JPH07278290A - Preparation of brominated polyphenylene ether - Google Patents
Preparation of brominated polyphenylene etherInfo
- Publication number
- JPH07278290A JPH07278290A JP6843394A JP6843394A JPH07278290A JP H07278290 A JPH07278290 A JP H07278290A JP 6843394 A JP6843394 A JP 6843394A JP 6843394 A JP6843394 A JP 6843394A JP H07278290 A JPH07278290 A JP H07278290A
- Authority
- JP
- Japan
- Prior art keywords
- brominated
- chloride
- halogen
- polyphenylene ether
- polymerization initiator
- 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.)
- Granted
Links
- 229920001955 polyphenylene ether Polymers 0.000 title claims abstract description 13
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 150000002989 phenols Chemical class 0.000 claims abstract description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 150000004707 phenolate Chemical class 0.000 claims abstract description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical class OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 abstract description 7
- -1 carboxylic acid halides Chemical class 0.000 abstract description 7
- ZSIAANIILFGLQH-UHFFFAOYSA-N C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 Chemical compound C1(=CC=CC=C1)[ClH]P(=O)(Cl)[ClH]C1=CC=CC=C1 ZSIAANIILFGLQH-UHFFFAOYSA-N 0.000 abstract description 3
- SVHOVVJFOWGYJO-UHFFFAOYSA-N pentabromophenol Chemical class OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br SVHOVVJFOWGYJO-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003015 phosphoric acid halides Chemical class 0.000 abstract description 3
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 abstract description 2
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000006068 polycondensation reaction Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001350 alkyl halides Chemical class 0.000 abstract 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002904 solvent Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OUCSIUCEQVCDEL-UHFFFAOYSA-N 2,3,4-tribromophenol Chemical compound OC1=CC=C(Br)C(Br)=C1Br OUCSIUCEQVCDEL-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZZHIDJWUJRKHGX-UHFFFAOYSA-N 1,4-bis(chloromethyl)benzene Chemical compound ClCC1=CC=C(CCl)C=C1 ZZHIDJWUJRKHGX-UHFFFAOYSA-N 0.000 description 1
- GTLWADFFABIGAE-UHFFFAOYSA-N 1-chloroethylbenzene Chemical compound CC(Cl)C1=CC=CC=C1 GTLWADFFABIGAE-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- RXNOYRCWKRFNIM-UHFFFAOYSA-N 2-carbonochloridoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(Cl)=O RXNOYRCWKRFNIM-UHFFFAOYSA-N 0.000 description 1
- ANHAEBWRQNIPEV-UHFFFAOYSA-N 2-chloroethyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCCl ANHAEBWRQNIPEV-UHFFFAOYSA-N 0.000 description 1
- ANGGPYSFTXVERY-UHFFFAOYSA-N 2-iodo-2-methylpropane Chemical compound CC(C)(C)I ANGGPYSFTXVERY-UHFFFAOYSA-N 0.000 description 1
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 1
- SSSVVNYPGJXKQO-UHFFFAOYSA-N 3,3-dichloropropyl dihydrogen phosphate Chemical compound OP(O)(=O)OCCC(Cl)Cl SSSVVNYPGJXKQO-UHFFFAOYSA-N 0.000 description 1
- UGCCFTIRTVRJSZ-UHFFFAOYSA-N 4,5-dibromo-7-oxabicyclo[4.1.0]hepta-1(6),2,4-triene Chemical compound BrC1=CC=C2OC2=C1Br UGCCFTIRTVRJSZ-UHFFFAOYSA-N 0.000 description 1
- UBQRAAXAHIKWRI-UHFFFAOYSA-N 4-(chloromethyl)-1,2-dimethylbenzene Chemical compound CC1=CC=C(CCl)C=C1C UBQRAAXAHIKWRI-UHFFFAOYSA-N 0.000 description 1
