JPH04145125A - Production of terminal carboxylic acid-modified polyphenylene ether - Google Patents
Production of terminal carboxylic acid-modified polyphenylene etherInfo
- Publication number
- JPH04145125A JPH04145125A JP26627790A JP26627790A JPH04145125A JP H04145125 A JPH04145125 A JP H04145125A JP 26627790 A JP26627790 A JP 26627790A JP 26627790 A JP26627790 A JP 26627790A JP H04145125 A JPH04145125 A JP H04145125A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyphenylene ether
- formula
- carboxylic acid
- ether
- 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 61
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000005843 halogen group Chemical group 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 3
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- -1 benzyl halide Chemical class 0.000 abstract description 11
- 229920006351 engineering plastic Polymers 0.000 abstract description 4
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract 3
- 150000002367 halogens Chemical class 0.000 abstract 2
- 230000001588 bifunctional effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000001797 benzyl group Chemical class [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000003607 modifier Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003444 phase transfer catalyst Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- WCOCCXZFEJGHTC-UHFFFAOYSA-N 2-[4-(bromomethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CBr)C=C1 WCOCCXZFEJGHTC-UHFFFAOYSA-N 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
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003849 aromatic solvent 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
- 229920001400 block copolymer Polymers 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920000578 graft copolymer Polymers 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000005691 oxidative coupling reaction Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- GJNNLILROAPGRC-UHFFFAOYSA-N 2-[4-(chloromethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CCl)C=C1 GJNNLILROAPGRC-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
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 description 1
- KMSXQYUJNMLISE-UHFFFAOYSA-N 4-(chloromethyl)-2-benzofuran-1,3-dione Chemical compound ClCC1=C2C(C(=O)OC2=O)=CC=C1 KMSXQYUJNMLISE-UHFFFAOYSA-N 0.000 description 1
- OITNBJHJJGMFBN-UHFFFAOYSA-N 4-(chloromethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CCl)C=C1 OITNBJHJJGMFBN-UHFFFAOYSA-N 0.000 description 1
- YAQXNRWTOHVQBD-UHFFFAOYSA-N 5-(chloromethyl)-2-benzofuran-1,3-dione Chemical compound ClCC1=CC=C2C(=O)OC(=O)C2=C1 YAQXNRWTOHVQBD-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical group C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-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 compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- SWOUFHQZGLYKTP-UHFFFAOYSA-N ClCC1=C(C(C(=O)O)=CC=C1)C(=O)O Chemical compound ClCC1=C(C(C(=O)O)=CC=C1)C(=O)O SWOUFHQZGLYKTP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 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
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 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】
（産業上の利用分野ン
本発明は、ポリフェニレンエーテルの末端フェノール性
水酸基の変性による末端カルボン酸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 Field of Application) The present invention relates to a method for producing terminal carboxylic acid-modified polyphenylene ether by modifying the terminal phenolic hydroxyl group of polyphenylene ether.
本発明の製造方法による末端カルボン酸変性ポリフェニ
レンエーテルは、未変性ポリフェニレンエーテルに比較
して他の樹脂等とブレンドした場合、ブレンド樹脂の官
能基と反応して、樹脂間の相溶性を高め、これにより組
成物の衝撃強度を高める等の効果があり、また、グラフ
ト又はブロック共重合体の前駆体としても有用である。Compared to unmodified polyphenylene ether, the terminal carboxylic acid-modified polyphenylene ether produced by the production method of the present invention reacts with the functional groups of the blended resin to increase the compatibility between the resins and improve the compatibility between the resins. This has the effect of increasing the impact strength of the composition, and is also useful as a precursor for graft or block copolymers.
（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６しかしながら、この樹脂はガラス転移温
度が高いことに関連して溶融粘度が高く、このため成形
加工性が悪く、またエンジニアリングプラスチックとし
ては耐衝撃性が劣るなどの欠点を有している。(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. However, this resin has a high melt viscosity due to its high glass transition temperature, which results in poor moldability and poor impact resistance as an engineering plastic. It has the following disadvantages.
