JPH03250026A - Production of terminal-modified polyphenylene ether - Google Patents
Production of terminal-modified polyphenylene etherInfo
- Publication number
- JPH03250026A JPH03250026A JP4565490A JP4565490A JPH03250026A JP H03250026 A JPH03250026 A JP H03250026A JP 4565490 A JP4565490 A JP 4565490A JP 4565490 A JP4565490 A JP 4565490A JP H03250026 A JPH03250026 A JP H03250026A
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- group
- acid
- formula
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 5
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000004952 Polyamide Substances 0.000 abstract description 2
- 229920002647 polyamide Polymers 0.000 abstract description 2
- 229920000728 polyester Polymers 0.000 abstract description 2
- 229920000098 polyolefin Polymers 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 3
- 230000002542 deteriorative effect Effects 0.000 abstract 2
- 150000003977 halocarboxylic acids Chemical class 0.000 abstract 2
- 150000002367 halogens Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- -1 n-amyl Chemical group 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000003444 phase transfer catalyst Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- KOUAQOCYMAENKN-UHFFFAOYSA-N ethyl 2-bromohexanoate Chemical compound CCCCC(Br)C(=O)OCC KOUAQOCYMAENKN-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 2
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 description 2
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- IUDGNRWYNOEIKF-UHFFFAOYSA-N 11-bromo-undecanoic acid Chemical compound OC(=O)CCCCCCCCCCBr IUDGNRWYNOEIKF-UHFFFAOYSA-N 0.000 description 1
- YYKBWYBUCFHYPR-UHFFFAOYSA-N 12-bromododecanoic acid Chemical compound OC(=O)CCCCCCCCCCCBr YYKBWYBUCFHYPR-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 description 1
- UEBARDWJXBGYEJ-UHFFFAOYSA-N 2-bromo-3-methylbutanoic acid Chemical compound CC(C)C(Br)C(O)=O UEBARDWJXBGYEJ-UHFFFAOYSA-N 0.000 description 1
- YAQLSKVCTLCIIE-UHFFFAOYSA-N 2-bromobutyric acid Chemical compound CCC(Br)C(O)=O YAQLSKVCTLCIIE-UHFFFAOYSA-N 0.000 description 1
- HZTPKMIMXLTOSK-UHFFFAOYSA-N 2-bromohexanoic acid Chemical compound CCCCC(Br)C(O)=O HZTPKMIMXLTOSK-UHFFFAOYSA-N 0.000 description 1
- GTGTXZRPJHDASG-UHFFFAOYSA-N 2-bromooctanoic acid Chemical compound CCCCCCC(Br)C(O)=O GTGTXZRPJHDASG-UHFFFAOYSA-N 0.000 description 1
- WMFATTFQNRPXBQ-UHFFFAOYSA-N 2-bromopentanoic acid Chemical compound CCCC(Br)C(O)=O WMFATTFQNRPXBQ-UHFFFAOYSA-N 0.000 description 1
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical compound CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- IAWIJHCUEPVIOO-UHFFFAOYSA-N 2-imidazol-1-yl-1-[4-(2-phenylethyl)phenyl]ethanol Chemical compound C=1C=C(CCC=2C=CC=CC=2)C=CC=1C(O)CN1C=CN=C1 IAWIJHCUEPVIOO-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical group CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 1
- KMRNTNDWADEIIX-UHFFFAOYSA-N 3-Iodopropanoic acid Chemical compound OC(=O)CCI KMRNTNDWADEIIX-UHFFFAOYSA-N 0.000 description 1
- DHXNZYCXMFBMHE-UHFFFAOYSA-N 3-bromopropanoic acid Chemical compound OC(=O)CCBr DHXNZYCXMFBMHE-UHFFFAOYSA-N 0.000 description 1
- QEYMMOKECZBKAC-UHFFFAOYSA-N 3-chloropropanoic acid Chemical compound OC(=O)CCCl QEYMMOKECZBKAC-UHFFFAOYSA-N 0.000 description 1
- GRHQDJDRGZFIPO-UHFFFAOYSA-N 4-bromobutanoic acid Chemical compound OC(=O)CCCBr GRHQDJDRGZFIPO-UHFFFAOYSA-N 0.000 description 1
- IPLKGJHGWCVSOG-UHFFFAOYSA-N 4-chlorobutanoic acid Chemical compound OC(=O)CCCCl IPLKGJHGWCVSOG-UHFFFAOYSA-N 0.000 description 1
- WNXNUPJZWYOKMW-UHFFFAOYSA-N 5-bromopentanoic acid Chemical compound OC(=O)CCCCBr WNXNUPJZWYOKMW-UHFFFAOYSA-N 0.000 description 1
- YSXDKDWNIPOSMF-UHFFFAOYSA-N 5-chloropentanoic acid Chemical compound OC(=O)CCCCCl YSXDKDWNIPOSMF-UHFFFAOYSA-N 0.000 description 1
- NVRVNSHHLPQGCU-UHFFFAOYSA-N 6-bromohexanoic acid Chemical compound OC(=O)CCCCCBr NVRVNSHHLPQGCU-UHFFFAOYSA-N 0.000 description 1
