JPS62172021A - Production of polyphenylene ether - Google Patents
Production of polyphenylene etherInfo
- Publication number
- JPS62172021A JPS62172021A JP1333286A JP1333286A JPS62172021A JP S62172021 A JPS62172021 A JP S62172021A JP 1333286 A JP1333286 A JP 1333286A JP 1333286 A JP1333286 A JP 1333286A JP S62172021 A JPS62172021 A JP S62172021A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- low molecular
- polymerization
- solvent
- low
- 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 description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 12
- 229910000039 hydrogen halide Inorganic materials 0.000 claims abstract description 8
- 239000012433 hydrogen halide Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 3
- 239000010941 cobalt Substances 0.000 claims abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004064 recycling Methods 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 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 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 12
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 abstract description 11
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000011572 manganese Substances 0.000 abstract description 5
- 150000001412 amines Chemical class 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000006866 deterioration Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JPWUOWNCHOYFEN-UHFFFAOYSA-N 2,6-bis(2-chloroethyl)phenol Chemical compound OC1=C(CCCl)C=CC=C1CCCl JPWUOWNCHOYFEN-UHFFFAOYSA-N 0.000 description 1
- IKWYDWRGPXTPHV-UHFFFAOYSA-N 2,6-bis(2-chlorophenoxy)phenol Chemical compound C1=CC=C(OC=2C(=CC=CC=2)Cl)C(O)=C1OC1=CC=CC=C1Cl IKWYDWRGPXTPHV-UHFFFAOYSA-N 0.000 description 1
- PXPHPCSQPDHQNI-UHFFFAOYSA-N 2,6-bis(2-methylphenyl)phenol Chemical compound CC1=CC=CC=C1C1=CC=CC(C=2C(=CC=CC=2)C)=C1O PXPHPCSQPDHQNI-UHFFFAOYSA-N 0.000 description 1
- DUCSXVAAPCQAEP-UHFFFAOYSA-N 2,6-dibenzylphenol Chemical compound C1=CC=C(CC=2C=CC=CC=2)C(O)=C1CC1=CC=CC=C1 DUCSXVAAPCQAEP-UHFFFAOYSA-N 0.000 description 1
- RGWXSQCOYFRTKU-UHFFFAOYSA-N 2,6-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCC)=C1O RGWXSQCOYFRTKU-UHFFFAOYSA-N 0.000 description 1
- NAILKKRDWBJCNH-UHFFFAOYSA-N 2,6-dipropylphenol Chemical compound CCCC1=CC=CC(CCC)=C1O NAILKKRDWBJCNH-UHFFFAOYSA-N 0.000 description 1
- IEURJKJFIZRKAG-UHFFFAOYSA-N 2-ethyl-4-octadecoxyphenol Chemical compound CCCCCCCCCCCCCCCCCCOC1=CC=C(O)C(CC)=C1 IEURJKJFIZRKAG-UHFFFAOYSA-N 0.000 description 1
- FVWLNKQRYYNYKJ-UHFFFAOYSA-N 3-chloro-2,6-dimethylphenol Chemical compound CC1=CC=C(Cl)C(C)=C1O FVWLNKQRYYNYKJ-UHFFFAOYSA-N 0.000 description 1
- VWYKSJIPZHRLNO-UHFFFAOYSA-N 4-chloro-2,6-dimethylphenol Chemical compound CC1=CC(Cl)=CC(C)=C1O VWYKSJIPZHRLNO-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OHHLQFCWNFSQEY-UHFFFAOYSA-N O.O.O.O.[Na].[Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O Chemical compound O.O.O.O.[Na].[Na].[Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O OHHLQFCWNFSQEY-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- -1 hydrogen halides Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- SRGBVXWKCOEGJK-UHFFFAOYSA-N octane-1,2,7,8-tetramine Chemical compound NCC(N)CCCCC(N)CN SRGBVXWKCOEGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Landscapes
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
（利用分野）
本発明は、対モノマー収率の攪ｆ１．たポリフェニレン
エーテルの製造法に関し、史に詳しくは、フェノール類
の酸化重合のｍＦこ生成する低分子城体金乗合糸へリサ
イクルしてモノマー原単位全同上させる方法に関するも
のでａ５る。DETAILED DESCRIPTION OF THE INVENTION (Field of Application) The present invention relates to agitation f1. of monomer yield. Regarding the manufacturing method of polyphenylene ether, the detailed history relates to a method in which mF produced by oxidative polymerization of phenols is recycled into low-molecular-weight Kinenori yarn to produce monomer basic units.
