSGJRIJJRRK-UHFFFAOYSA-N 0.000 description 1
- PZDAAZQDQJGXSW-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)benzene Chemical group C1=CC(F)=CC=C1C1=CC=C(F)C=C1 PZDAAZQDQJGXSW-UHFFFAOYSA-N 0.000 description 1
- 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
- SLPUTJFVMJPMKV-UHFFFAOYSA-N 1-methylpyrrolidin-3-one Chemical compound CN1CCC(=O)C1 SLPUTJFVMJPMKV-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical class C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- QIOCFZAEFQTCSO-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C=2C=C(C)C(O)=C(C)C=2)(C(F)(F)F)C(F)(F)F)=C1 QIOCFZAEFQTCSO-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- WSNMPAVSZJSIMT-UHFFFAOYSA-N COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 Chemical compound COc1c(C)c2COC(=O)c2c(O)c1CC(O)C1(C)CCC(=O)O1 WSNMPAVSZJSIMT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 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
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- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 238000005338 heat storage Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
Definitions
- the present invention relates to a process for producing a polymer composition
- a process for producing a polymer composition comprising
- the present invention relates to polymer compositions obtainable by the process, to mixtures which comprise these polyarylene ethers and to the use of the polymer compositions according to the invention for the toughening of epoxy resins.
- Polyarylene ethers belong to the group of high-performance thermoplastics and are used in highly stressed applications because of their high heat resistance and chemical resistance. See G. Blinne, M. Knoll, D. Müller, K. Schlichting, Kunststoffe 75, 219 (1985), EM Koch, H .-M. Walter, Kunststoffe 80, 1 146 (1990) and D. Döring, Kunststoffe 80, 1149 (1990).
- a widely used product for this application is Sumikaexcel® 5003 P from Sumitomo.
- the preparation of this product is carried out by condensation of the corresponding monomers in diphenyl sulfone and subsequent purification of the material by extraction with organic solvents.
- This process is expensive and also provides a polymer composition which has a high proportion of phenolate end groups and thus of potassium (> 700 ppm), which is disadvantageous for further processing. If such polymer compositions are isolated by precipitation, finely divided precipitates are formed, which are difficult to handle for industrial processes.
- the preparation of the polyarylene ethers is usually carried out by polycondensation of suitable starting compounds in dipolar aprotic solvents at elevated temperature (RN Johnson et al., J. Polym. Sci. A-15 (1967) 2375, JE McGrath et al. Polymer 25 (1984) 1827). McGrath et al., Polymer 30 (1989), 1552 also discloses that, after the condensation reaction has ended, the proportion of amino end groups can be reduced by the addition of acetic acid during the workup of polyarylene ethers.
- the object of the present invention was to provide reactive, d. H. OH-terminated polyarylene ether. It was the object of the present invention to avoid the disadvantages of the prior art. It was a further object of the present invention to provide a process for the preparation of OH-terminated polyarylene ethers wherein the product is obtained as a readily handleable precipitate.
- the polymer compositions obtainable in this way should have high color stability and temperature stability. In particular, the OH-terminated polyarylene ethers should discolor as little as possible when processed in the melt.
- the process for their preparation should be easy to carry out and provide a high polymer yield.
- the process for the preparation of polyarylene ethers comprises the following steps in the sequence a-b-c:
- t, q independently of one another 0, 1, 2 or 3
- Ar, Ar 1 independently of one another an arylene group having from 6 to 18 carbon atoms,
- phenolate end groups are understood as meaning negatively charged oxygen atoms in the form of an end group which are bonded to an aromatic nucleus. These end groups are derived from the phenolic end groups by removal of a proton.
- a phenolic end group is understood as meaning a hydroxy group which is bonded to an aromatic nucleus.
- the aromatic nuclei mentioned are preferably 1,4-phenylene groups.
- the polyarylene ethers (P) of the present invention may, on the one hand, have phenolate or phenolic OH end groups and, on the other hand, halogen end groups.
- the polymer composition of the present invention preferably consists essentially of polyarylene ethers having predominantly phenolic end groups, i. from OH-terminated polyarylene ethers.