- WTCJJEJMYYASNT-UHFFFAOYSA-N 7-chloro-1-(2,4-difluorophenyl)-6-fluoro-4-oxo-1,8-naphthyridine-3-carboxylic acid Chemical compound C12=NC(Cl)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1=CC=C(F)C=C1F WTCJJEJMYYASNT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BKJFDZSBZWHRNH-UHFFFAOYSA-N 8-bromooctanoic acid Chemical compound OC(=O)CCCCCCCBr BKJFDZSBZWHRNH-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100024133 Coiled-coil domain-containing protein 50 Human genes 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 101000910772 Homo sapiens Coiled-coil domain-containing protein 50 Proteins 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VJGNLOIQCWLBJR-UHFFFAOYSA-M benzyl(tributyl)azanium;chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 VJGNLOIQCWLBJR-UHFFFAOYSA-M 0.000 description 1
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 1
- WGLNUYFDFWHHQG-UHFFFAOYSA-N bromo dodecanoate Chemical compound CCCCCCCCCCCC(=O)OBr WGLNUYFDFWHHQG-UHFFFAOYSA-N 0.000 description 1
- YJRGMUWRPCPLNH-UHFFFAOYSA-N butyl 2-chloroacetate Chemical compound CCCCOC(=O)CCl YJRGMUWRPCPLNH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- DYFVMVODIGRODW-UHFFFAOYSA-N ethyl 12-bromododecanoate Chemical compound CCOC(=O)CCCCCCCCCCCBr DYFVMVODIGRODW-UHFFFAOYSA-N 0.000 description 1
- XIMFCGSNSKXPBO-UHFFFAOYSA-N ethyl 2-bromobutanoate Chemical compound CCOC(=O)C(Br)CC XIMFCGSNSKXPBO-UHFFFAOYSA-N 0.000 description 1
- GNCLPIAYAPQPOU-UHFFFAOYSA-N ethyl 2-bromoheptanoate Chemical compound CCCCCC(Br)C(=O)OCC GNCLPIAYAPQPOU-UHFFFAOYSA-N 0.000 description 1
- ORSIRXYHFPHWTN-UHFFFAOYSA-N ethyl 2-bromopentanoate Chemical compound CCCC(Br)C(=O)OCC ORSIRXYHFPHWTN-UHFFFAOYSA-N 0.000 description 1
- ARFLASKVLJTEJD-UHFFFAOYSA-N ethyl 2-bromopropanoate Chemical compound CCOC(=O)C(C)Br ARFLASKVLJTEJD-UHFFFAOYSA-N 0.000 description 1
- JEAVBVKAYUCPAQ-UHFFFAOYSA-N ethyl 2-chloropropanoate Chemical compound CCOC(=O)C(C)Cl JEAVBVKAYUCPAQ-UHFFFAOYSA-N 0.000 description 1
- FQTIYMRSUOADDK-UHFFFAOYSA-N ethyl 3-bromopropanoate Chemical compound CCOC(=O)CCBr FQTIYMRSUOADDK-UHFFFAOYSA-N 0.000 description 1
- ZCLGVXACCAZJOX-UHFFFAOYSA-N ethyl 3-chloropropanoate Chemical compound CCOC(=O)CCCl ZCLGVXACCAZJOX-UHFFFAOYSA-N 0.000 description 1
- XBPOBCXHALHJFP-UHFFFAOYSA-N ethyl 4-bromobutanoate Chemical compound CCOC(=O)CCCBr XBPOBCXHALHJFP-UHFFFAOYSA-N 0.000 description 1
- OPXNFHAILOHHFO-UHFFFAOYSA-N ethyl 4-chlorobutanoate Chemical compound CCOC(=O)CCCCl OPXNFHAILOHHFO-UHFFFAOYSA-N 0.000 description 1
- AFRWBGJRWRHQOV-UHFFFAOYSA-N ethyl 5-bromopentanoate Chemical compound CCOC(=O)CCCCBr AFRWBGJRWRHQOV-UHFFFAOYSA-N 0.000 description 1
- DXBULVYHTICWKT-UHFFFAOYSA-N ethyl 6-bromohexanoate Chemical compound CCOC(=O)CCCCCBr DXBULVYHTICWKT-UHFFFAOYSA-N 0.000 description 1
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 1
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 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
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- JDNTWHVOXJZDSN-UHFFFAOYSA-N iodoacetic acid Chemical compound OC(=O)CI JDNTWHVOXJZDSN-UHFFFAOYSA-N 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- HFNPVFKUZYCDIB-UHFFFAOYSA-N methyl 11-bromoundecanoate Chemical compound COC(=O)CCCCCCCCCCBr HFNPVFKUZYCDIB-UHFFFAOYSA-N 0.000 description 1
- QNXOHINFQALBQN-UHFFFAOYSA-N methyl 12-bromododecanoate Chemical compound COC(=O)CCCCCCCCCCCBr QNXOHINFQALBQN-UHFFFAOYSA-N 0.000 description 1
- YDCHPLOFQATIDS-UHFFFAOYSA-N methyl 2-bromoacetate Chemical compound COC(=O)CBr YDCHPLOFQATIDS-UHFFFAOYSA-N 0.000 description 1
- MGMWQSVSOGNGPL-UHFFFAOYSA-N methyl 2-bromopentanoate Chemical compound CCCC(Br)C(=O)OC MGMWQSVSOGNGPL-UHFFFAOYSA-N 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- JLEJCNOTNLZCHQ-UHFFFAOYSA-N methyl 2-chloropropanoate Chemical compound COC(=O)C(C)Cl JLEJCNOTNLZCHQ-UHFFFAOYSA-N 0.000 description 1
- KQEVIFKPZOGBMZ-UHFFFAOYSA-N methyl 3-bromopropanoate Chemical compound COC(=O)CCBr KQEVIFKPZOGBMZ-UHFFFAOYSA-N 0.000 description 1
- GZGJIACHBCQSPC-UHFFFAOYSA-N methyl 3-chloropropanoate Chemical compound COC(=O)CCCl GZGJIACHBCQSPC-UHFFFAOYSA-N 0.000 description 1