（先行技ｖ１σン
ポリフェニレンエーテルは一般に芳香族炭化水素溶媒ま
たは芳香族炭化水素とアルコールの混合溶媒を用いて、
銅、マンガンを含有する錯体触媒の存在下にフェノール
類を強化重合して得られる。(Prior art V1σ polyphenylene ether is generally prepared using an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon and an alcohol.
Obtained by reinforced polymerization of phenols in the presence of a complex catalyst containing copper and manganese.
しかし該重合体液中には、分子量が約１０００以下のｂ
わゆる低分子量体が約５〜１０％存在し、この低分子量
体は、１合体液中の不純物、例えば触媒をアルコールの
洗浄等で除去する工程で浴媒ニ溶解してロスとなり、ポ
リフェニレンエーテルの回収率全低下させ、いわゆるモ
ノマー原単位を悪化させる。However, in the polymer liquid, b having a molecular weight of about 1000 or less is present.
Approximately 5 to 10% of so-called low molecular weight substances exist, and these low molecular weight substances are dissolved in a bath medium and become a loss during the process of removing impurities, such as catalysts, in the combined liquid by washing with alcohol, etc., and become a loss in polyphenylene ether. The total recovery rate of monomers decreases, and the so-called monomer consumption rate worsens.
この様な低分子を体は、溶剤回収系で蒸・ｍ塔の釜残液
中に回収され、さらに薄膜蒸発器等で脱浴媒された後焼
却されるのが一般的である。Generally, such low-molecular substances are recovered in the bottom liquid of the steam column using a solvent recovery system, and then incinerated after being removed as a bathing medium using a thin film evaporator or the like.
低分子１体を回収して、製品と混合すれば、１」収率は
向上するが、この様にして得らｊ’したボリフ工二しン
エーテルヲ用いるト、ポリフェニレンエーテル樹脂成形
体又は他の樹脂との混むＶこよ０樹）ｊｎ成形体の機械
的強度が者しく低下したり、色１シ′踊が犬さく悪化す
る。If one low molecule is recovered and mixed with the product, the yield will be improved by 1, but if the borifice engineered ether obtained in this way is used, polyphenylene ether resin moldings or other resins. The mechanical strength of the molded product is markedly reduced, and the color variation is significantly deteriorated.
（発明の概要）
本発明はかかる点に着目してなされたものであって、芳
香族炭化水素溶媒または芳香族炭化水素とアルコールの
混合溶媒を用いて、銅、マンガンを含有する錯体触媒の
存在下にフェノール類を酸化重合せしめ、得られた重合
反応液から低分子量体を回収し、該低分子量体をハロゲ
ン化水素と接触させた後、重合系ヘリサイクルすること
を特徴とするポリフェニレンエーテルの製造法を提供す
るものである。(Summary of the Invention) The present invention has been made with attention to this point, and the present invention is directed to the presence of a complex catalyst containing copper and manganese using an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon and an alcohol. A method for producing polyphenylene ether, which is characterized in that phenol is oxidatively polymerized, a low molecular weight substance is recovered from the resulting polymerization reaction solution, the low molecular weight substance is brought into contact with hydrogen halide, and then recycled to the polymerization system. It provides a manufacturing method.
（作用効果ン
不発明は、低分子重体をハロゲン化水素と接触させるこ
とにより、重合系ヘリサイクル出来るようにしたもので
ある。(The function and effect of the invention is that by bringing a low-molecular weight substance into contact with hydrogen halide, it can be recycled into a polymerization system.