- predominantly phenolate end groups is to be understood as meaning that more than 50% of the end groups present are phenolate end groups. Accordingly, the term “predominantly phenolic end groups” is to be understood as meaning that more than 50% of the end groups present are phenolic in nature ,
- the determination of the proportion of phenolate end groups is preferably carried out by determining the OH end groups by potentiometric titration and determination of the organically bound halogen end groups by means of atomic spectroscopy and subsequent calculation of the respective numerical proportions in%. Corresponding methods are known to the person skilled in the art. Alternatively, the determination of the proportions of the respective end groups can be carried out by means of 13 C nuclear magnetic resonance spectroscopy.
- step (a) the provision of the polyarylene ether or of the polyarylene ethers (P) with predominantly phenolate end groups in step (a) is carried out by reaction at least one starting compound of the structure X-Ar-Y (A1) with at least one starting compound of the structure HO-ArI-OH (A2) in the presence of a solvent (L) and a base (B), wherein
- - Y is a halogen atom
- - X is selected from halogen atoms and OH
- Ar and Ar 1 independently represent an arylene group having 6 to 18 carbon atoms.
- step (a) of the process according to the invention at least one polyarylene ether (P) is provided in the presence of a solvent (L), wherein the at least one polyarylene ether (P) is built up from building blocks of the general formula I with the meanings as defined above and predominantly phenolate end groups:
- the polyarylene ether (P) preferably has at least 60%, particularly preferably at least 80%, in particular at least 90% of phenolate end groups, based on the total number of end groups.
- the provision of the polyarylene ether (P) is preferably carried out in the form of a solution in the solvent (L).
- Q, T and Y in formula (II) are independently selected from -O- and -SO 2 -, provided that at least one of Q, T and Y is -SO 2 -.
- R a and R b are each independently a hydrogen atom or a C 1 -C 12 alkyl, C 1 -C 12 alkoxy or C 6 -C 18 aryl group.
- C 1 -C 12 -alkyl groups include linear and branched, saturated alkyl groups having from 1 to 12 carbon atoms.
- the following radicals are to C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, 2- or 3-methyl-pentyl and longer-chain radicals such as unbranched heptyl, octyl, nonyl , Decyl, undecyl, lauryl and the mono- or poly-branched analogs thereof.
- Suitable alkyl radicals in the abovementioned usable C 1 -C 12 -alkoxy groups are the alkyl groups having from 1 to 12 carbon atoms defined above.
- Preferred cycloalkyl radicals include in particular C 3 -C 12 -CCCl-alkyl radicals, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclpentylethyl, -propyl, -butyl , -pentyl, -hexyl, cyclohexylmethyl, -dimethyl, -trimethyl.
- Ar and Ar 1 independently represent a C 1 -C 6 -arylene group.
- Ar is preferably derived from an electron-rich, readily electrophilically attackable aromatic substance, which is preferably selected from the group consisting of hydroquinone, resorcinol, dihydroxynaphthalene, in particular 2,7-dihydroxynaphthalene, and 4,4 '. -Bisphenol is selected.
- Ar 1 is an unsubstituted C 6 or C 12 arylene group.
- Phenylene groups such as 1, 2, 1, 3 and 1, 4-phenylene, naphthylene groups, such as, for example, 1, 6, 1, 7, and 2,6, are used as C 6 -C 18 -arylene groups Ar and Ar 1 - And 2,7-naphthylene, and derived from anthracene, phenanthrene and naphthacene arylene groups into consideration.
- Ar and Ar 1 in the preferred embodiment according to formula (I) are preferably selected independently from the group consisting of 1, 4-phenylene, 1, 3-phenylene, naphthylene, in particular 2, 7-dihydroxynaphthalene, and 4,4'- biphenylene.
- polyarylene ether (P) preferably present blocks are those which contain at least one of the following recurring structural units Ia to Io:
- those building blocks are also preferred in which one or more 1,4-dihydroxyphenyl units are replaced by resorcinol or dihydroxynaphthalene units.