- ZZUYIRISBMWFMV-UHFFFAOYSA-N methyl 4-chlorobutanoate Chemical compound COC(=O)CCCCl ZZUYIRISBMWFMV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 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
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- KPFSGNRRZMYZPH-UHFFFAOYSA-M potassium;2-chloroacetate Chemical compound [K+].[O-]C(=O)CCl KPFSGNRRZMYZPH-UHFFFAOYSA-M 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- VODRWDBLLGYRJT-UHFFFAOYSA-N propan-2-yl 2-chloroacetate Chemical compound CC(C)OC(=O)CCl VODRWDBLLGYRJT-UHFFFAOYSA-N 0.000 description 1
- JJJIDWYYEJSHCR-UHFFFAOYSA-M sodium 5-chloropentanoate Chemical compound [Na+].[O-]C(=O)CCCCCl JJJIDWYYEJSHCR-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JWPMAIDKYSIYRO-UHFFFAOYSA-M sodium;11-bromoundecanoate Chemical compound [Na+].[O-]C(=O)CCCCCCCCCCBr JWPMAIDKYSIYRO-UHFFFAOYSA-M 0.000 description 1
- SESSOVUNEZQNBV-UHFFFAOYSA-M sodium;2-bromoacetate Chemical compound [Na+].[O-]C(=O)CBr SESSOVUNEZQNBV-UHFFFAOYSA-M 0.000 description 1
- AGDSCTQQXMDDCV-UHFFFAOYSA-M sodium;2-iodoacetate Chemical compound [Na+].[O-]C(=O)CI AGDSCTQQXMDDCV-UHFFFAOYSA-M 0.000 description 1
- PCVKFNSNKBXJFZ-UHFFFAOYSA-M sodium;3-bromopropanoate Chemical compound [Na+].[O-]C(=O)CCBr PCVKFNSNKBXJFZ-UHFFFAOYSA-M 0.000 description 1
- UWHWTUHOJMSSBX-UHFFFAOYSA-M sodium;6-bromohexanoate Chemical compound [Na+].[O-]C(=O)CCCCCBr UWHWTUHOJMSSBX-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、ポリフェニレンエーテルの末端フェノール性
水酸基の官能化による末端基変性ポリフェニレンエーテ
ルの製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing terminal group-modified polyphenylene ether by functionalizing the terminal phenolic hydroxyl group of polyphenylene ether.
［従来の技術］
ポリフェニレンエーテルは、優れた耐熱性、機械的特性
、電気的特性、耐水性、耐酸性、耐アルカリ性、自己消
火性を備えた極めて有用な熱可塑性樹脂であり、エンジ
ニアリングプラスチック材料として、多くの応用展開が
図られている。しかしながら、ポリフェニレンエーテル
は、本質的に脆性を示す樹脂であるため、エラストマー
のような耐衝撃改質剤とブレンドして用いられることが
多い、また、自動車外板用には、ポリアミド系樹脂とブ
レンドし耐溶剤性を改良している。しかし、このような
ブレンドは相分離等を起こし衝撃強度を低下させること
が多い。[Prior Art] Polyphenylene ether is an extremely useful thermoplastic resin with excellent heat resistance, mechanical properties, electrical properties, water resistance, acid resistance, alkali resistance, and self-extinguishing properties, and is used as an engineering plastic material. , many applications are being developed. However, since polyphenylene ether is an inherently brittle resin, it is often blended with impact modifiers such as elastomers, and is blended with polyamide resins for automobile exterior panels. Improved solvent resistance. However, such blends often cause phase separation and the like, resulting in a decrease in impact strength.
これを改良するものとして、ポリフェニレンエーテルを
、不飽和結合を持つ酸無水物又はカルボン酸、好ましく
は無水マレイン酸で官能化してポリアミド樹脂とブレン
ドする方法が、特開昭！１７６−２６９１３号及び特開
昭５６−４９７５３号各公報に開示されている。特表昭
６３−５００８０３号公報には、不飽和結合とカルボン
酸を併せ持つ化合物によるポリフェニレンエーテルの官
能化が示されている。To improve this, a method has been proposed in JP-A-Sho, in which polyphenylene ether is functionalized with an acid anhydride or carboxylic acid having an unsaturated bond, preferably maleic anhydride, and blended with a polyamide resin. It is disclosed in Japanese Patent Laid-Open No. 176-26913 and Japanese Patent Application Laid-Open No. 56-49753. Japanese Patent Publication No. 63-500803 discloses the functionalization of polyphenylene ether with a compound having both an unsaturated bond and a carboxylic acid.
これらの方法によるカルボキシル基官能化ポリフェニレ
ンエーテルは、官能化剤の不飽和結合がポリフェニレン
エーテルの主鎖に付加していると報告されている（Ｊｏ
ｕｒｎａｌ ｏｆ Ｐｏ１ｙ＋＊ｅｒＳｃｉｅｎｃｅ：
Ｐａｒｔ＾： Ｐｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ
、 ２７巻、Ｐ、３３７１．１９８９参照）、また、こ
れらの方法によるポリフェニレンエーテルの変性には、
高温又はラジカルの存在下での反応が必要であり、ポリ
フェニレンエーテルの劣化問題等が発生し、未だ解決す
べき課題が多い。It has been reported that the carboxyl group-functionalized polyphenylene ether obtained by these methods has an unsaturated bond of the functionalizing agent added to the main chain of the polyphenylene ether (Jo
Urnal of Poly+*erScience:
Part＾: Polymer Chemistry
, Vol. 27, P, 3371.1989), and for the modification of polyphenylene ether by these methods,
Reactions are required at high temperatures or in the presence of radicals, leading to problems such as deterioration of polyphenylene ether, and there are still many problems to be solved.