ハロゲン化水素と接触させた低分子重体は、フェノール
類の酸化重合において分子量増大に恐影Ｖを及ぼさない
。さらに低分子重体そのものが高分子量化さ几るため、
モノマー原単位も向上し、得られるポリフェニレンエー
テルの樹脂成形体又は他の樹脂との混合による樹脂成形
体の機械的強度、色調に何ら影Ｉ＃を与えない。Low molecular weight polymers brought into contact with hydrogen halide do not affect molecular weight increase in the oxidative polymerization of phenols. Furthermore, since the low molecular weight substance itself becomes high molecular weight,
The monomer basic unit is also improved, and there is no influence on the mechanical strength and color tone of the obtained polyphenylene ether resin molding or the resin molding obtained by mixing with other resins.
この様なことは全く驚りべきことであり、かかる知見か
ら本発明を提供するに到ったものである。This finding is completely surprising, and this knowledge led us to provide the present invention.
（具体的説明）
本発明に使用されるフェノール類は、次式で示される構
造を有するフェノール系単量体である。(Specific Description) The phenols used in the present invention are phenolic monomers having a structure represented by the following formula.
（式中、Ｘは水素原子、塩素原子、炭素原子、およびヨ
ウ素原子の中から選ばれた１員、Ｒ１はアルキル基、ア
ルコキシ基並びにハロゲン原子とフェノール核との間に
少なくとも２個の炭素原子を有するハロゲン化アルキル
基およびハロゲン化アルコキシ基の中から選ばれた１価
の置換基、Ｒ２はＲ１に関して列挙された基およびハロ
ゲン原子の中から選ばれたｌ員％ Ｒ，の谷々はＲ２に
関して列挙された基および水素原子の中から選ばれた１
員である。）
具体的には、２，６−シメチルフエノール、２．６−ジ
ニチルフエノール、２．６−ジフチルフエノール、２，
６−ジラウリルフェノール、２，６−ジプロピルフェノ
ール、２．６−ジフェニルフェノール、２．６−シメト
キシフエノール、２．３．６−トリメチルフエノール、
２，３，５．６−チトラメチルフエノー／ｌ／、２．６
−シエトキシフエノール、２−エチル−４−ステアリル
オキシフェノール、２．６−ジ（クロルフェノキシ）フ
ェノール、２．６−シメチルー３−クロルフェノール、
２，６−シメチルー４−クロルフェノール、２．６−シ
メチルー３−クロル５−フロムフェノール、２，６−ジ
（クロルエチル）フェノール、２−メチル−６−イツプ
チルフエノール、２−）ｆルー６−フェニルフェノール
、２．６−ジベンジルフェノール、２，６−ジトリルフ
エノール、２．６−シ（クロルプロピル〕フェノ−、Ｉ
＋／、３−メチル−６−タージャリーブチルフェノール
などがあげられる。(In the formula, a monovalent substituent selected from halogenated alkyl groups and halogenated alkoxy groups, R2 is a 1-membered substituent selected from the groups listed for R1 and halogen atoms. 1 selected from the groups and hydrogen atoms listed for
member. ) Specifically, 2,6-dimethylphenol, 2.6-dinitylphenol, 2.6-diphthylphenol, 2,
6-dilaurylphenol, 2,6-dipropylphenol, 2.6-diphenylphenol, 2.6-simethoxyphenol, 2.3.6-trimethylphenol,
2,3,5.6-titramethylphenol/l/, 2.6
-Siethoxyphenol, 2-ethyl-4-stearyloxyphenol, 2,6-di(chlorophenoxy)phenol, 2,6-dimethyl-3-chlorophenol,
2,6-dimethyl-4-chlorophenol, 2,6-dimethyl-3-chloro5-fromphenol, 2,6-di(chloroethyl)phenol, 2-methyl-6-yptylphenol, 2-) f-6- Phenylphenol, 2,6-dibenzylphenol, 2,6-ditolylphenol, 2,6-cyclopropylphenol, I
+/, 3-methyl-6-terjarybutylphenol, and the like.
これらは、それぞれ単独で用いることもでさるし、また
、他のフェノール系単撞体と共に用いて共重合体の装造
に供することもできる。Each of these can be used alone, or can be used together with other phenolic monostrands to prepare a copolymer.
これらの中で２，６−シメチルフエノールが特に好適で
ある。Among these, 2,6-dimethylphenol is particularly preferred.