- Particularly preferred building blocks of the general formula I are the building blocks Ia, Ig and Ik. It is also particularly preferred if the polyarylene ethers of the polyarylene ethers (P) are essentially composed of one kind of building blocks of the general formula I, in particular of one building block selected from Ia, Ig and Ik.
- PESU polyethersulfone
- the polyarylene ethers (P) which are provided in the context of step (a) predominantly comprise phenolate end groups according to the invention.
- the phenolate end groups are converted in the course of the process according to the invention to phenolic end groups.
- the polyarylene ether thus has phenolic end groups.
- polyarylene ethers with predominantly phenolic end groups are referred to below as reactive polyarylene ethers.
- the polyarylene ethers (P) have average molecular weights M n (number average) in the range from 2,000 to 60,000 g / mol, in particular 5,000 to 40,000 g / mol, determined by gel permeation chromatography in the solvent dimethylacetamide against narrow-distribution polymethyl methacrylate as standard.
- the polyarylene ethers (P) preferably have relative viscosities of from 0.20 to 0.95 dl / g, in particular from 0.30 to 0.80. Depending on the solubility of the polyarylene ether sulfones, the relative viscosities are measured either in 1% strength by weight N-methylpyrrolidone solution, in mixtures of phenol and dichlorobenzene or in 96% strength sulfuric acid at 20 ° C. and 25 ° C., respectively.
- polyarylene ethers (P) can in principle be carried out in various ways.
- a corresponding polyarylene ether (P) may be contacted directly with a suitable solvent and directly, i. H. without further implementation, be used in the process according to the invention.
- prepolymers of polyarylene ethers can be used and brought to reaction in the presence of a solvent, wherein the described polyarylene (P) arise in the presence of the solvent.
- the polyarylene ethers (P) are prepared starting from suitable starting compounds, in particular starting from monomers in the presence of a solvent (L) and a base (B). Such production methods are known per se to the person skilled in the art.
- step (a) of this preferred embodiment the reaction of at least one starting compound of the structure X-Ar-Y (A1) with at least one starting compound of the structure HO-Ar 1 -OH (A2) takes place in the presence of a Solvent (L) and a base (B), wherein
- Y is a halogen atom
- - X is selected from halogen atoms and OH, preferably from halogen atoms, in particular F, Cl, or Br and
- Ar and Ar 1 independently represent an arylene group having 6 to 18 carbon atoms.
- the ratio of (A1) and (A2) is chosen so that the number of phenolic or phenolate end groups exceeds the number of halogen end groups.
- a polyarylene ether is thus prepared which is in contact with a solvent (L) and is preferably dissolved therein.
- Suitable starting compounds are known to the person skilled in the art and are not subject to any fundamental restriction, provided that the abovementioned substituents are sufficiently reactive in the context of a nucleophilic aromatic substitution.
- the reaction in step (a) is simultaneously a polycondensation with arithmetic elimination of hydrogen halide.
- Preferred starting compounds are difunctional in the context of AF-vz.
- Difunctional means that the number of reactive groups in the nucleophilic aromatic substitution is two per starting compound.
- Another criterion for a suitable difunctional starting compound is sufficient solubility in the solvent, as explained in more detail below.
- preferred compounds (A2) are those having two phenolic hydroxyl groups.
- reaction of the phenolic OH groups preferably takes place in the presence of a base in order to increase the reactivity with respect to the halogeno substituents of the starting compound (A1).
- Step (a) is preferably carried out starting from monomers and not starting from prepolymers.
- the starting compound (A1) used is a dihalodiphenylsulfone.
- the starting compound (A2) used is preferably dihydroxydiphenylsulfone.
- Suitable starting compounds (A1) are, in particular, dihalodiphenylsulfones, such as 4,4'-dichlorodiphenylsulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dibromodiphenylsulfone, bis (2-chlorophenyl) sulfones, 2,2'-dichlorodiphenylsulfone and 2,2'-dichloromethane.
- Difluordiphenylsulfon, with 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl are particularly preferred.