これらの欠点を改良することを目的として、ボりオレフ
ィン又は他のエンジニアリングプラスチックとのブレン
ドが実施されているが、両者のポリマーは本質的に相溶
性に乏しく、得られる組成物は脆く、機械的強度及び衝
撃強度が低下し、実用に供し得ないものである。この問
題を解決するために相溶化剤が用いられているが、相溶
化剤の多くは両者のポリマーのグラフト又はブロック共
重合体である。これらの共重合体を合成する場合、ポリ
フェニレンエーテルの末端フェノール性水酸基を他のポ
リマー中の官能基と反応させることが考えられる。Blending with polyolefins or other engineering plastics has been carried out with the aim of improving these shortcomings, but the two polymers are inherently poorly compatible and the resulting compositions are brittle and have poor mechanical properties. The strength and impact strength are reduced and it cannot be put to practical use. Compatibilizers have been used to solve this problem, and most compatibilizers are graft or block copolymers of both polymers. When synthesizing these copolymers, it is conceivable to react the terminal phenolic hydroxyl group of polyphenylene ether with a functional group in another polymer.
しかしながら、末端フェノール性水酸基と反応可能な他
のポリマーの官能基種は限られており、その利用範囲は
自ずと限定されている。そこで、ポリフェニレンエーテ
ルの反応性を高める目的で多くの末端基変性ポリフェニ
レンエーテルが提案されている。However, the types of functional groups of other polymers that can react with the terminal phenolic hydroxyl group are limited, and the scope of their use is naturally limited. Therefore, many terminal group-modified polyphenylene ethers have been proposed for the purpose of increasing the reactivity of polyphenylene ethers.
ポリフェニレンエーテルをカルボン酸変性する方法とし
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変性
する方法が特開昭５６−２６９１３号及び特開昭５６−
４９７５３号各公報等に開示されている。As a method for modifying polyphenylene ether with carboxylic acid, a method of modifying polyphenylene ether with an acid anhydride or carboxylic acid having an unsaturated bond, preferably maleic anhydride, is disclosed in JP-A-56-26913 and JP-A-56-
No. 49753 and other publications.
これらの方法によるカルボン酸変性ポリフェニレンエー
テルは、変性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（Ｊｏｕｒｎａ
ｌ ｏｆ Ｐｏｌｙｍｅｒ ５ｃｉｅｎｃｅ： Ｐａｒ
ｔ ＡＰｏｌｙｍｅｒ Ｃｈｅｍｉｓｔｒｙ、 ２７巻
、ｐ、３３７１゜１９８９年参照）。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、未だ解決ずべき課題
が多い。It has been reported that carboxylic acid-modified polyphenylene ether produced by these methods has an unsaturated bond of the modifier added to the main chain of the polyphenylene ether (Journa
l of Polymer 5science: Par
(see AP Polymer Chemistry, Vol. 27, p. 3371, 1989). Furthermore, modification of polyphenylene ether by these methods requires reaction at high temperatures or in the presence of radicals, which causes problems such as deterioration of polyphenylene ether, and there are still many problems to be solved.
また、無水トリメリド酸クロリドを用いて、ポリフェニ
レンエーテルの末端基を酸変性する方法が特開昭６２−
４３４５５号公報に開示されているが、金属腐食性のあ
る酸クロリドを用いる点及び官能基がエステル結合で結
ばねているため、加水分解しやすい等の問題がある。In addition, a method for acid-modifying the end groups of polyphenylene ether using trimellidic anhydride chloride was disclosed in Japanese Patent Application Laid-Open No. 62-1999.
Although it is disclosed in Japanese Patent No. 43455, it uses acid chloride, which is corrosive to metals, and because the functional groups are connected by ester bonds, there are problems such as easy hydrolysis.
（発明が解決しようとする課題）
本発明は、変性ポリオレフィン、ポリエステル、ポリア
ミド等の樹脂と相溶性の良好な組成物を形成し得る末端
カルボン酸変性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 terminal carboxylic acid-modified polyphenylene ether that can form a composition with good compatibility with resins such as modified polyolefins, polyesters, and polyamides. With the goal.
（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（Ｄ末端フェノ
ール性水酸基をハロゲン化ベンジル誘導体を用いて変性
することにより、従来の方法に比較して容易に末端カル
ボン酸変性ポリフェニレンエーテルが得られることを見
出し、本発明を完成した。(Means for Solving the Problems) The present inventors have discovered that by modifying polyphenylene ether (the D-terminal phenolic hydroxyl group using a halogenated benzyl derivative), polyphenylene ether modified with a terminal carboxylic acid can be easily produced compared to conventional methods. They discovered that ether can be obtained and completed the present invention.