本発明の重合反応液は、フェノール類を芳香族炭化水素
溶媒または芳香族炭化水素とアルコールの混合溶媒中で
、銅、マンガン又はコバルトを含有する錯体触媒の存在
下に酸素又は酸素含有気体と接触せしめることによって
酸化重合することによって得られる。The polymerization reaction solution of the present invention involves contacting phenols with oxygen or an oxygen-containing gas in an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon and alcohol in the presence of a complex catalyst containing copper, manganese, or cobalt. It can be obtained by oxidative polymerization by letting it stand.
銅を含有する錯体触媒として、例えば銅塩−アミンよシ
成る触媒（％公昭３６−１８６９２号、特公昭３９−２
９３７３号、特開昭４９−４９０等）があげられ、マン
ガンを含有する錯体触媒として、例えばマンガン塩−ア
ミンより成る触媒（特公昭４２−３１９！５号等ンおよ
びマンガン塩−各種キレート化剤−アミンよりなる触媒
（特開昭５１−３４９９６号、特開昭５６−３２５２３
号、特開昭５８−１２２９１９号等ンがあげられるＯ
ｇｉとしては、ベンゼン、トルエン、キシレン等の芳香
族炭化水素溶媒を単独で、あるいはこれ等芳香族炭化水
素溶媒とメタノール、エタノール、イソプロパツール等
のアルコール類とを混合した混合溶媒が使用される。Examples of copper-containing complex catalysts include copper salt-amine catalysts (%Kokoku No. 36-18692, Japanese Patent Publication No. 39-2
9373, JP-A No. 49-490, etc.), and examples of complex catalysts containing manganese include catalysts consisting of manganese salts and amines (Japanese Patent Publication No. 42-319!5, etc.) and manganese salts-various chelating agents. - Catalysts consisting of amines (JP-A-51-34996, JP-A-56-32523)
Examples of Ogi include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, or aromatic hydrocarbon solvents such as methanol, ethanol, and isopropanol. A mixed solvent containing alcohol such as tools is used.
混合溶媒として用いる場合には、アルコール／芳香族炭
化水禦溶媒の容盪比ｉ５／９５〜７０／３０の範囲とす
るのが好ましい。When used as a mixed solvent, the stirring ratio of alcohol/aromatic hydrocarbon solvent is preferably in the range of 5/95 to 70/30.
重合温度は一般に２０℃〜７０℃のＹＩＪＬ度で行なわ
れる。The polymerization temperature is generally 20 DEG C. to 70 DEG C. YIJL.
ポリフェニレンエーテルの分子量は、反応時間、触媒量
、溶媒種、溶媒組成等でコントロールされる。重合体液
中には極限粘度が０．３０以上の分子量のポリフェニレ
ンエーテルを含有する。The molecular weight of polyphenylene ether is controlled by reaction time, catalyst amount, solvent type, solvent composition, etc. The polymer liquid contains polyphenylene ether having a molecular weight and an intrinsic viscosity of 0.30 or more.
なお、本発明においてポリフェニレンエーテルの極限粘
度は、クロロホルム中で３０℃の温度で測定したもので
ある。In the present invention, the intrinsic viscosity of polyphenylene ether is measured in chloroform at a temperature of 30°C.
重合反応液中のポリマーは、重合溶媒の種類によって、
浴液状であることも、スラリー状であることもあり、い
ずれも本発明を利用することができる。The polymer in the polymerization reaction solution varies depending on the type of polymerization solvent.
The present invention can be applied to either a bath liquid form or a slurry form.
この様に重合された重合反応液中には、重合が充分に進
行せず途中で停止したいわゆる低分子量体５〜１０係程
度が溶解した状態で含有される。The polymerization reaction solution polymerized in this manner contains in a dissolved state about 5 to 10 percent of so-called low molecular weight substances whose polymerization did not proceed sufficiently and was stopped midway.
ここにいう低分子量体とは極限粘度で０．１０以下で、
フェノール類の５〜６ｉ：体までのものである０
重合反応液は、触媒分解及び触媒残渣除去のために後処
理に付される。The low molecular weight substance mentioned here has an intrinsic viscosity of 0.10 or less,
The polymerization reaction solution containing up to 5-6i:phenols is subjected to post-treatment for catalyst decomposition and catalyst residue removal.