- Preferred starting compounds (A2) having two phenolic hydroxyl groups are selected from the following compounds:
- Dihydroxynaphthalenes in particular 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;
- Dihydroxybiphenyls especially 4,4'-biphenol and 2,2'-biphenol;
- Bisphenyl ethers especially bis (4-hydroxyphenyl) ether and bis (2-hydroxyphenyl) ether;
- Bis-phenylpropanes especially 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, and 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane;
- Bisphenylmethanes especially bis (4-hydroxyphenyl) methane
- Bisphenylsulfones especially bis (4-hydroxyphenyl) sulfone
- Bisphenyl sulfides especially bis (4-hydroxyphenyl) sulfide
- - Bisphenylketone in particular bis (4-hydroxyphenyl) ketone
- Bis-phenylhexafluoropropanes especially 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) hexafluoropropane
- Bisphenylfluorenes especially 9,9-bis (4-hydroxyphenyl) fluorene.
- aromatic dihydroxy compounds (A2) it is preferable, starting from the abovementioned aromatic dihydroxy compounds (A2), to prepare their dipotassium or disodium salts by addition of a base (B) and to react with the starting compound (A1).
- the aforementioned compounds can also be used individually or as a combination of two or more of the aforementioned compounds.
- Hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, and 4,4'-bisphenol are particularly preferred as the starting compound (A2).
- trifunctional compounds In this case, branched structures arise. If a trifunctional starting compound (A2) is used, 1,1,1-tris (4-hydroxyphenylethane) is preferred.
- the proportions to be used arise, in principle, from the stoichiometry of the polycondensation reaction proceeding with the computational elimination of hydrogen chloride and are set by a person skilled in the art in a known manner. However, to increase the number of phenolic OH end groups, an excess of OH end groups is preferable.
- polyaryl ethers with simultaneous control of the end groups is known per se to the person skilled in the art and will be described in more detail below.
- the known polyarylene ethers usually have phenolic halogen, especially -F or -Cl, or phenolic OH or O ⁇ end groups, the latter usually being further reacted in the prior art, in particular to CHsO groups.
- the molar ratio (A2) / (A1) is particularly preferably from 1.005 to 1.2, in particular 1.01 to 1.15, very particularly preferably 1.02 to 1.1.
- an excess of hydroxy groups is set by addition of the starting compound (A2).
- the ratio of the phenolic end groups used to halogen is preferably from 1.01 to 1.2, in particular 1. 03 to 1.15, very particularly preferably 1.05 to 1.1.
- the conversion in the polycondensation in the context of AF-vz according to step (a) in the preferred embodiment is at least 0.9, whereby a sufficiently high molecular weight is ensured.
- the degree of polymerization refers to the number of actual monomers.
- Preferred solvents (L) for the purposes of the present invention are aprotic polar solvents. Suitable solvents also have a boiling point in the range of 80 to 320 ° C, especially 100 to 280 ° C, preferably 150 to 250 ° C. Suitable aprotic polar solvents are, for example, high-boiling ethers, esters, ketones, asymmetrically halogenated hydrocarbons, anisole, dimethylformamide, dimethyl sulfoxide, sulfolane and N-methyl-2-pyrrolidone.
- a preferred solvent is in particular N-methyl-2-pyrrolidone.
- reaction of the starting compounds (A1) and (a2) in said aprotic polar solvents (L), in particular N-methyl-2-pyrrolidone is particularly preferable.
- reaction of the starting compounds (A1) and (A2) takes place in the presence of a base (B).
- the bases are anhydrous.
- Suitable bases are, in particular, anhydrous alkali metal carbonate, preferably sodium, potassium, calcium carbonate or mixtures thereof, with potassium carbonate being particularly preferred, especially potassium carbonate having a volume-weighted mean particle size of less than 100 micrometers, determined by means of a particle size measuring device in a suspension in N. methyl-2-pyrrolidone.
- a particularly preferred combination is N-methyl-2-pyrrolidone as solvent (L) and potassium carbonate as base (B).