［発明が解決しようとする課題］
本発明は、ポリアミド、ポリエステル、ポリオレフィン
等の樹脂とのブレンド時に相溶性のある組成物を形成し
得るカルボン酸官能化ポリフェニレンエーテルの極めて
容易な製造方法を提供することを目的とする。[Problems to be Solved by the Invention] The present invention provides an extremely easy method for producing carboxylic acid-functionalized polyphenylene ethers that can form compatible compositions when blended with resins such as polyamides, polyesters, and polyolefins. The purpose is to
［課題を解決するための手段〕
本発明者らは、ポリフェニレンエーテルの末端フェノー
ル性水酸基をハロゲン化カルボン酸類を用いてカルボキ
シル基官能化することにより、従来の方法に比較して劣
化の少ない官能化ポリフェニレンエーテルが容易に得ら
れることを見出し、本発明を完成した。[Means for Solving the Problem] The present inventors functionalized the terminal phenolic hydroxyl group of polyphenylene ether with a carboxyl group using halogenated carboxylic acids, thereby achieving functionalization with less deterioration compared to conventional methods. The present invention was completed based on the discovery that polyphenylene ether can be easily obtained.
本発明は一般式
（式中Ｑｌは各々ハロゲン原子、第−級若しくは第二級
アルキル基、フェニル基、アミノアルキル基、炭化水素
オキシ基又はハロ炭化水素オキシ基を表わし、Ｑ、は各
々水素原子、ハロゲ県子。The present invention is based on the general formula (wherein each Ql represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and each Q represents a hydrogen atom) , Haroge Kenko.
第−級若しくは第二級アルキル基、フェニル基。Primary or secondary alkyl group, phenyl group.
ハロアルキル基、炭化水素オキシ基又はハロ炭化水素オ
キシ基を表わす１ｍは１０以上の数を表わす）
で示されるポリフェニレンエーテルに、−量大
％式％（）
（式中、Ｒ１は炭素数１〜１２のアルキレン基。(1m representing a haloalkyl group, hydrocarbonoxy group, or halohydrocarbonoxy group represents a number of 10 or more) alkylene group.
Ｒ２は水素原子、炭素数１〜１０の炭化水素基又はアル
カリ金属原子を表わし、Ｘはハロゲン原子を表わす）
で示されるハロゲン化カルボン酸類を反応させることを
特徴とする。R2 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkali metal atom, and X represents a halogen atom).
一般式 （式中、 Ｑ １、 Ｑ２、 ｍ。general formula (In the formula, Q1, Q2, m.
Ｒ１、
Ｒ２は前記と同
じ）
で示される末端基変性ポリフェニレンエーテルの製造方
法である。R1 and R2 are the same as above) This is a method for producing a terminal group-modified polyphenylene ether.
本発明で使用するポリフェニレンエーテルは、の構造単
位を有する単独重合体又は共重合体である。ＱＩ及びＱ
２の第一低級アルキル基の好適な例は、メチル、エチル
、ｎ−プロピル、ｎ−ブチル、ｎ−アミル、イソアミル
、２−メチルブチル、ｎ−ヘキシル、２．３−ジメチル
ブチル、２−１３−又は４−メチルペンチル又はヘプチ
ルである。第二級アルキル基の例は、イソプロピル、５
ｅｃ−ブチル又はｌ−エチルプロピルである。多くの場
合、Ｑｌはアルキル基又はフェニル基、特に炭素ｆｉ１
〜４のアルキル基であり、Ｑ２は水素原子である。The polyphenylene ether used in the present invention is a homopolymer or copolymer having the structural unit. QI and Q
Suitable examples of the first lower alkyl group in 2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5
ec-butyl or l-ethylpropyl. Often Ql is an alkyl or phenyl group, especially the carbon fi1
-4 alkyl group, and Q2 is a hydrogen atom.
好適なポリフェニレンエーテルの単独重合体としては、
例えば、２．６−シメチルー１．４−フェニレンエーテ
ル単位からなるものである。好適な共重合体としては、
上記単位と２．３．６−ドリメチルー１．４−フェニレ
ンエーテル単位との組合せからなるランダム共重合体で
ある。多くの好適な単独重合体又はランダム共重合体が
、特許、文献に記載されている０例えば１分子量、溶融
粘度及び／又は衝撃強度等の特性を改良する分子構成部
分を含むポリフェニレンエーテルも、また好適である０
例えばアクリロニトリル又はスチレン等のビニル芳香族
化合物などのビニルモノマーあるいはポリスチレン又は
そのエラストマーなどのポリマーをポリフェニレンエー
テル上にグラフトさせたポリフェニレンエーテル等であ
る。Suitable polyphenylene ether homopolymers include:
For example, it is composed of 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include:
It is a random copolymer consisting of a combination of the above units and 2,3,6-drimethyl-1,4-phenylene ether units. Many suitable homopolymers or random copolymers have been described in the patent literature, including polyphenylene ethers containing molecular moieties that improve properties such as molecular weight, melt viscosity, and/or impact strength. 0 is preferred
Examples include polyphenylene ether in which a vinyl monomer such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof is grafted onto polyphenylene ether.
ポリフェニレンエーテルの分子量は通常クロロホルム中
、３０℃の固有粘度が０．２〜０．８ｄｌ／ｇ程度であ
る。Polyphenylene ether usually has an inherent viscosity of about 0.2 to 0.8 dl/g at 30°C in chloroform.