後処理方法に関しては、特に制限はないが例えば、重合
反応液に塩酸等の酸またはエチレンジアミン四酢酸四ナ
トリウム四水塩等のようなキレート剤を加えて触媒を失
活させた後、ポリマーを分離し、ポリマーはアルコール
等の溶剤で洗浄し乾燥される。There are no particular restrictions on the post-treatment method, but for example, an acid such as hydrochloric acid or a chelating agent such as ethylenediaminetetraacetic acid tetrasodium tetrahydrate may be added to the polymerization reaction solution to deactivate the catalyst, and then the polymer may be separated. The polymer is then washed with a solvent such as alcohol and dried.
このようにしてポリマーと分離された重合反応液中には
、触媒残渣および低分子量体が含まれ、溶剤回収ととも
に低分子量体が回収される。The polymerization reaction liquid separated from the polymer in this manner contains catalyst residues and low molecular weight substances, and the low molecular weight substances are recovered together with the solvent recovery.
低分子量体の回収方法は、特に制限がなく、例えば、ポ
リマーを分離した重合反応液を水と接触させ、触媒残渣
を水相に抽出した後、水分を除去し、低分子量体を溶液
として回収することができる。There are no particular restrictions on the method for recovering the low molecular weight substance; for example, the polymerization reaction solution from which the polymer has been separated is brought into contact with water, the catalyst residue is extracted into the aqueous phase, the water is removed, and the low molecular weight substance is recovered as a solution. can do.
また、触媒残渣を除去した溶液をロータリーエバポレー
ター、薄膜蒸発器等の蒸発器で脱溶媒して低分子量体を
固状として回収することができる。Furthermore, the solution from which the catalyst residue has been removed can be desolvated with an evaporator such as a rotary evaporator or a thin film evaporator, and the low molecular weight substance can be recovered as a solid.
このようにして回収された低分子量体はハロゲン化水素
で処理した後重合系にリサイクルされる。The low molecular weight substances thus recovered are treated with hydrogen halide and then recycled to the polymerization system.
ハロゲン化水素による接触処理は、低分子量体が溶液状
でないときは、重合溶媒、あるいは重合溶媒の成分とし
て使用される溶媒に溶解して行なわれる。溶液中の低分
子量体濃度は１０ Ｖ／ｌ〜５００り／ｌの範囲が好ま
しい。When the low molecular weight substance is not in solution, the contact treatment with hydrogen halide is carried out by dissolving it in the polymerization solvent or a solvent used as a component of the polymerization solvent. The concentration of the low molecular weight substance in the solution is preferably in the range of 10 V/l to 500 V/l.
ここにいうハロゲン化水素とは塩化水素、臭化水素、ヨ
ウ化水素、フッ化水素等であり、いずれも水溶液として
低分子量体溶液に添加し、攪拌することにより接触処理
が行なわ几る。The hydrogen halides referred to herein include hydrogen chloride, hydrogen bromide, hydrogen iodide, hydrogen fluoride, etc., and all of them are added to the low molecular weight solution as an aqueous solution and the contact treatment is carried out by stirring.
低分子量体と接触させるハロゲン化水素の量は、低分子
量体に含Ｍされる窒素原子の量（触媒として使用するア
ミンに由来する）Ｋ応じて決められ、窒素のダラム原子
量と同量以上のモル数が使用される。一般には同量から
１０倍程度使用される。The amount of hydrogen halide to be brought into contact with the low molecular weight body is determined depending on the amount of nitrogen atoms (derived from the amine used as a catalyst) contained in the low molecular weight body, and is equal to or more than the Durham atomic weight of nitrogen. Moles are used. Generally, the same amount to about 10 times more is used.
接触させる温度は、任意であるが、一般に２０℃〜１５
０℃の範囲である。The contact temperature is arbitrary, but generally 20°C to 15°C.
It is in the range of 0°C.
接触させる時間も、任意であ夛、一般にＯ，Ｓ時間〜５
時間の範囲である。The contact time can be changed as desired, but generally O,S hours ~ 5
It is a range of time.