- the reaction of the appropriate starting compounds (A1) and (A2) is carried out at a temperature of 80 to 250 ° C, preferably 100 to 220 ° C, the upper limit of the temperature being determined by the boiling point of the solvent.
- the reaction is preferably carried out in a time interval of 2 to 12 h, in particular from 3 to 8 h.
- step (a) the amount of the polyarylene ether (P) based on the total weight of the mixture of polyarylene ether (P) and solvent (L) of 10 to 70 wt .-%, preferably from 15 to 50% by weight.
- step (b) of the process according to the invention at least one polyfunctional carboxylic acid is added to the polyarylene ether (P) from step (a), preferably to dissolve the polyarylene ether (P) in the solvent (L).
- polyfunctional is meant a functionality of at least 2. The functionality is the (optionally average) number of COOH groups per molecule. "" More functionality is understood to mean a functionality of two or higher. "” Carboxylic acids preferred in the context of the present invention are " and trifunctional carboxylic acids.
- polyfunctional carboxylic acid can be carried out in various ways, in particular in solid or liquid form or in the form of a solution, preferably in a solvent which is miscible with the solvent (L).
- the polyfunctional carboxylic acid has a number average molecular weight of at most 1500 g / mol, in particular at most 1200 g / mol.
- the polyfunctional carboxylic acid preferably has a number-average molecular weight of at least 90 g / mol.
- Suitable polyfunctional carboxylic acids are in particular those according to general structure II:
- R represents a hydrocarbon radical having from 2 to 20 carbon atoms, which optionally contains further functional groups, preferably selected from OH and COOH.
- Preferred polyfunctional carboxylic acids are C 4 to C 10 dicarboxylic acids, in particular succinic acid, glutaric acid, adipic acid, and tricarboxylic acids, in particular citric acid.
- Particularly preferred polyfunctional carboxylic acids are succinic acid and citric acid.
- step (b) of the process according to the invention preference is given to a polyfunctional carboxylic acid in an amount of from 25 to 200 mol% of carboxyl groups, preferably from 50 to 150 mol% of carboxyl groups, particularly preferably from 75 to 125 mol% of carboxyl groups , determined to add based on the amount of phenolate or phenolic end groups determined.
- step (c) of the process according to the invention the recovery of the polymer composition takes place as a solid.
- the preferred precipitation can be carried out in particular by mixing the solvent (L) with a poor solvent (L ').
- a poor solvent is a solvent in which the polymer composition does not dissolve. Such a poor solvent is preferably a mixture of a non-solvent and a solvent.
- a preferred non-solvent is water.
- a preferred solvent (L ') mixture with a non-solvent is preferably a mixture of the solvent (L), especially N-methyl-4-pyrrolidone, and water. It is preferable to add the polymer solution from step (b) to the poor solvent (L '), resulting in the precipitation of the polymer composition. In this case, an excess of the poor solvent is preferably used.
- the addition of the polymer solution from step (a) takes place in finely divided form, in particular in drop form.
- a poor solvent (L ') a mixture of water and N-methyl-2-pyrrolidone (NMP) in combination with N-methyl-2-pyrrolidone as the solvent (L) is preferred.
- NMP N-methyl-2-pyrrolidone
- Particularly preferred as a poor solvent (L ') is a mixture NMP / water of 1: 3 to 1:50, in particular 1: 4 to 1: 30.
- the precipitation is particularly efficient if the content of the polymer composition in the solvent (L) is from 10 to 50% by weight, preferably from 15 to 35% by weight, based on the total weight of the mixture of polymer composition and solvent (L) ,
- the purification of the polyarylene ether copolymers is carried out by methods known to the person skilled in the art, for example washing with suitable solvents in which the polyarylene ether copolymers according to the invention are preferably largely insoluble.
- the polymer composition according to the invention essentially consists of the building blocks of the polyarylene ether or of the polyarylene ether (P), of which predominantly phenolate end groups are present as phenolic end groups, ie OH-terminated.