- DENKGPBHLYFNGK-UHFFFAOYSA-N 4-bromobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Br)C=C1 DENKGPBHLYFNGK-UHFFFAOYSA-N 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- DAKPRQYLVWIZGJ-UHFFFAOYSA-N C(CC)[ClH]P(=O)(Cl)[ClH]CCC Chemical compound C(CC)[ClH]P(=O)(Cl)[ClH]CCC DAKPRQYLVWIZGJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XMGGCBJKTROPMA-UHFFFAOYSA-N ClP(Cl)(=O)[ClH]C1=CC=CC=C1 Chemical compound ClP(Cl)(=O)[ClH]C1=CC=CC=C1 XMGGCBJKTROPMA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- UXJHQBVRZUANLK-UHFFFAOYSA-N azanylidyne(dichloro)-$l^{5}-phosphane Chemical compound ClP(Cl)#N UXJHQBVRZUANLK-UHFFFAOYSA-N 0.000 description 1
- AQIHMSVIAGNIDM-UHFFFAOYSA-N benzoyl bromide Chemical compound BrC(=O)C1=CC=CC=C1 AQIHMSVIAGNIDM-UHFFFAOYSA-N 0.000 description 1
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YTKRILODNOEEPX-NSCUHMNNSA-N crotyl chloride Chemical compound C\C=C\CCl YTKRILODNOEEPX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IBDMRHDXAQZJAP-UHFFFAOYSA-N dichlorophosphorylbenzene Chemical compound ClP(Cl)(=O)C1=CC=CC=C1 IBDMRHDXAQZJAP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HTRJDXQPCKIFIU-UHFFFAOYSA-N silver;ethanol;nitrate Chemical compound [Ag+].CCO.[O-][N+]([O-])=O HTRJDXQPCKIFIU-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【０００１】[0001]
【０００２】本発明は高分子材料の難燃剤として使用さ
れる臭素化ポリフェニレンエーテルの製法に関するもの
である。The present invention relates to a method for producing a brominated polyphenylene ether used as a flame retardant for polymeric materials.
【０００３】[0003]
【従来の技術】臭素化ポリフェニレンエーテルの製造法
としては、例えば特公昭５６−２１００号公報に、ペル
オクソ硫酸塩、次亜塩素酸塩、フェリシアン化物、塩化
第二鉄、金属酸化物、ハロゲン等の重合開始剤を使用し
た方法が記載されている。2. Description of the Related Art As a method for producing brominated polyphenylene ether, for example, Japanese Patent Publication No. 56-2100 discloses a peroxosulfate, hypochlorite, ferricyanide, ferric chloride, metal oxide, halogen, etc. The method of using the polymerization initiator of is described.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、このよ
うな従来の方法にあっては、重合開始剤の効果が充分で
無いため収量が悪い、得られた重合物が褐色に着色し淡
色樹脂には使用できない、現場での製造作業上取り扱い
に危険を伴う、産業廃棄物の観点から製造時の排水処理
が困難である等の問題があった。本発明は、このような
問題点を解決する新規な製法を提供することを課題とす
る。However, in such a conventional method, the yield of the resulting polymer is poor because the effect of the polymerization initiator is not sufficient. There are problems that it cannot be used, there is a danger of handling it in the field during manufacturing work, and wastewater treatment during manufacturing is difficult from the viewpoint of industrial waste. An object of the present invention is to provide a new manufacturing method that solves such problems.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、臭
素化フェノラートを縮重合させて臭素化ポリフェニレン
エーテルを製造するにおいて、重合開始剤として硝酸又
は硝酸銀反応で陽性を呈するハロゲン含有有機化合物
（以下、含ハロゲン化合物と称す）を使用することを特
徴とする臭素化ポリフェニレンエーテルの製法である。Means for Solving the Problems That is, in the present invention, when a brominated phenolate is polycondensed to produce a brominated polyphenylene ether, a halogen-containing organic compound (hereinafter , A halogen-containing compound) is used for the production of a brominated polyphenylene ether.
【０００６】（１）臭素化フェノラート 本発明の臭素化フェノラートとしては、トリブロモフェ
ノールからペンタブロモフェノールまでの臭素化フェノ
ールの金属塩等が挙げられる。(1) Brominated phenolate Examples of the brominated phenolate of the present invention include metal salts of brominated phenols from tribromophenol to pentabromophenol.