この様にして調整された低分子量体は、溶媒および触媒
を含んだフェノール類の酸化重合調整液と混合し、酸素
を通じて再び重合に供される。The low molecular weight substance prepared in this way is mixed with a phenol oxidative polymerization adjustment solution containing a solvent and a catalyst, and subjected to polymerization again through oxygen.
以下具体例により本発明を説明するが、あくまで本発明
の一態様にすぎず限定されるものではない０
実施例−１（低分子量体の回収）
攪拌機、温度計、コンデンサー及び酸素導入管を備えた
容量１０Ｊのジャケット付攪拌槽に２，６−キシレノー
ル１０００ ｆ （８，１８モル）、ベンゼン３．２５
１およびメタノール１．７５１ ｆ仕込み均一な溶液と
なした後、臭化第２鋼５．０ ？ （０，０２２モル）
テトラメチレンエチレンジアミン４．Ｏｆ （０，０３
４モル）およびジブチルアミン９７．Ｏｒ （０，７５
３モル）を添加した。The present invention will be described below with reference to specific examples, which are merely one aspect of the present invention and are not intended to be limiting. 1000 f (8.18 mol) of 2,6-xylenol and 3.25 mol of benzene were placed in a jacketed stirring tank with a capacity of 10 J.
1 and methanol 1.751 f to form a homogeneous solution, then brominated steel 5.0 ? (0,022 mol)
Tetramethylene ethylene diamine 4. Of (0,03
4 mol) and dibutylamine 97. Or (0,75
3 mol) was added.
ついで内容物を激しくかきまぜながら酸素を３．Ｏｔｌ
−の速さで反応混合物中へ吹き込んだ。The contents were then stirred vigorously and oxygenated for 3 minutes. Otl
- into the reaction mixture at a rate of -.
反応温度を５０℃に維持し、酸素の吹き込み開始から４
時間経過した時点で酸素の供給を停止した。The reaction temperature was maintained at 50°C, and 4 hours after the start of oxygen blowing.
When the time elapsed, the oxygen supply was stopped.
この重合体液中のポリフェニレンエーテルの極限粘度は
０．４３５であった。この重合体液に３５チ塩酸水６２
．０ｄ加え５０℃で１時間攪拌し、メタノールを帆５を
加えた後重合体を濾過し、さらにメタノール３ｔで洗浄
し濾過して乾燥させてポリフェニレンエーテル粉体９１
５Ｐ１！た。The intrinsic viscosity of polyphenylene ether in this polymer liquid was 0.435. Add 35% hydrochloric acid and 62% to this polymer solution.
．． After adding 0 d of methanol and stirring at 50°C for 1 hour, the polymer was filtered, washed with 3 t of methanol, filtered and dried to obtain polyphenylene ether powder 91.
5P1! Ta.
このポリフェニレンエーテルの極限粘度は０．４５７で
あった。また、モノマー原単位は１．０９２（ｇ −２
，６キｙレノール／ホリフエニレンエーテル）であった
。The intrinsic viscosity of this polyphenylene ether was 0.457. In addition, the monomer basic unit is 1.092 (g -2
, 6-kylenol/holophenylene ether).
一方戸液を回収し、この戸液に同量の水を加えて静置し
て、上相部を回収し、ロータリーエバポレーターにて脱
溶媒し、低分子量体８５ｆを得た。On the other hand, the solution was collected, and the same amount of water was added to the solution and allowed to stand. The upper phase was collected and the solvent was removed using a rotary evaporator to obtain a low molecular weight substance 85f.
この低分子量体の極限粘度を測定した所帆０７７であっ
た。また窒素含有量は４８００ ｐｐｍ であった。The limiting viscosity of this low molecular weight substance was measured as 077. Further, the nitrogen content was 4800 ppm.
実施例−２
攪拌機、温度計、コンデンサー及び酸素導入管を備えた
容量１ｔのジャケット付攪拌槽に、実施例−１で回収し
た低分子量体１０ｙ（窒素原子として０．００３４モル
原子含む）、ベンゼン３２．５ｄ１メタノール１７．５
ｗｌ、および３５重量％塩酸水ｘ、２Ｆ（塩化水素とし
て０．０１１５モル）を加え５０℃で１時間処理した。Example 2 In a jacketed stirring tank with a capacity of 1 ton equipped with a stirrer, a thermometer, a condenser, and an oxygen introduction tube, the low molecular weight substance 10y (containing 0.0034 mol atoms as nitrogen atoms) recovered in Example 1 and benzene were placed. 32.5d1 methanol 17.5
wl, and 35% by weight hydrochloric acid water x, 2F (0.0115 mol as hydrogen chloride) were added, and the mixture was treated at 50°C for 1 hour.