- the proportion of the phenolic end groups of the polymer composition of the present inventive method is at least 0.1 wt .-% OH calculated as the amount by weight OH based on the total amount of the polymer composition, in particular at least 0.12 wt .-%, particularly preferably at least O, 15% by weight.
- the determination of the phenolic end groups as the amount by weight of OH in relation to the total amount of the polyarylene ether is carried out by means of potentiometric titration.
- the polymer is dissolved in dimethylformamide and titrated with a solution of tetrabutylammonium hydroxide in toluene / methanol. Endpoint detection is potentiometric.
- the polymer composition according to the present invention preferably has a potassium content of at most 600 ppm.
- the potassium content is determined in the context of the present invention by means of atomic spectrometry.
- Another object of the present invention are mixtures, preferably reactive resins, in particular epoxy resins containing the polymer compositions of the invention.
- Such reactive resins are known to those skilled in the art and consist of reactive polymers which, depending on the reaction conditions, with the addition of suitable hardeners, give a thermosetting plastic of high strength and chemical resistance.
- polymer compositions according to the invention for the toughening of reactive resins, in particular epoxy resins, is preferred.
- the viscosity number of the polyarylene ethers (P) was determined in 1% solution in N-methyl-2-pyrrolidone at 25 ° C according to ISO 1628.
- the proportion of OH groups was determined by potentiometric titration.
- the potassium content was determined by atomic spectroscopy.
- the precipitation is assessed according to the following criteria:
- the precipitation was carried out by adding dropwise a polymer solution having a polymer content between 20 and 22 wt .-% in a mixture of water / NMP in the ratio 80/20 at room temperature.
- the polyarylene ether (P-1) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 509.72 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept under nitrogen atmosphere at 190 ° C for 6 hours. Thereafter, the reaction was diluted by adding 1000 ml of NMP, the solid was separated by filtration and the polymer was isolated by precipitation in NMP / water 1/4. After careful washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 55.2 ml / g.
- the polyarylene ether (P-2) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenyl sulfone, 509.72 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept under nitrogen atmosphere at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 5.54 g of succinic acid was added and stirred for 30 minutes. The polymer was then isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 54.9 ml / g.
- the polyarylene ether (P-3) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 52.5 ml / g.
- the polyarylene ether (P-4) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Then, at 80 ° C, 6.2 g of succinic acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After careful washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 52.6 ml / g.
- the polyarylene ether (P-5) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 8.13 ml of phosphoric acid (85%) was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 52.4 ml / g.
- the polyarylene ether (P-6) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the influence of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Then, at 80 ° C, 10.1 g of citric acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 hours. The viscosity number of the product was 52.6 ml / g.
- the polyarylene ether (P-7) was obtained by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 516.07 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 38.3 ml / g.
- the polyarylene ether (P-8) was prepared by nucleophilic aromatic polycondensation of 574.16 g of dichlorodiphenylsulfone, 512.09 g of dihydroxydiphenylsulfone, under the action of 290.24 g of potassium carbonate in 1000 ml of NMP. This mixture was kept at 190 ° C for 6 hours. Thereafter, the batch was diluted by adding 1000 ml of NMP, the solid components were separated by filtration. Subsequently, at 80 ° C, 13.1 g of citric acid was added and stirred for 30 minutes. Thereafter, the polymer was isolated by precipitation in NMP / water 1/4. After thorough washing with water, the product was dried in vacuo at 120 ° C for 12 h. The viscosity number of the product was 39.4 ml / g.
- the polymer compositions of the present invention have high temperature and color stability.
- the discoloration and turbidity is significantly reduced compared to the use of acetic acid or mineral acids.
- the polymer compositions also have a significantly reduced potassium content.