ポリフェニレンエーテルは、通常前記のモノマーの酸化
カップリングにより製造される。ポリフェニレンエーテ
ルの酸化カップリング重合に関しては、数多くの触媒系
が知られている。触媒の選択に関しては特に制限はなく
、公知の触媒のいずれも用いることができる０例えば、
銅、マンガン、コバルト等の重金属化合物の少なくとも
一種を通常は種々の他の物質との組合せで含むもの等で
ある。Polyphenylene ethers are usually produced by oxidative coupling of the monomers described above. A number of catalyst systems are known for the oxidative coupling polymerization of polyphenylene ethers. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used.For example,
These include at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.
本発明で用いる官能化剤は、ハロゲン化カルボン酸、ハ
ロゲン化カルボン酸アルキルエステル及びハロゲン化カ
ルボン酸アルカリ金属塩のうちから選ばれた少なくとも
１種である。ハロゲン原子は、塩素原子、臭素原子、ヨ
ウ素原子等である。The functionalizing agent used in the present invention is at least one selected from halogenated carboxylic acids, halogenated carboxylic acid alkyl esters, and alkali metal salts of halogenated carboxylic acids. The halogen atom is a chlorine atom, a bromine atom, an iodine atom, or the like.
ハロゲン化カルボン酸アルキルエステルのアルキル基は
、一般に炭素数１〜１０のものであり、アリール基で置
換されたアルキル基を含むことができる。ハロゲン化カ
ルボン酸アルカリ金属塩のアルカリ金属は、リチウム、
ナトリウム、カリウム等である。ハロゲン化カルボン酸
類を構成するアルキレン基は、炭素数１−１２である。The alkyl group of the halogenated carboxylic acid alkyl ester generally has 1 to 10 carbon atoms, and can include an alkyl group substituted with an aryl group. The alkali metal of the halogenated carboxylic acid alkali metal salt is lithium,
These include sodium and potassium. The alkylene group constituting the halogenated carboxylic acid has 1 to 12 carbon atoms.
ハロゲン化カルボン酸類の具体例を挙げると、クロル酢
酸。A specific example of halogenated carboxylic acids is chloroacetic acid.
ブロム酢酸、ヨード酢酸、２−クロルプロピオン酸、３
−クロルプロピオン酸、２−ブロムプロピオン酸、３−
ブロムプロピオン酸、３−ヨードプロピオン酸、４−ク
ロル酪酸、２−ブロム酪酸、４−ブロム酪酸、２−ブロ
ム−２−メチルプロピオン酸、３−クロル−２，２−ジ
メチルプロピオン酸、５−クロル吉草酸、２−ブロム−
３−メチル酪酸、２−ブロム吉草酸、５−ブロム吉草酸
、２−ブロムヘキサン酸、６−ブロムヘキサン酸、２−
ブロムオクタン酸、８−ブロムオクタン酸、１１−ブロ
ムウンデカン酸、１２−ブロムドデカン酸１、クロル酢
酸ナトリウム、クロル酢酸カリウム、ヨード酢酸ナトリ
ウム、ブロム酢酸ナトリウム、３−ブロムプロピオン酸
ナトリウム、３−ヨードプロピオン酸ナトリウム、４−
クロル酪酸ナトリウム、５−クロル吉草酸ナトリウム、
６−ブロムヘキサン酸ナトリウム、８−ブロムオクタン
酸ナトリウム、１１−ブロムウンデカン酸ナトリウム、
１２−ブロムドデカン酸ナトリウム、クロル酢酸メチル
エステル、クロル酢酸エチルエスチル、クロル酢酸ビニ
ルエステル、クロル酢酸アリルエステル、クロル酢酸ブ
チルエステル、クロル酢酸イソプロピルエステル、ブロ
ム酢酸メチルエステル、ブロム酢酸エチルエステル、２
−クロルプロピオン酸メチルエステル、２−クロルプロ
ピオン酸エチルエステル、３−クロルプロピオン酸メチ
ルエステル、３−クロルプロピオン酸エチルエステル、
２−ブロムプロピオン酸メチルエステル、２−ブロムプ
ロピオン酸エチルエステル。Bromoacetic acid, iodoacetic acid, 2-chloropropionic acid, 3
-Chlorpropionic acid, 2-bromopropionic acid, 3-
Bromopropionic acid, 3-iodopropionic acid, 4-chlorobutyric acid, 2-bromobutyric acid, 4-bromobutyric acid, 2-bromo-2-methylpropionic acid, 3-chloro-2,2-dimethylpropionic acid, 5-chloro Valeric acid, 2-bromo-
3-Methylbutyric acid, 2-bromovaleric acid, 5-bromovaleric acid, 2-bromohexanoic acid, 6-bromohexanoic acid, 2-
Bromooctanoic acid, 8-bromooctanoic acid, 11-bromoundecanoic acid, 12-bromododecanoic acid 1, sodium chloroacetate, potassium chloroacetate, sodium iodoacetate, sodium bromoacetate, sodium 3-bromopropionate, 3-iodopropion sodium acid, 4-
Sodium chlorobutyrate, sodium 5-chlorovalerate,
Sodium 6-bromohexanoate, sodium 8-bromooctanoate, sodium 11-bromoundecanoate,
12-Sodium bromododecanoate, chloroacetic acid methyl ester, chloroacetic acid ethyl ester, chloroacetic acid vinyl ester, chloroacetic acid allyl ester, chloroacetic acid butyl ester, chloroacetic acid isopropyl ester, bromoacetic acid methyl ester, bromoacetic acid ethyl ester, 2
-chloropropionate methyl ester, 2-chloropropionate ethyl ester, 3-chloropropionate methyl ester, 3-chloropropionate ethyl ester,
2-bromopropionic acid methyl ester, 2-bromopropionic acid ethyl ester.