【０００７】これらの臭素化フェラートは、あらかじめ
水にアルカリ、例えば水酸化ナトリウムや水酸化カリウ
ムを溶解し、冷却した水溶液に臭素化フェノールを添加
し、加熱するか、又は室温で完全に溶解することによっ
て得られる。この際、溶剤を添加することも可能で、添
加時期は臭素化フェノールの添加前でも、添加後でもよ
い。These brominated ferrates should be prepared by first dissolving an alkali such as sodium hydroxide or potassium hydroxide in water and adding brominated phenol to a cooled aqueous solution and then heating or completely dissolving it at room temperature. Obtained by At this time, a solvent may be added, and the addition time may be before or after the addition of brominated phenol.
【０００８】臭素化フェノールの溶解は、アルカリが過
剰の場合、短時間で溶解できる。得られた溶液は、ｐＨ
が１２．５以上の場合比較的安定である。それ以下では
重合開始剤がなくても重合が開始することがあるが、反
応時間のコントロ−ルができず、さらに、未反応の臭素
化フェノールが重合物中に残存し、除去するのが困難で
ある。The brominated phenol can be dissolved in a short time when the alkali is excessive. The resulting solution has a pH
Is 12.5 or more, it is relatively stable. If it is less than that, the polymerization may start without a polymerization initiator, but the reaction time cannot be controlled, and unreacted brominated phenol remains in the polymer and is difficult to remove. Is.
【０００９】しかし、アルカリが過剰では、重合開始剤
を消費し非経済であることから、重合開始剤を添加する
直前に酸で中和し、ｐＨを１２．５〜９．０、より好ま
しくは１０〜１１に調整する。However, when the alkali is excessive, the polymerization initiator is consumed and it is uneconomical. Therefore, the pH is 12.5 to 9.0, more preferably neutralized with an acid immediately before the addition of the polymerization initiator. Adjust to 10-11.
【００１０】なお、原料となる臭素化フェノールは、純
分が９８重量％以上のものが好ましい。純分が低く、不
純物にフェノール、モノブロモフェノール、ジブロモフ
ェノールを含む場合は縮重合反応が十分に行われない、
あるいは全く行われない場合が生じる。したがって、よ
り好ましくは不純物が１重量％以下である。The brominated phenol as a raw material preferably has a pure content of 98% by weight or more. If the purity is low and the impurities include phenol, monobromophenol and dibromophenol, the polycondensation reaction will not be carried out sufficiently.
Or the case where it is not performed at all occurs. Therefore, the amount of impurities is more preferably 1% by weight or less.
【００１１】（２）重合開始剤 本発明の重合開始剤としては、硝酸、含ハロゲン化合物
等の単独又は二種以上の混合物が挙げられる。(2) Polymerization initiator As the polymerization initiator of the present invention, nitric acid, a halogen-containing compound and the like may be used alone or in a mixture of two or more kinds.
【００１２】含ハロゲン化合物は、有機カルボン酸ハラ
イド、有機燐酸ハライド、脂肪族及び芳香族系アルキル
ハライド等である。The halogen-containing compound is an organic carboxylic acid halide, an organic phosphoric acid halide, an aliphatic or aromatic alkyl halide or the like.