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- Polyethers (AREA)
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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US13/130,139 US20110224386A1 (en) | 2008-11-20 | 2009-11-12 | Reactive polyarylene ether and method for the manufacture thereof |
JP2011536829A JP5645838B2 (ja) | 2008-11-20 | 2009-11-12 | 反応性ポリアリーレンエーテル、及びその製造方法 |
EP09755880A EP2358787B1 (de) | 2008-11-20 | 2009-11-12 | Verfahren zur herstellung eines reaktiven polyarylenethers |
CN200980146551.6A CN102224185B (zh) | 2008-11-20 | 2009-11-12 | 具有反应活性的聚芳醚及其制备方法 |
BRPI0920955A BRPI0920955A2 (pt) | 2008-11-20 | 2009-11-12 | processo para a preparação de uma composição polimérica , composição polimérica, misturas, e, uso da composição polimérica |
ES09755880T ES2399961T3 (es) | 2008-11-20 | 2009-11-12 | Método para la producción de un poliarilenéter reactivo |
KR1020117013933A KR101694276B1 (ko) | 2008-11-20 | 2009-11-12 | 반응성 폴리아릴렌 에테르 및 그의 제조 방법 |
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EP08169537.1 | 2008-11-20 | ||
EP08169537 | 2008-11-20 |
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PCT/EP2009/065035 WO2010057822A1 (de) | 2008-11-20 | 2009-11-12 | Reaktive polyarylenether und verfahren zu deren herstellung |
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US (1) | US20110224386A1 (ja) |
EP (1) | EP2358787B1 (ja) |
JP (1) | JP5645838B2 (ja) |
KR (1) | KR101694276B1 (ja) |
CN (1) | CN102224185B (ja) |
BR (1) | BRPI0920955A2 (ja) |
ES (1) | ES2399961T3 (ja) |
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WO (1) | WO2010057822A1 (ja) |
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US8524853B2 (en) | 2009-06-08 | 2013-09-03 | Basf Se | Segmented polyarylene ether block copolymers |
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WO2014177638A2 (en) | 2013-05-02 | 2014-11-06 | Basf Se | Block copolymers |
US8952109B2 (en) | 2011-08-05 | 2015-02-10 | Basf Se | Process for preparing a block copolymer |
EP3476883A4 (en) * | 2016-06-24 | 2019-12-18 | Sumitomo Chemical Company, Limited | AROMATIC POLYSULFONE AND AROMATIC POLYSULFONE COMPOSITION |
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- 2009-11-12 WO PCT/EP2009/065035 patent/WO2010057822A1/de active Application Filing
- 2009-11-12 JP JP2011536829A patent/JP5645838B2/ja active Active
- 2009-11-12 BR BRPI0920955A patent/BRPI0920955A2/pt not_active IP Right Cessation
- 2009-11-12 US US13/130,139 patent/US20110224386A1/en not_active Abandoned
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Cited By (8)
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---|---|---|---|---|
US8524853B2 (en) | 2009-06-08 | 2013-09-03 | Basf Se | Segmented polyarylene ether block copolymers |
CN103717638A (zh) * | 2011-08-05 | 2014-04-09 | 巴斯夫欧洲公司 | 制备嵌段共聚物的方法 |
US8952109B2 (en) | 2011-08-05 | 2015-02-10 | Basf Se | Process for preparing a block copolymer |
WO2014177638A2 (en) | 2013-05-02 | 2014-11-06 | Basf Se | Block copolymers |
US10144807B2 (en) | 2013-05-02 | 2018-12-04 | Basf Se | Block copolymers |
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EP3882298A4 (en) * | 2018-11-14 | 2022-08-24 | Sumitomo Chemical Company Limited | PROCESS FOR PRODUCTION OF AROMATIC POLYSULFONE |
Also Published As
Publication number | Publication date |
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JP5645838B2 (ja) | 2014-12-24 |
KR20110095370A (ko) | 2011-08-24 |
BRPI0920955A2 (pt) | 2016-01-05 |
ES2399961T3 (es) | 2013-04-04 |
EP2358787A1 (de) | 2011-08-24 |
CN102224185A (zh) | 2011-10-19 |
JP2012509375A (ja) | 2012-04-19 |
CN102224185B (zh) | 2013-03-27 |
US20110224386A1 (en) | 2011-09-15 |
KR101694276B1 (ko) | 2017-01-09 |
EP2358787B1 (de) | 2013-01-09 |
MY150816A (en) | 2014-02-28 |
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