本発明は、一般式
（式中、Ｑ’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
素オキシ基又はへロ炭化水素オキシ基を表し、Ｑ２は各
々水素原子、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、ハロアルキル基、炭化水素オキシ
基又はへロ炭化水素オキシ基を表し、ｎは１０以上の数
を表す）
で示されるポリフェニレンエーテルに、−数式
（式中、Ｒ′及びＲ２は各々水素原子又は炭素数１〜６
の炭化水素基を表し、Ｒ３は直接結合又は炭素数１〜３
２の二価の炭化水素基を表し、）′はＯＨ基又はカルボ
キシル基の反応性残基な表し、Ｘはハロゲン原子を表し
、ｍは１〜５の整数をｌＪわす）
で示されるハロゲン化ベンジル誘導体を反応させること
を特徴とする、
一般式
（式中、Ｑ’、Ｑ２、Ｒ１、Ｒ２、Ｒ３、Ｙ、ｍ及びｎ
は前記と同じ）
で示される末端カルボン酸変性ポリフェニレンエーテル
の製造方法である。The present invention is based on the general formula (wherein Q' each represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a heterohydrocarbonoxy group, and Q2 is (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 helohydrocarbonoxy group, and n represents a number of 10 or more) to the ether, - formula (wherein R' and R2 are each a hydrogen atom or a carbon number of 1 to 6
represents a hydrocarbon group, R3 is a direct bond or has 1 to 3 carbon atoms
represents a divalent hydrocarbon group of characterized by reacting a benzyl derivative with the general formula (wherein Q', Q2, R1, R2, R3, Y, m and n
is the same as above) This is a method for producing terminal carboxylic acid-modified polyphenylene ether.
本発明で使用するポリフェニレンエーテルは、−数式 の構造を有する単独重合体又は共重合体である。The polyphenylene ether used in the present invention has the formula - It is a homopolymer or copolymer having the structure.
Ｑ’及びＱ２の第一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−若しくは４−メチルペンチ
ル又はヘプチルである。第二級アルキルの好適な例は、
イソプロピル、５ｅｃ−ブチル又は１−メチルペンチル
である。多くの場合、Ｑ’はアルキル基又はフェニル基
、特に炭素数１〜４のアルキル基であり、Ｑ２は水素原
子である。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λ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−ｈリメ壬ルー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及びランダム共
重合体が、特許、文献に記載されている。例えば分子量
、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。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 examples of primary alkyl groups for Q' and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-
Dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Suitable examples of secondary alkyl are:
Isopropyl, 5ec-butyl or 1-methylpentyl. In most cases Q' is an alkyl or phenyl group, especially an alkyl group having 1 to 4 carbon atoms, and Q2 is a hydrogen atom. A suitable polyphenylene ether homopolymer is, for example, one consisting of 2,6-dimethyl-1,4-phenylene ether units. Suitable copolymers include the above units and 2.3.6-h rimel-1.4-
It is a random copolymer consisting of a combination of phenylene ether units. Many suitable homopolymers and random copolymers are described in the patent literature. Polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength are also suitable. 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 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
で、３０℃の固有粘度が０．２〜０．８８／ｇ程度に相
当するものである。The molecular weight of polyphenylene ether usually corresponds to an intrinsic viscosity of about 0.2 to 0.88/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、こ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。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 mentioned above, and a number of catalyst systems are known for this oxidative coupling polymerization. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example, those containing at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.
ポリフェニレンエーテルの変性に用いる一般式（ＩＩＩ
）のハロゲン化ベンジル誘導体は、ハロゲン化ベンジ
ル基とカルボキシル基を少なくとも１個以上同時に有す
る化合物である。ここで、Ｘは、ハロゲン原子を表し具
体的には、フッ素、塩素、臭素、ヨウ素等を表す。General formula (III) used for modification of polyphenylene ether
) is a compound having at least one halogenated benzyl group and at least one carboxyl group. Here, X represents a halogen atom, specifically fluorine, chlorine, bromine, iodine, etc.