【００１３】有機カルボン酸ハライドは、例えばフタル
酸クロライド、塩化ベンゾイル、臭化ベンゾイル、塩化
ｐ−ブロモベンゾイル、塩化ｎ−ブチリル、イソラク酸
クロライド、ラウリン酸クロライド、２−エチルヘキシ
ル酸クロライド、アクリル酸クロライド、メタクリル酸
クロライド、フェニル酢酸クロライド、塩化クロチル等
であり、有機燐酸ハライドは、例えばフェニルホスホン
酸ジクロライド、ジクレジルホスホン酸クロライド、フ
ェニル燐酸クロライド、ジフェニル燐酸クロライド、キ
シレニル燐酸ジクロライド、ホスホニトリルクロライ
ド、ジプロピル燐酸クロライド、ジクロロプロピル燐酸
ジクロライド、クロロエチル燐酸ジクロライド等であ
り、Organic carboxylic acid halides include, for example, phthalic acid chloride, benzoyl chloride, benzoyl bromide, p-bromobenzoyl chloride, n-butyryl chloride, isolacic acid chloride, lauric acid chloride, 2-ethylhexyl acid chloride, acrylic acid chloride, Methacrylic acid chloride, phenylacetic acid chloride, crotyl chloride, etc., and organic phosphoric acid halides include, for example, phenylphosphonic acid dichloride, dicresylphosphonic acid chloride, phenylphosphoric acid chloride, diphenylphosphoric acid chloride, xylenylphosphoric acid dichloride, phosphonitrile chloride, dipropylphosphoric acid chloride. , Dichloropropylphosphoric acid dichloride, chloroethylphosphoric acid dichloride, etc.,
【００１４】脂肪族及び芳香族系アルキルハライドは、
例えば塩化トリフェニルメチル、塩化ｐ−キシリレン、
塩化３，４−ジメチルベンジル、塩化ｔ−ブチル、臭化
ｔ−ブチル、ヨウ化ｔ−ブチル、塩化ベンサル、クロル
ギ酸メチル、塩化ジフェニルメチル、アリルクロライ
ド、アリルブロマイド、塩化メチルベンジル、エチレン
ブロムヒドリン、ベンジルクロライド、ベンジルブロマ
イド等である。Aliphatic and aromatic alkyl halides are
For example, triphenylmethyl chloride, p-xylylene chloride,
3,4-Dimethylbenzyl chloride, t-butyl chloride, t-butyl bromide, t-butyl iodide, benzal chloride, methyl chloroformate, diphenylmethyl chloride, allyl chloride, allyl bromide, methylbenzyl chloride, ethylene bromhydrin. , Benzyl chloride, benzyl bromide and the like.
【００１５】含ハロゲン化合物が硝酸銀反応で陽性を呈
するか、否かの確認方法は、試料２ｇを２０ｍｌのエタ
ノールに溶解し、次に０．１Ｎの硝酸銀−エタノール溶
液１ｍｌを加え撹拌混合し、塩化銀が沈殿するか、否か
を確認する。沈殿が生じたものを陽性、沈殿が生じない
ものを陰性と判定する。To confirm whether or not the halogen-containing compound is positive in the silver nitrate reaction, 2 g of the sample is dissolved in 20 ml of ethanol, then 1 ml of 0.1 N silver nitrate-ethanol solution is added, and the mixture is stirred and mixed to form chloride. Check if silver precipitates. Those with precipitation are judged as positive, and those without precipitation are judged as negative.
【００１６】重合開始剤の添加量は、臭素化フェノール
に対して０．２〜１８重量％、好ましくは０．２〜１０
重量％である。The amount of the polymerization initiator added is 0.2 to 18% by weight, preferably 0.2 to 10% by weight based on the brominated phenol.
% By weight.
【００１７】なお、重合開始剤は、必要に応じて適宜、
水、溶剤等に溶解して使用することもできる。The polymerization initiator may be appropriately used, if necessary.
It can also be used by dissolving it in water, a solvent or the like.
【００１８】重合開始剤を溶解するために使用する溶剤
は、トリブロモフェノール溶解の際に使用するものと同
じでもよく、好ましくは例えばメチレンジクロライド、
クロロホルム、四塩化炭素、ジクロルエタン、トリクロ
ルエチレン、パークロルエチレン、テトラクロルエタン
等のハロゲン化炭化水素類、ベンゼン、トルエン、キシ
レン等の芳香族炭化水素類、ヘキサン等の飽和炭化水素
類、クロルベンゼン等のハロゲン置換炭化水素類、メチ
ルエチルケトン、イソブチルケトン等のケトン類であ
る。これらの溶剤は２種類以上使用することもできる。
なお、溶剤として例示したハロゲン化炭化水素類は、硝
酸銀反応で陰性を示し、重合開始剤としての効果はな
い。The solvent used for dissolving the polymerization initiator may be the same as that used for dissolving the tribromophenol, preferably, for example, methylene dichloride,
Chloroform, carbon tetrachloride, dichloroethane, trichloroethylene, perchlorethylene, tetrachloroethane and other halogenated hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons, hexane and other saturated hydrocarbons, chlorobenzene, etc. The halogen-substituted hydrocarbons, ketones such as methyl ethyl ketone and isobutyl ketone. Two or more kinds of these solvents can be used.