３−ブロムプロピオン酸メチルエステル、３−ブロムプ
ロピオン酸エチルエステル、４−クロル酪酸メチルエス
テル、４−クロル酪酸エチルエステル、２−ブロム酪酸
エチルエステル、４−ブロム酪酸エチルエステル、２−
ブロム吉草酸メチルエステル、２−ブロム吉草酸エチル
エステル、５−ブロム吉草酸エチルエステル、２−ブロ
ムヘキサン酸エチルエステル、６−ブロムヘキサン酸エ
チルエステル、２−ブロムヘプタン酸エチルエステル、
１１−ブロムウンデカン酸メチルエステル、１２−ブロ
ムドデカン酸メチルエステル、１２−ブロムドデカン酸
エチルエステル等である。3-bromopropionic acid methyl ester, 3-bromopropionic acid ethyl ester, 4-chlorobutyric acid methyl ester, 4-chlorobutyric acid ethyl ester, 2-bromobutyric acid ethyl ester, 4-bromobutyric acid ethyl ester, 2-
Bromovaleric acid methyl ester, 2-bromovaleric acid ethyl ester, 5-bromovaleric acid ethyl ester, 2-bromohexanoic acid ethyl ester, 6-bromohexanoic acid ethyl ester, 2-bromoheptanoic acid ethyl ester,
These include methyl 11-bromundecanoate, methyl 12-bromododecanoate, ethyl 12-bromododecanoate, and the like.
本発明の官能化されたポリフェニレンエーテルは、以下
の方法により製造される。すなわち、ポリフェニレンエ
ーテルが溶解可能な有機溶媒と水溶性の無機塩基性化合
物を溶解させた水の混合溶媒中、相間移動触媒の存在下
、ポリフェニレンエーテルとハロゲン化カルボン酸類を
反応させることにより容易に製造できる。この反応は、
２０〜１００℃、好ましくは、５０〜１００℃の温度範
囲で行なう。The functionalized polyphenylene ether of the present invention is produced by the following method. That is, it is easily produced by reacting polyphenylene ether with halogenated carboxylic acids in the presence of a phase transfer catalyst in a mixed solvent of an organic solvent in which polyphenylene ether can be dissolved and water in which a water-soluble inorganic basic compound is dissolved. can. This reaction is
The temperature range is 20 to 100°C, preferably 50 to 100°C.
本反応で使用する有機溶媒の例としては、ベンゼン、ト
ルエン、キシレン等の芳香族系溶媒；クロロホルム、ジ
クロルエタン、トリクロルエタン等のハロゲン化脂肪族
炭化水素系溶媒；クロルベンゼン、ジクロルベンゼン等
のハロゲン化芳香族炭化水素系溶媒等が挙げられる。前
記の水溶性の無機塩基性化合物としては、アルカリ金属
又はアルカリ土類金属の水酸化物又は炭酸塩が挙げられ
る。具体的には、水酸化ナトリウム、水酸化カリウム、
炭酸ナトリウム等が好ましい、前記の相間移動触媒とし
ては、第四級アンモニウム塩化合物、第四級ホスフォニ
ウム塩化合物、第四級スルホニウム塩化合物が挙げられ
る。好ましくは、第四級アンモニウム塩化合物であり、
その具体的例として、ベンジルトリメチルアンモニウム
クロライド、ベンジルトリエチルアンモニウムクロライ
ド、ベンジルトリブチルアンモニウムクロライド、テト
ラブチルアンモニウムブロマイド、テトラブチルアンモ
ニウムハイドロジエンサルフェート、トリオクチルメチ
ルアンモニウムクロライド等が挙げられる。Examples of organic solvents used in this reaction include aromatic solvents such as benzene, toluene, and xylene; halogenated aliphatic hydrocarbon solvents such as chloroform, dichloroethane, and trichloroethane; and halogenated solvents such as chlorobenzene and dichlorobenzene. Examples include aromatic hydrocarbon solvents. Examples of the water-soluble inorganic basic compound include hydroxides or carbonates of alkali metals or alkaline earth metals. Specifically, sodium hydroxide, potassium hydroxide,
Examples of the phase transfer catalyst, preferably sodium carbonate, include quaternary ammonium salt compounds, quaternary phosphonium salt compounds, and quaternary sulfonium salt compounds. Preferably, it is a quaternary ammonium salt compound,
Specific examples include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride, and the like.
本反応に用いるポリフェニレンエーテル（ＩＩ）とハロ
ゲン化カルボン酸類（ＩＩＩ ）の反応量比は、ポリフ
ェニレンエーテルの末端フェノール性水酸基１モルに対
し、ハロゲン化カルボン酸類１〜２０モルであり、好ま
しくは、５〜１０モルである。相間移動触媒及び水溶性
の無機塩基性化合物の使用量は、ポリフェニレンエーテ
ル１００重量部に対して、それぞれｏ、ｉ−ｉ重量部及
び０．４〜５００重量部である。塩基性化合物は１０重
量部以上用いるのが好ましい、前記範囲未満では５反応
率が低下する。The reaction amount ratio of polyphenylene ether (II) and halogenated carboxylic acid (III) used in this reaction is 1 to 20 mol of halogenated carboxylic acid per 1 mol of terminal phenolic hydroxyl group of polyphenylene ether, preferably 5 ~10 moles. The amounts of the phase transfer catalyst and the water-soluble inorganic basic compound used are o, i-i parts and 0.4 to 500 parts by weight, respectively, based on 100 parts by weight of polyphenylene ether. It is preferable to use 10 parts by weight or more of the basic compound; if it is less than the above range, the reaction rate will decrease.