ハロゲン化ベンジル誘導体の好適な具体例を挙げると、
ｐ−クロルメチルフェニル酢酸、ｐ−プロムメヂルフェ
ニル酢酸、４−クロルメチル安息香酸、４−ブロムメチ
ル安息香酸、無水４−クロルメチルフタル酸、無水３−
クロルメチルフタル酸等が挙げられる。Preferred specific examples of halogenated benzyl derivatives include:
p-Chloromethylphenylacetic acid, p-promedylphenylacetic acid, 4-chloromethylbenzoic acid, 4-bromomethylbenzoic acid, 4-chloromethylphthalic anhydride, 3-chloromethylphthalic anhydride
Examples include chloromethylphthalic acid.
本発明で製造する一般式（Ｉ）で示す末端カルボン酸変
性ポリフェニレンエーテルは、−４１式（ＩＩ ）で示
すポリフェニレンエーテルと一般式（ｒｌＩ）で示すハ
ロゲン化ベンジル誘導体を塩基性触媒の存在下、有ｔＵ
容媒中で反応させることにより、あるいは、ポリフェニ
レンエーテルを溶解可能な有機溶媒と水溜性の無機塩基
性触媒の水溶液の混合溶媒中、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ベンジル誘導体を
反応させることにより容易に製造することができる。The terminal carboxylic acid-modified polyphenylene ether represented by the general formula (I) produced in the present invention is produced by combining the polyphenylene ether represented by the -41 formula (II) and the halogenated benzyl derivative represented by the general formula (rlI) in the presence of a basic catalyst. There is tU
By reacting in a medium, or in a mixed solvent of an organic solvent in which polyphenylene ether can be dissolved and an aqueous solution of a water-retaining inorganic basic catalyst, in the presence of a phase transfer catalyst,
It can be easily produced by reacting polyphenylene ether with a halogenated benzyl derivative.
ここで使用する有機溶媒は、ポリフェニレンエーテルを
溶解できることが望ましい。具体的には、ベンゼン、ト
ルエン、キシレン等の芳香族溶媒：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瀉媒；クロロホル
ム、トリクロルエチレン、四塩化炭素等のハロゲン化炭
化水素溶媒等が挙げられる。The organic solvent used here is desirably capable of dissolving polyphenylene ether. Specifically, aromatic solvents such as benzene, toluene, and xylene; halogenated aromatic solvents such as chlorobenzene and dichlorobenzene; halogenated hydrocarbon solvents such as chloroform, trichloroethylene, and carbon tetrachloride, etc. .
前記の塩基性触媒としては、ナトリウムメトキシド、ナ
トリウムエトキシド等のアルコラード。Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide.
ベンジルジメチルアミン、トリエチルアミン、トリブチ
ルアミン、１．８−ジアザビシクロ［５，４，０］−７
−ウンデセン（ＤＢＵ）等の第三級アミンが挙げられる
。水溶性の無機塩基性触媒としては、水酸化ナトリウム
、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナト
リウム、炭酸カリウム等のアルカリ金属炭酸塩等が挙げ
られる。Benzyldimethylamine, triethylamine, tributylamine, 1,8-diazabicyclo[5,4,0]-7
-Tertiary amines such as undecene (DBU) can be mentioned. Examples of water-soluble inorganic basic catalysts include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate.
相間移動触媒としては、第四級アンモニウム塩、第四級
ホスホニウム塩又は第三級スルホニウム塩等が挙げられ
る。好ましくは、第四級アンモニウム塩であり、その具
体的な例としてはベンジルトリメチルアンモニウムクロ
リド、ベンジルトリエチルアンモニウムクロリド、ベン
ジルトリブチルアンモニウムクロリド、テトラブチルア
ンモニウムプロミド、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又はトリオクチルメチルアンモニ
ウムクロリド等が挙げられる。Examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, and tertiary sulfonium salts. Preferred are quaternary ammonium salts, specific examples of which include benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrogen sulfate, or trioctylmethylammonium. Examples include chloride.