The halogenated hydrocarbons exemplified as the solvent are negative in the silver nitrate reaction and have no effect as a polymerization initiator.
【００１９】（３）臭素化ポリフェニレンエーテルの製
法 臭素化フェノラートとして例えばトリブロモフェノラー
トを使用する場合、トリブロモフェノラートの溶液を攪
拌しながら、重合開始剤を単独で又は溶剤に溶解して添
加し、さらに攪拌を続ける。この時の反応温度は特に限
定されないが、トリブロモフェノラ−トが溶解するに必
要な最低温度から反応時に使用される溶剤の沸点以内が
好ましく、さらには重合開始剤の分解を引き延ばすため
に５〜５０℃の範囲がより好ましい。反応終了後、生成
した重合物を還元剤で脱色後分離し水洗あるいは溶剤で
洗浄して、目的の臭素化ポリフェニレンエーテルを得
る。なお、精製は、重合物を溶剤に溶解した後、重合物
が不溶のアルコール等の溶剤に添加する再結晶法が好ま
しい。(3) Method for producing brominated polyphenylene ether When, for example, tribromophenolate is used as the brominated phenolate, the polymerization initiator is added alone or in a solvent while stirring the solution of tribromophenolate. And continue stirring. The reaction temperature at this time is not particularly limited, but it is preferably within the boiling point of the solvent used during the reaction from the minimum temperature required for the tribromophenolate to dissolve, and further, in order to prolong the decomposition of the polymerization initiator, The range of -50 ° C is more preferable. After completion of the reaction, the produced polymer is decolorized with a reducing agent, separated, and washed with water or a solvent to obtain the desired brominated polyphenylene ether. The purification is preferably performed by a recrystallization method in which the polymer is dissolved in a solvent and then added to a solvent such as alcohol in which the polymer is insoluble.
【００２０】（４）その他の添加剤等 本発明においては、必要に応じて適宜、分散剤等の界面
活性剤、樹脂添加剤、安定剤、無機物等も併用すること
ができる。(4) Other Additives, etc. In the present invention, a surfactant such as a dispersant, a resin additive, a stabilizer, an inorganic substance and the like can be used in combination, if necessary.
【００２１】[0021]
【実施例】次に、本発明を実施例により説明するが、本
発明はかかる実施例のみに限定されるものではない。な
お、実施例に示す『％』は、重量％で表す。EXAMPLES The present invention will now be described with reference to examples, but the present invention is not limited to these examples. In addition, "%" shown in the examples is represented by% by weight.
【００２２】実施例１．水２００ｇに、水酸化ナトリウ
ム２５．７ｇ（０．６４３ｍｏｌ）を溶解し、トリブト
モフェノール（以下、ＴＢＰとも称す）２１２．３ｇ
（０．６４１ｍｏｌ）加え、完全に溶解する。この溶液
１０ｇを２０ｍｌの試験管に計り取り、試験管撹拌装置
で撹拌しながら、各種の重合開始剤を単独で又は溶剤に
溶かし１０％溶液にして所定量添加する。その後２０分
間撹拌を続け、水酸化ナトリウム５％水溶液１０ｍｌを
添加し、生成した重合物を濾別し水洗後乾燥して目的物
を得た。同様に比較実験も行った。結果を表１に示す。Example 1. Sodium hydroxide 25.7 g (0.643 mol) is dissolved in water 200 g, and tributomophenol (hereinafter also referred to as TBP) 212.3 g
(0.641 mol) is added, and it is completely dissolved. 10 g of this solution is weighed into a 20 ml test tube, and various polymerization initiators are dissolved alone or in a solvent to make a 10% solution while stirring with a test tube stirring device, and a predetermined amount is added. Then, stirring was continued for 20 minutes, 10 ml of a 5% aqueous solution of sodium hydroxide was added, and the produced polymer was separated by filtration, washed with water and dried to obtain the desired product. Similarly, a comparative experiment was conducted. The results are shown in Table 1.