一方、ハロゲン化カルボン酸アルキルエステルを用いた
場合に限って、相間移動触媒及び水の非存在下の系で、
少量のメタノール、エタノール等の低級アルコールを加
えることにより目的のカルボキシル基官能化ポリフェニ
レンエーテルを製造することができる。On the other hand, only when using a halogenated carboxylic acid alkyl ester, in a system in the absence of a phase transfer catalyst and water,
By adding a small amount of lower alcohol such as methanol or ethanol, the desired carboxyl group-functionalized polyphenylene ether can be produced.
［実施例Ｊ
本発明の官能化されたポリフェニレンエーテルの製造法
を、実施例によって以下に、説明する。Example J The method for preparing the functionalized polyphenylene ether of the present invention is illustrated below by way of example.
なお、ポリフェニレンエーテル樹脂の末端フェノール性
水酸基の反応率は、ジャーナル・オブ・アプライド・ポ
リマー・サイエンス・アプライド・ポリマー・シンポジ
ウム（Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌ
ｙｍｅｒ ５ｃｉｅｎｃｅ：ＡｐｐｌｉｅｄＰｏｌｙｍ
ｅｒ Ｓｙａ＋ｐｏｓｉｕｍ ） 、 ３４巻（１９７
８年）、１０３〜１１７頁に記載の方法に準じて、反応
前後の末端フェノール性水酸基を定量して計算した。Note that the reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether resin is based on the Journal of Applied Polymer Science Applied Polymer Symposium (Journal of Applied Polymer Symposium).
ymer 5science: Applied Polym
er Sya+posium), Volume 34 (197
The terminal phenolic hydroxyl groups before and after the reaction were quantitatively determined and calculated according to the method described in 8th Year), pp. 103-117.
実施例１〜６
ポリ（２，６−シメチルー１．４−フェニレンエーテル
）（ＰＰＥ、３０℃においてクロロホルム中で測定した
固有粘度：実施例１では０，５１ｄｌ／ｇ、実施例２〜
６では０．３１ｄｌ／ｇ）、クロル酢酸ナトリウム、ト
ルエン、水酸化ナトリウム、水及び相間移動触媒を表１
に示した配合量に従って、反応器に仕込み、加熱撹拌し
て、反応させた１反応器合物を冷却後、６規定の塩酸で
中和した後、大量のメタノール中に注ぎ、生成した変性
樹脂を沈澱させた。これを）戸別した後水洗し、更にメ
タノールで２回洗浄した。１００℃で減圧加熱乾燥して
、カルボキシル基官能化ポリフェニレンエーテルを得た
。結果を表１に示した。Examples 1-6 Poly(2,6-dimethyl-1,4-phenylene ether) (PPE, intrinsic viscosity measured in chloroform at 30°C: 0,51 dl/g in Example 1, Examples 2-6
6, 0.31 dl/g), sodium chloroacetate, toluene, sodium hydroxide, water and phase transfer catalyst in Table 1
The reaction mixture was charged into a reactor according to the amounts shown in , heated and stirred, and reacted. After cooling, the reactor mixture was neutralized with 6N hydrochloric acid, and then poured into a large amount of methanol to obtain the resulting modified resin. was precipitated. This was then washed with water and then twice with methanol. The mixture was dried under reduced pressure at 100° C. to obtain a carboxyl group-functionalized polyphenylene ether. The results are shown in Table 1.
これらの官能化ポリフェニレンエーテルは、その赤外線
吸収スペクトルの１７００ｃｍ−’付近にカルボキシル
基に由来すると考えれらる吸収を示した。These functionalized polyphenylene ethers exhibited absorption considered to originate from carboxyl groups near 1700 cm-' in their infrared absorption spectra.
実施例１で得たカルボキシル基官能化ポリフェニレンエ
ーテルのクロロホルム溶液より調製したキャストフィル
ムの赤外線吸収スペクトルを第１図に示した。The infrared absorption spectrum of a cast film prepared from a chloroform solution of the carboxyl group-functionalized polyphenylene ether obtained in Example 1 is shown in FIG.
実施例６で得たカルボキシル基官能化ポリフェニレンエ
ーテルのクロロホルム溶液より調製したキャストフィル
ムの赤外線吸収スペクトルを第２図に示した。The infrared absorption spectrum of a cast film prepared from a chloroform solution of the carboxyl group-functionalized polyphenylene ether obtained in Example 6 is shown in FIG.
実施例７〜８
ポリ（２，６−シメチルーフ二二しンエーテル）（３０
℃において、クロロホルム中で測定した固有粘度： ０
．３１ｄｌ／ｇ）、クロル酢酸メチルエステル、トルエ
ン、及びメタノールに溶解した水酸化ナトリウムを表２
に示した配合量に従って、反応器に仕込み撹拌し溶解し
た。この混合物を加熱撹拌し、表２に示した温度、時間
で反応させた。Examples 7-8 Poly(2,6-dimethylphinidine ether) (30
Intrinsic viscosity measured in chloroform at °C: 0
．． 31 dl/g), sodium hydroxide dissolved in methyl chloroacetate, toluene, and methanol in Table 2.
The mixture was charged into a reactor and stirred to dissolve according to the amount shown in . This mixture was heated and stirred to react at the temperature and time shown in Table 2.
反応混合物を大量のメタノール中に注ぎ、生成した変性
樹脂を沈澱させた。これを決別した後、水洗し、更にメ
タノールで２回洗浄した。１００℃で減圧加熱乾燥して
、官能化ポリフエニレンエーテ・ルを得た。The reaction mixture was poured into a large amount of methanol to precipitate the resulting modified resin. After separating this, it was washed with water and then twice with methanol. The mixture was dried under reduced pressure at 100° C. to obtain a functionalized polyphenylene ether.