本反応は、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、−数式（ＩＩＩ）で示す変性剤１
〜３０モル、好ましくは２〜２０モルを用いる。有機溶
媒は、ポリフェニレンエーテル１００重量部に対して３
００〜１０００重量部使用する。塩基性触媒は、使用す
る変性剤１当量あたり、１＝ｌＯ当量、好ましくは、１
〜３当量用いる。相間移動触媒はポリフェニレンエーテ
ル１００重量部あたり１〜１０重量部用いる。In this reaction, 1 mole of the terminal phenolic hydroxyl group of polyphenylene ether is treated with 1 mole of the modifier represented by the formula (III).
~30 moles are used, preferably 2 to 20 moles. The organic solvent is 3 parts by weight per 100 parts by weight of polyphenylene ether.
00 to 1000 parts by weight are used. The basic catalyst contains 1=lO equivalent per equivalent of modifier used, preferably 1
~3 equivalents are used. The phase transfer catalyst is used in an amount of 1 to 10 parts by weight per 100 parts by weight of polyphenylene ether.
末端カルボン酸変性ポリフェニレンエーテル（Ｉ）の具
体的製造手順を説明すると、ポリフェニレンエーテル（
］Ｔ）を有機溶媒に加熱して溶解させ、次いで塩基性触
媒を添加するか、あるいは無機塩基性触媒の水滴液及び
相間移動触媒を添加し、室温から使用する有機溶媒の沸
点を超＾ない温度で変性剤であるハロゲン化ベンジル誘
導体を加えて反応させ、更に反応が完結するまで加熱撹
拌することにより製造する。To explain the specific manufacturing procedure of terminal carboxylic acid-modified polyphenylene ether (I), polyphenylene ether (
]T) in an organic solvent by heating and then adding a basic catalyst, or adding a water droplet of an inorganic basic catalyst and a phase transfer catalyst, and increasing the temperature from room temperature to a temperature that does not exceed the boiling point of the organic solvent used. It is produced by adding a halogenated benzyl derivative, which is a modifier, to react at high temperature, and then heating and stirring until the reaction is completed.
（実施例） 以下に、本発明を実施例により詳細に説明する。(Example) The present invention will be explained in detail below using examples.
これらの実施例で用いたポリフェニレンエーテルは、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 ０． ３０ｄ！！／ｇ）である。The polyphenylene ether used in these examples was poly(2,6-dimethyl-1,4-phenylene ether).
(PPE, intrinsic viscosity measured in chloroform at 30° C. 0.30 d!!/g).
ポリフェニレンエーテルの末端フェノール性水酸基の反
応率は、ジャーナル・才ブ アプライド・ポリマー・サ
イエンスニアブライド・ポリマー・シンポジウム（Ｊｏ
ｕｒｎａｌ ｏｆ ＡｐｐｌｉｅｄＰｏｌｙｍｅｒ ５
ｃｉｅｎｃｅ： Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓ
ｙｍｐｏｓｉｕｍｌ、３４巻（１９７８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。The reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether was reported in the Journal of Applied Polymer Science Near Bride Polymer Symposium (Jo
Urnal of Applied Polymer 5
Science: Applied Polymer S
ymposiuml, vol. 34 (1978), 103-
The calculation was performed by quantifying the terminal phenolic hydroxyl groups before and after the reaction according to the method described on page 117.
実施例１
ポリフェニレンエーテル２０．０ｇ及びトルエン２００
ｍ１を反応器に仕込み、８０℃で加熱撹拌してポリフェ
ニレンエーテルを溶解させた。続いて、塩基性触媒とし
てナトリウムエトキシド１．５ｇを加えた後、９０℃に
反応混合物の温度を上げ、３０分撹拌を続けた。この温
度を保ったまま、５．１ｇのｐ−ブロムメチルフェニル
酢酸を１５分かけて添加した。更に、７時間加熱撹拌後
、反応混合物をメタノール１．５ｆ２に注ぎ、生成した
変性樹脂を沈澱させた。これを）戸別した復水１℃で洗
浄し、更に、メタノール１ｉで洗浄したにのものを８０
℃で減圧加熱乾燥して末端カルボン酸変性ポリフェニレ
ンエーテルを得た。収率は、１００％、ポリフェニレン
エーテルの末端フェノール性水酸基の反応率は３０３％
であった。Example 1 20.0 g of polyphenylene ether and 200 g of toluene
ml was charged into a reactor and heated and stirred at 80°C to dissolve polyphenylene ether. Subsequently, after adding 1.5 g of sodium ethoxide as a basic catalyst, the temperature of the reaction mixture was raised to 90° C. and stirring was continued for 30 minutes. While maintaining this temperature, 5.1 g of p-bromomethylphenylacetic acid was added over 15 minutes. Furthermore, after heating and stirring for 7 hours, the reaction mixture was poured into 1.5 f2 of methanol to precipitate the produced modified resin. This was washed separately with condensed water at 1°C, and then washed with methanol 11°C.