【００２３】なお、収率は、トリブロモフェノールがす
べて重合してポリ（ジブロムフェニレンエーテル）に変
化した際の収率を１００％として算出した。以下同じ。The yield was calculated with 100% as the yield when all the tribromophenol was polymerized and changed to poly (dibromophenylene ether). same as below.
【００２４】[0024]
【表１】 [Table 1]
【００２５】実施例２．フラスコに、水２００ｇ、水酸
化ナトリウム２６．５ｇ（０．６６３ｍｏｌ）加え、撹
拌しながら溶解する。つぎに、トリブロモフェノール２
１２．３ｇ（０．６４１ｍｏｌ）加え、３０〜４０℃で
溶解する。その後、塩酸でｐＨ＝１０．５に調整し、２
０℃まで冷却し、２０〜３０℃の範囲で重合開始剤を所
定量添加する。添加数分後に重合物が生成し始め３時間
保持し、水酸化ナトリウム２６％水溶液を加え、ｐＨ＝
１２以上に調整し、重合物を濾別する。つぎに重合物に
ｉｓｏ−ブチルアルコール３００ｍｌを加え撹拌する。
さらにヒドラジン８０％水溶液１．５ｍｌ加え、還流温
度で１時間還元脱色する。つぎに３０℃以下まで冷却
し、重合物を濾別し乾燥して目的物を得た。同様に比較
実験も行った。結果を表２に示す。Example 2. 200 g of water and 26.5 g (0.663 mol) of sodium hydroxide are added to the flask and dissolved with stirring. Next, tribromophenol 2
Add 12.3 g (0.641 mol) and dissolve at 30-40 ° C. After that, adjust the pH to 10.5 with hydrochloric acid and adjust to 2
After cooling to 0 ° C, a predetermined amount of a polymerization initiator is added within the range of 20 to 30 ° C. A few minutes after the addition, a polymer starts to be formed and is kept for 3 hours, and a 26% aqueous solution of sodium hydroxide is added to adjust the pH =
Adjust to 12 or more and filter the polymer. Next, 300 ml of iso-butyl alcohol is added to the polymer and stirred.
Further, 1.5 ml of 80% aqueous hydrazine solution is added, and the mixture is subjected to reductive decolorization at reflux temperature for 1 hour. Next, it was cooled to 30 ° C. or lower, the polymer was separated by filtration and dried to obtain the desired product. Similarly, a comparative experiment was conducted. The results are shown in Table 2.