結果を表２に示した。The results are shown in Table 2.
応用例１
実施例６で得た末端基変性ポリフェニレンエーテル２．
８４ｇとグリシジルメタクリレートで変性したポリプロ
ピレン（グリシジルメタクリレート含量６．５重量％、
メルトフローレート０．９２ｇ／１０分）１．ＯＯｇに
キシレン２００−を加え、１２５℃で８時間反応させた
。Application example 1 End group-modified polyphenylene ether obtained in Example 6 2.
84 g of polypropylene modified with glycidyl methacrylate (glycidyl methacrylate content 6.5% by weight,
Melt flow rate 0.92g/10min)1. Xylene 200- was added to OOg and reacted at 125°C for 8 hours.
反応混合物をメタノール１２中で注ぎ、生成したポリマ
ーを沈澱させ、ン戸別回収した。更に、このポリマーを
メタノールＩＩ２で洗浄した。８５℃で減圧加熱乾燥し
て、３．７３ｇのポリマーを得た。The reaction mixture was poured into 12 methanol to precipitate the polymer formed and collected separately. Furthermore, this polymer was washed with methanol II2. It was dried under reduced pressure at 85° C. to obtain 3.73 g of polymer.
次に、得られたポリマー１．２２ｇをクロロホルム２０
０−を溶媒として使用し、ソックスレー抽出器により抽
出を行い、未反応のポリフェニレンエーテルを除去した
。その結果、クロロホルム可溶分として抽出された未反
応ポリフェニレンエーテルは０．８０ｇであった。この
ことより。Next, 1.22 g of the obtained polymer was added to 20 g of chloroform.
0- as a solvent, extraction was performed using a Soxhlet extractor to remove unreacted polyphenylene ether. As a result, 0.80 g of unreacted polyphenylene ether was extracted as a chloroform-soluble component. From this.
得られたポリフエニレンエーテルーポリプロピレン共重
合体中のポリフェニレンエーテル含有量は、２３．８重
量％であることが判明した。The polyphenylene ether content in the obtained polyphenylene ether-polypropylene copolymer was found to be 23.8% by weight.
［発明の効果］
実施例に示したように、カルボキシル基官能化ポリフェ
ニレンエーテルは、本発明の方法によって、容易に製造
することができ、このものは更に、応用例１に示したよ
うに、処理されたポリプロピレンと容易に、共重合させ
ることができた。[Effects of the Invention] As shown in the Examples, carboxyl group-functionalized polyphenylene ether can be easily produced by the method of the present invention, and this product can be further treated as shown in Application Example 1. It could be easily copolymerized with polypropylene.
第１図は、実施例１で得られたカルボキシル基官能化ポ
リフェニレンエーテル（クロロホルム溶液より調製した
キャストフィルム）の赤外線吸収スペクトルを示す、第
２図は、実施例６で得られたカルボキシル基官能化ポリ
フェニレンエーテル（クロロホルム溶液より調製したキ
ャストフィルム）の赤外線吸収スペクトルを示す。Figure 1 shows the infrared absorption spectrum of the carboxyl-functionalized polyphenylene ether (cast film prepared from a chloroform solution) obtained in Example 1. Figure 2 shows the infrared absorption spectrum of the carboxyl-functionalized polyphenylene ether obtained in Example 6. The infrared absorption spectrum of polyphenylene ether (cast film prepared from chloroform solution) is shown.
Claims (1)
級アルキル基、フェニル基、アミノアルキル基、炭化水
素オキシ基又はハロ炭化水素オキシ基を表わし、Ｑ＿２
は各々水素原子、ハロゲン原子、第一級若しくは第二級
アルキル基、フェニル基、ハロアルキル基、炭化水素オ
キシ基又はハロ炭化水素オキシ基を表わす。ｍは１０以
上の数を表わす） で示されるポリフェニレンエーテルに、 一般式 ▲数式、化学式、表等があります▼（III） （式中、Ｒ＾１は炭素数１〜１２のアルキレン基、Ｒ＾
２は水素原子、炭素数１〜１０の炭化水素基又はアルカ
リ金属原子を表わし、Ｘはハロゲン原子を表わす） で示されるハロゲン化カルボン酸類を反応させることを
特徴とする、 一般式 ▲数式、化学式、表等があります▼（ I ） （式中、Ｑ＿１、Ｑ＿２、ｍ、Ｒ＾１、Ｒ＾２は前記と
同じ） で示される末端基変性ポリフェニレンエーテルの製造方
法。[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (II) (In the formula, Q_1 is each a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbon oxy group or halohydrocarbonoxy group, Q_2
each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group. (m represents a number of 10 or more) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R^1 is an alkylene group having 1 to 12 carbon atoms, R^
2 represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or an alkali metal atom, and X represents a halogen atom) General formula ▲ Numerical formula, chemical formula , tables, etc. ▼(I) (In the formula, Q_1, Q_2, m, R^1, and R^2 are the same as above.) A method for producing a terminal group-modified polyphenylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4565490A JPH03250026A (en) | 1990-02-28 | 1990-02-28 | Production of terminal-modified polyphenylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4565490A JPH03250026A (en) | 1990-02-28 | 1990-02-28 | Production of terminal-modified polyphenylene ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03250026A true JPH03250026A (en) | 1991-11-07 |
Family
ID=12725367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4565490A Pending JPH03250026A (en) | 1990-02-28 | 1990-02-28 | Production of terminal-modified polyphenylene ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03250026A (en) |
-
1990
- 1990-02-28 JP JP4565490A patent/JPH03250026A/en active Pending
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