The mixture was dried under reduced pressure at °C to obtain terminal carboxylic acid-modified polyphenylene ether. The yield is 100%, and the reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether is 303%.
Met.
実施例２
ポリフェニレンエーテル２００ｇ及びトルエン２００ｗ
１１を反応器に仕込み、８０℃で加熱撹拌してポリフェ
ニレンエーテルを溶解させた。続いて、塩基性触媒とし
て５０％水酸化ナトリウム水溶液５．０ｇを添加し、更
にトリオクチルメチルアンモニウムクロリド１０ｇを加
え、９０℃に反応混合物の温度を上げ、３０分撹拌を続
けた。Example 2 200g of polyphenylene ether and 200w of toluene
11 was charged into a reactor and heated and stirred at 80°C to dissolve polyphenylene ether. Subsequently, 5.0 g of a 50% aqueous sodium hydroxide solution was added as a basic catalyst, and 10 g of trioctylmethylammonium chloride was further added, the temperature of the reaction mixture was raised to 90° C., and stirring was continued for 30 minutes.
この温度を保ったまま、３．８ｇの４−クロルメチル安
思香酸の水溶液を１５分かけて添加した。While maintaining this temperature, 3.8 g of an aqueous solution of 4-chloromethylbensikoic acid was added over 15 minutes.
以後は実施例１と同様に処理して、末端カルボン酸変性
ポリフェニレンエーテルを得た。収率９４．９％、ポリ
フェニレンエーテルの末端フェノール性水酸基の反応率
は９８．８％であった。Thereafter, the same treatment as in Example 1 was carried out to obtain terminal carboxylic acid-modified polyphenylene ether. The yield was 94.9%, and the reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether was 98.8%.
得られた末端カルボン酸変性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。１７００ｃｍ−’
付近に、カルボキシル基のカルボニル基によると推定さ
れる吸収が観測された。FIG. 1 shows the infrared absorption spectrum of a cast film prepared from a chloroform solution of the obtained terminal carboxylic acid-modified polyphenylene ether. 1700cm-'
Absorption presumed to be due to the carbonyl group of the carboxyl group was observed nearby.
実施例３
反応混合物の温度を８８℃とし、また変性剤として、５
．０ｇのｐ−ブロムメチルフェニル酢酸の水滴液を使用
した以外は実施例２と同様に実施して、末端カルボン酸
変性ポリフェニレンエーテルを得た。収率は、１００％
、ポリフェニレンエーテルの末端フェノール性水酸基の
反応率は８０．３％であった。Example 3 The temperature of the reaction mixture was 88°C, and as a modifier, 5
．． A terminal carboxylic acid-modified polyphenylene ether was obtained in the same manner as in Example 2 except that 0 g of aqueous p-bromomethylphenylacetic acid was used. Yield is 100%
The reaction rate of the terminal phenolic hydroxyl group of polyphenylene ether was 80.3%.
応用例１
実施例２で得た末端カルボン酸変性ポリフェニレンエー
テル３．０ｇとヒドロキシル基変性ポリプロピレン（数
平均分子量６２．０’００、重量平均分子量４５０．０
００、ヒドロキシル基含量０５重量％）３０ｇ及び反応
の触媒としてアルミニウムイソプロポキシド０．１ｇを
キシレン１００１１１１に溶解して、窒素雰囲気下にて
７時間加熱還流した。Application example 1 3.0 g of terminal carboxylic acid-modified polyphenylene ether obtained in Example 2 and hydroxyl group-modified polypropylene (number average molecular weight 62.0'00, weight average molecular weight 450.0
00, hydroxyl group content 05% by weight) and 0.1 g of aluminum isopropoxide as a reaction catalyst were dissolved in xylene 1001111 and heated under reflux for 7 hours under a nitrogen atmosphere.