その後ベンゼン２９２．５ ｗｊ、メタノール１５７゜
５ｍ（、２，６キ７レノール１ｏｏｐ（ｏ、ｓｘｓモル
）を処理液に加え、さらに臭化第２銅０．５０ ｙ （
ｏ。Thereafter, 292.5 wj of benzene, 157.5 m of methanol (1 oop (o, sxs mol) of 2,6-7-lenol) were added to the treatment solution, and 0.50 y of cupric bromide (
o.
００２２モル）、テトジメチレンエチレンジアミン０．
４０ ｆ （０，０３４モル）およびジブチルアミン９
．７１ （ｏ、ｏ ７ ｓ ３モル）を添加した。0022 mol), tetodimethyleneethylenediamine 0.
40 f (0,034 mol) and dibutylamine 9
．． 71 (o, o 7 s 3 mol) was added.
ついで内容物を激しくかきまぜながら酸素を３ｏｏｇ／
ｍの速度で反応混合物中へ吹き込んだ。Then, while stirring the contents vigorously, add 3 oog of oxygen.
into the reaction mixture at a rate of m.
反応温度を５０℃に維持し、酸素の吹き込み開始から４
時間経過した時点で酸素の供給を停止した。The reaction temperature was maintained at 50°C, and 4 hours after the start of oxygen blowing.
When the time elapsed, the oxygen supply was stopped.
この重合体液中のポリフェニレンエーテルの極限粘度は
０．４３０であった。この重合体液を実施例−１で塩酸
水、メタノールの量を１／工０量にした他は実施例−１
と同様に後処理を行なった。The intrinsic viscosity of polyphenylene ether in this polymer liquid was 0.430. This polymer liquid was prepared in Example-1 except that the amount of hydrochloric acid water and methanol was changed to 1/work 0 amount.
Post-processing was performed in the same manner.
かくしてポリフェニレンエーテル１００．４ｙを得た。In this way, 100.4y of polyphenylene ether was obtained.
この粉体の極限粘度は０．４５０であった。The intrinsic viscosity of this powder was 0.450.
本実施例でわかるように低分子量体を重合系ヘリサイク
ルしても、２，６キシレノールの酸化重合に影響しない
のみならず、モノマー原単位も０．９９６（ｇ−２，６
キシレノ一ル／ｇポリフェニレンエーテル）と向上して
いることがわかる。As can be seen in this example, recycling low molecular weight substances into the polymerization system not only does not affect the oxidative polymerization of 2,6 xylenol, but also reduces the monomer consumption to 0.996 (g-2,6 xylenol).
It can be seen that the amount of polyphenylene ether (xylenol/g polyphenylene ether) has improved.
比較例−１
実施例−２で低分子量体の塩酸処理を行なわない以外は
実施例−２と同様に重合を行なった。Comparative Example 1 Polymerization was carried out in the same manner as in Example 2, except that the low molecular weight substance was not treated with hydrochloric acid.
重合体液中のポリフェニレンエーテルの極限粘度は０．
１７０まで低下しており、低分子量体が２．６キシレノ
ールの重合を阻害していることがわかる。The intrinsic viscosity of polyphenylene ether in the polymer liquid is 0.
It decreases to 170, indicating that the low molecular weight substance inhibits the polymerization of 2.6 xylenol.
実施例３〜５
実施例２で塩酸を臭化水素に変更し、臭化水素の量およ
び低分子量体の量を変化はせた以外は実施例−２と同様
に重合および後処理を行なった。Examples 3 to 5 Polymerization and post-treatment were carried out in the same manner as in Example-2, except that hydrochloric acid in Example 2 was changed to hydrogen bromide and the amount of hydrogen bromide and the amount of low molecular weight substances were changed. .
結果を表−１に示す。The results are shown in Table-1.