【００２６】なお、色相（ＧＮｏ）は、２０ｗｔ／ｖ％
のクロロホルム溶液で測定した。耐熱色相（ＧＮｏ）
は、重合物を３００℃×３０分間加熱後２ｗｔ／ｖ％の
クロロホルム溶液で測定した。以下同じHue (GNo) is 20 wt / v%
Was measured with a chloroform solution of. Heat resistant hue (GNo)
Was measured with a 2 wt / v% chloroform solution after heating the polymer at 300 ° C. for 30 minutes. same as below
【００２７】[0027]
【表２】 [Table 2]
【００２８】実施例３．フラスコに、水１５０ｇ、水酸
化カリウム４３ｇ（０．７６６ｍｏｌ）を加え溶解す
る。次に、４０℃以下で塩化メチレン２５０ｇ、トリブ
ロモフェノール２００ｇ（０．６０４ｍｏｌ）、ペンタ
ブロモフェノール５０ｇ（０．１０２ｍｏｌ）を加え溶
解する。さらに硫酸を加え、ｐＨ＝１０に調整し、１０
〜３５℃で重合開始剤としてトルエン５０％溶液５ｇを
１５分間かけて滴下する。その後、３時間保持し、水酸
化ナトリウム４８％水溶液２ｍｌとヒドラジン８０％水
溶液１ｍｌを加え２時間脱色する。静置分離し、下層の
油相をメタノール１０００ｍｌ中へ滴下し、重合物を分
別する。乾燥後、目的物を得た。同様に比較実験も行っ
た。結果を表３に示す。Example 3. To the flask, 150 g of water and 43 g (0.766 mol) of potassium hydroxide are added and dissolved. Next, 250 g of methylene chloride, 200 g (0.604 mol) of tribromophenol and 50 g (0.102 mol) of pentabromophenol are added and dissolved at 40 ° C. or lower. Further add sulfuric acid to adjust the pH to 10 and adjust to 10
At −35 ° C., 5 g of 50% toluene solution as a polymerization initiator is added dropwise over 15 minutes. Then, the mixture is maintained for 3 hours, and 2 ml of 48% aqueous sodium hydroxide solution and 1 ml of 80% hydrazine aqueous solution are added to decolor for 2 hours. The mixture is allowed to stand, and the lower oil phase is added dropwise to 1000 ml of methanol to separate the polymer. After drying, the target product was obtained. Similarly, a comparative experiment was conducted. The results are shown in Table 3.
【００２９】なお、収率は、収量１９２．８ｇを収率１
００％として計算した。外観色相は肉眼で判定した。The yield is 192.8 g and the yield is 1.
Calculated as 00%. The appearance hue was visually judged.
【００３０】[0030]
【表３】 [Table 3]
【００３１】実施例４．フラスコに、水６００ｇ、水酸
化ナトリウム７９．５ｇ（１．９９ｍｏｌ）を加え、撹
拌しながら溶解する。つぎに、トリブロモフェノール６
３７ｇ（１．９２ｍｏｌ）を加え、４０〜５０℃で溶解
する。その後、硫酸でｐＨ＝１１．５に調整し、２０℃
まで冷却し、２０〜３０℃の範囲で重合開始剤（１）１
５ｇを添加する。添加数分後に重合物が生成し始め、２
時間保持する。次いで、重合開始剤（２）４．５ｇをト
ルエン１５ｇに溶解して添加し１時間後に、徐々に４５
℃まで昇温する。次に４５℃でトリエチルアミン０．５
ｇとヒドラジン８０％水溶液５ｇを加え、さらに昇温し
８０〜９０℃で２時間還元脱色する。その後、４０℃迄
冷却し、水酸化ナトリウム２６％水溶液を加えｐＨ＝１
２以上に調整し、遠心分離機で重合物を濾別、乾燥して
目的物を得る。同様に比較実験も行った。結果を表４に
示す。Example 4. 600 g of water and 79.5 g (1.99 mol) of sodium hydroxide are added to the flask and dissolved with stirring. Next, tribromophenol 6
Add 37 g (1.92 mol) and dissolve at 40-50 ° C. After that, adjust to pH = 11.5 with sulfuric acid, and 20 ℃
And the polymerization initiator (1) 1 in the range of 20 to 30 ° C.
Add 5 g. Polymers started to form a few minutes after the addition, 2
Hold for time. Then, 4.5 g of the polymerization initiator (2) was dissolved in 15 g of toluene and added, and after 1 hour, gradually added to 45 g.
Raise the temperature to ℃. Then at 45 ° C. triethylamine 0.5
g and 5 g of 80% hydrazine aqueous solution are added, and the temperature is further raised to carry out reductive decolorization at 80 to 90 ° C. for 2 hours. After that, it is cooled to 40 ° C., a 26% aqueous solution of sodium hydroxide is added, and the pH is 1
After adjusting to 2 or more, the polymer is separated by filtration with a centrifuge and dried to obtain the desired product. Similarly, a comparative experiment was conducted. The results are shown in Table 4.