反応終了後、反応混合物をメタノールＩＩ２中に注ぎ、
反応したポリマーを沈澱させた。炉別後型に、メタノー
ル１℃で洗浄後、８０℃で減圧加熱乾燥させたところ６
．０ｇのポリマーを回収した。After the reaction was completed, the reaction mixture was poured into methanol II2,
The reacted polymer was precipitated. After cleaning the mold with methanol at 1℃, it was heated and dried under reduced pressure at 80℃.6
．． 0g of polymer was recovered.
次に、得られたポリマー１．６４６ｇをクロロホルム２
００＋ａｌ’を溶媒として、ソックスレー抽出を７時間
行い、グラフト反応しなかったポリフェニレンエーテル
を抽出除去した。その結果、抽出除去されたポリフェニ
レンエーテルは、０．５９５ｇであり、この結果グラフ
ト体中のポリフェニレンエーテルの含量は、２１７重量
％であることが判明した。Next, 1.646 g of the obtained polymer was added to chloroform 2
Soxhlet extraction was performed for 7 hours using 00+al' as a solvent, and the polyphenylene ether that did not undergo the graft reaction was extracted and removed. As a result, it was found that the amount of polyphenylene ether extracted and removed was 0.595 g, and the content of polyphenylene ether in the graft body was 217% by weight.
（発明の効果）
実施例に示したように、本発明の末端カルボン酸変性ポ
リフェニレンエーテルの製造方法は極めて容易であり、
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。(Effects of the Invention) As shown in the examples, the method for producing terminal carboxylic acid-modified polyphenylene ether of the present invention is extremely easy;
This can also easily be treated with polypropylene, as shown in Application Example 1.
グラフト結合させることができた。We were able to perform a graft connection.
第１図は、実施例２で得た末端カルボン酸変性ポリフェ
ニレンエーテル（クロロホルム溶ン夜より調製したキャ
ストフィルム）の赤外線吸収スペクトルを示す。FIG. 1 shows the infrared absorption spectrum of the terminal carboxylic acid-modified polyphenylene ether obtained in Example 2 (cast film prepared by dissolving in chloroform).
Claims (1)
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し、ｎは１０以上
の数を表す） 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及びＲ＾２は各々水素原子又は炭素数１
〜６の炭化水素基を表し、Ｒ＾３は直接結合又は炭素数
１〜３２の二価の炭化水素基を表し、ＹはＯＨ基又はカ
ルボキシル基の反応性残基を表し、Ｘはハロゲン原子を
表し、ｍは１〜５の整数を表わす） で示されるハロゲン化ベンジル誘導体を反応させること
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、Ｒ＾１、Ｒ＾２、Ｒ＾３、Ｙ
、ｍ及びｎは前記と同じ） で示される末端カルボン酸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, Represents a hydrocarbon oxy group or a halohydrocarbon oxy 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, and n represents a number of 10 or more) Ether has a general formula▲mathematical formula, chemical formula, table, etc.▼(III) (In the formula, R^1 and R^2 are each a hydrogen atom or a carbon number of 1
~6 hydrocarbon group, R^3 represents a direct bond or a divalent hydrocarbon group having 1 to 32 carbon atoms, Y represents a reactive residue of an OH group or a carboxyl group, and X is a halogen atom (where m represents an integer from 1 to 5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, Q^ 1, Q^2, R^1, R^2, R^3, Y
, m and n are the same as above) A method for producing a terminal carboxylic acid-modified polyphenylene ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26627790A JPH04145125A (en) | 1990-10-05 | 1990-10-05 | Production of terminal carboxylic acid-modified polyphenylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26627790A JPH04145125A (en) | 1990-10-05 | 1990-10-05 | Production of terminal carboxylic acid-modified polyphenylene ether |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04145125A true JPH04145125A (en) | 1992-05-19 |
Family
ID=17428727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26627790A Pending JPH04145125A (en) | 1990-10-05 | 1990-10-05 | Production of terminal carboxylic acid-modified polyphenylene ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04145125A (en) |
-
1990
- 1990-10-05 JP JP26627790A patent/JPH04145125A/en active Pending
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