（以下余白）
実施例−６〜１０
実施例−１〜５で得られたポリフェニレンエーテル４５
重量部およびゴム変性耐衝撃性スチレン樹脂（三菱モン
サンド社製ＨＴ−７６）５５重量部とをブラベンダープ
ラストグラフを用いて２５００１０分間混練して樹脂組
成物を製造した。(Left below) Examples-6 to 10 Polyphenylene ether 45 obtained in Examples-1 to 5
Parts by weight and 55 parts by weight of a rubber-modified impact-resistant styrene resin (HT-76 manufactured by Mitsubishi Monsando) were kneaded for 2,500,010 minutes using a Brabender Plastograph to produce a resin composition.
該組成物からプレス成形によって厚’ｇ３．２ｍｍのノ
ツチ付きアイゾツト衝撃強度測定用試験片を作成し、測
定した。結果を表−２に示す。A notched test piece for measuring Izot impact strength with a thickness of 3.2 mm was prepared from the composition by press molding, and the test piece was measured. The results are shown in Table-2.
比較例−２〜４
実施例−１で得たポリフェニレンエーテル４５重量部、
ゴム変性耐衝撃性スチレン樹脂（三菱モンサンド社ｇＨ
Ｔ−７６）５５重量部および実施例−１で回収した低分
子量体を２．５〜７．５重量部加えた以外は実施例−６
と同様にしてノツチ付きアイゾツト衝撃強度を測定した
。結果を表−２に示す。Comparative Examples-2 to 4 45 parts by weight of polyphenylene ether obtained in Example-1,
Rubber-modified impact-resistant styrene resin (Mitsubishi Monsando gH
Example-6 except that 55 parts by weight of T-76) and 2.5 to 7.5 parts by weight of the low molecular weight substance recovered in Example-1 were added.
Notched Izo impact strength was measured in the same manner as above. The results are shown in Table-2.
Claims (1)
の混合溶媒を用いて、銅、マンガン又はコバルトを含有
する錯体触媒の存在下にフェノール類を酸化重合せしめ
、得られた重合反応液から低分子量体を回収し、該低分
子量体をハロゲン化水素処理した後重合系へリサイクル
することを特徴とするポリフェニレンエーテルの製造法
。Phenols are oxidatively polymerized using an aromatic hydrocarbon solvent or a mixed solvent of aromatic hydrocarbon and alcohol in the presence of a complex catalyst containing copper, manganese, or cobalt, and low molecular weight products are obtained from the resulting polymerization reaction liquid. A method for producing polyphenylene ether, which comprises recovering the low molecular weight substance, treating the low molecular weight substance with hydrogen halide, and then recycling it into a polymerization system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333286A JPH0615611B2 (en) | 1986-01-24 | 1986-01-24 | Method for producing polyphenylene ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1333286A JPH0615611B2 (en) | 1986-01-24 | 1986-01-24 | Method for producing polyphenylene ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62172021A true JPS62172021A (en) | 1987-07-29 |
| JPH0615611B2 JPH0615611B2 (en) | 1994-03-02 |
Family
ID=11830180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1333286A Expired - Lifetime JPH0615611B2 (en) | 1986-01-24 | 1986-01-24 | Method for producing polyphenylene ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0615611B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089146A (en) * | 2008-10-10 | 2010-04-22 | Kawajiri Kogyo Kk | Hot plate and press machine |
| JP5960901B1 (en) * | 2015-06-02 | 2016-08-02 | 旭化成株式会社 | Process for producing polyphenylene ether |
| JP2020015878A (en) * | 2018-07-27 | 2020-01-30 | 旭化成株式会社 | Method for producing polyphenylene ether resin |
-
1986
- 1986-01-24 JP JP1333286A patent/JPH0615611B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010089146A (en) * | 2008-10-10 | 2010-04-22 | Kawajiri Kogyo Kk | Hot plate and press machine |
| JP5960901B1 (en) * | 2015-06-02 | 2016-08-02 | 旭化成株式会社 | Process for producing polyphenylene ether |
| JP2020015878A (en) * | 2018-07-27 | 2020-01-30 | 旭化成株式会社 | Method for producing polyphenylene ether resin |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0615611B2 (en) | 1994-03-02 |
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