【００３２】なお、遠心分離機内の重合物は、水３００
ｇとメタノール３００ｇを振りかけ洗浄する。The polymer in the centrifuge is water 300
and 300 g of methanol are sprinkled and washed.
【００３３】[0033]
【表４】 [Table 4]
【００３４】[0034]
【発明の効果】本発明の臭素化ポリフェニレンエーテル
の製法は、作業上安全で、且つ環境問題への影響が少な
い製法で、色相の良い重合物が高収率で得られる。INDUSTRIAL APPLICABILITY The process for producing a brominated polyphenylene ether of the present invention is a process that is safe in operation and has little influence on environmental problems, and a polymer having a good hue can be obtained in a high yield.
Claims (2)
化ポリフェニレンエーテルを製造するにおいて、重合開
始剤として硝酸又は硝酸銀反応で陽性を呈するハロゲン
含有有機化合物を使用することを特徴とする臭素化ポリ
フェニレンエーテルの製法。1. A brominated polyphenylene ether characterized by using a halogen-containing organic compound which is positive in a nitric acid or silver nitrate reaction as a polymerization initiator in the production of a brominated polyphenylene ether by polycondensing a brominated phenolate. Manufacturing method.
ルに対して０．２〜１８重量％である請求項１記載の臭
素化ポリフェニレンエーテルの製法。2. The method for producing a brominated polyphenylene ether according to claim 1, wherein the amount of the polymerization initiator added is 0.2 to 18% by weight based on the brominated phenol.
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|---|---|---|---|
| JP6068433A JP2622814B2 (en) | 1994-04-06 | 1994-04-06 | Preparation of brominated polyphenylene ether |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6068433A JP2622814B2 (en) | 1994-04-06 | 1994-04-06 | Preparation of brominated polyphenylene ether |
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| Publication Number | Publication Date |
|---|---|
| JPH07278290A true JPH07278290A (en) | 1995-10-24 |
| JP2622814B2 JP2622814B2 (en) | 1997-06-25 |
Family
ID=13373573
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550551B2 (en) | 2006-08-22 | 2009-06-23 | Chemtura Corporation | Brominated flame retardant |
| CN105968344A (en) * | 2016-07-08 | 2016-09-28 | 潍坊日兴化工有限公司 | Synthetic method of bromide polyphenylene oxide |
| CN106188530A (en) * | 2016-07-22 | 2016-12-07 | 潍坊玉成化工有限公司 | A kind of preparation method of brominated polyphenylether |
| CN108456304A (en) * | 2018-02-22 | 2018-08-28 | 潍坊玉成化工有限公司 | A kind of preparation method and applications of Noryl |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041093A (en) * | 1984-07-06 | 1985-03-04 | 日本電気株式会社 | Indication of plasma display panel |
-
1994
- 1994-04-06 JP JP6068433A patent/JP2622814B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041093A (en) * | 1984-07-06 | 1985-03-04 | 日本電気株式会社 | Indication of plasma display panel |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7550551B2 (en) | 2006-08-22 | 2009-06-23 | Chemtura Corporation | Brominated flame retardant |
| US7718756B2 (en) | 2006-08-22 | 2010-05-18 | Chemtura Corporation | Brominated flame retardant |
| CN105968344A (en) * | 2016-07-08 | 2016-09-28 | 潍坊日兴化工有限公司 | Synthetic method of bromide polyphenylene oxide |
| CN105968344B (en) * | 2016-07-08 | 2018-10-12 | 山东日兴新材料股份有限公司 | A kind of synthetic method of brominated polyphenylether |
| CN106188530A (en) * | 2016-07-22 | 2016-12-07 | 潍坊玉成化工有限公司 | A kind of preparation method of brominated polyphenylether |
| CN108456304A (en) * | 2018-02-22 | 2018-08-28 | 潍坊玉成化工有限公司 | A kind of preparation method and applications of Noryl |
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| Publication number | Publication date |
|---|---|
| JP2622814B2 (en) | 1997-06-25 |
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