JPH0233046B2 - SHINKIRIBINGUHORIMAAOYOBISONOSEIZOHOHO - Google Patents
SHINKIRIBINGUHORIMAAOYOBISONOSEIZOHOHOInfo
- Publication number
- JPH0233046B2 JPH0233046B2 JP4535086A JP4535086A JPH0233046B2 JP H0233046 B2 JPH0233046 B2 JP H0233046B2 JP 4535086 A JP4535086 A JP 4535086A JP 4535086 A JP4535086 A JP 4535086A JP H0233046 B2 JPH0233046 B2 JP H0233046B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- vinyl monomer
- hydrogen atom
- group
- anionic polymerization
- 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.)
- Expired - Lifetime
Links
- 239000000178 monomer Substances 0.000 claims description 28
- 229920000642 polymer Polymers 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 19
- -1 acid amide compound Chemical class 0.000 claims description 16
- 239000012320 chlorinating reagent Substances 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 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 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000005968 oxazolinyl group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000003505 polymerization initiator Substances 0.000 description 13
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000003708 ampul Substances 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012086 standard solution Substances 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- IRQWEODKXLDORP-UHFFFAOYSA-N 4-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=C)C=C1 IRQWEODKXLDORP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NJBYQXATMUPPBX-UHFFFAOYSA-N 2-(4-ethenylphenyl)-4,4-dimethyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC(C=C)=CC=2)=N1 NJBYQXATMUPPBX-UHFFFAOYSA-N 0.000 description 3
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- DGZXVEAMYQEFHB-UHFFFAOYSA-N 4-ethenylbenzoyl chloride Chemical compound ClC(=O)C1=CC=C(C=C)C=C1 DGZXVEAMYQEFHB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 125000006239 protecting group Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- YUCOVHFIYPJDDN-UHFFFAOYSA-N 4-prop-1-en-2-ylbenzoic acid Chemical compound CC(=C)C1=CC=C(C(O)=O)C=C1 YUCOVHFIYPJDDN-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- QHGFJRYNEDVKAK-UHFFFAOYSA-M cesium;4-ethenylbenzoate Chemical compound [Cs+].[O-]C(=O)C1=CC=C(C=C)C=C1 QHGFJRYNEDVKAK-UHFFFAOYSA-M 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BWBPUYJIIQMIAS-UHFFFAOYSA-M lithium;4-ethenylbenzoate Chemical compound [Li+].[O-]C(=O)C1=CC=C(C=C)C=C1 BWBPUYJIIQMIAS-UHFFFAOYSA-M 0.000 description 1
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- RMHHXELLJFQJRG-UHFFFAOYSA-M potassium;4-ethenylbenzoate Chemical compound [K+].[O-]C(=O)C1=CC=C(C=C)C=C1 RMHHXELLJFQJRG-UHFFFAOYSA-M 0.000 description 1
- ZYBHSWXEWOPHBJ-UHFFFAOYSA-N potassium;propan-2-ylbenzene Chemical class [K+].C[C-](C)C1=CC=CC=C1 ZYBHSWXEWOPHBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- ZPAICLPTNKAJHB-UHFFFAOYSA-M sodium;4-ethenylbenzoate Chemical compound [Na+].[O-]C(=O)C1=CC=C(C=C)C=C1 ZPAICLPTNKAJHB-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、芳香族系ビニル化合物のリビングポ
リマー及びその製造方法に関する。
〔従来の技術〕
分子中に反応性基を有するビニルモノマーから
は、反応性基中の活性水素やカルボニル炭素のた
め、直接それらビニルモノマーのアニオンリビン
グポリマーは得られていない。
本発明者らは、先に、水酸基、アミノ基、フオ
ルミル基等の反応性基を持つ芳香族系ビニルモノ
マーの反応性基を、予め置換基で保護した後、ア
ニオン重合開始剤を作用させることにより、保護
された反応性基を有する芳香族ビニルモノマーの
アニオンリビングポリマーが得られることを見出
した〔特開昭59−53509号公報；高分子予稿集、
34巻、２号、195頁（1985）〕。
〔発明が解決しようとする問題点〕
本発明は、カルボキシル基を持つ芳香族系ビニ
ルモノマーのカルボキシル基を保護したモノマー
のアニオンリビングポリマーを合成することを目
的とする。
〔問題点を解決するための手段〕
本発明者等は鋭意研究を重ねた結果、該芳香族
系ビニルモノマーのカルボキシル基を４，４−置
換オキサゾリン骨格からなる置換基に変換して保
護することにより、４，４−置換オキサゾリニル
基を有する芳香族系ビニルモノマーの繰り返し単
位をもつリビングポリマーが生成することを見出
して本発明を完成した。
すなわち、本発明は
一般式
〔式中、R1、R2は同一か異なるアルキル基、R3
は水素原子又はメチル基、ｎは２以上の整数を示
す。〕の繰り返し単位を持つ新規リビングポリマ
ー（）及び、
一般式
〔式中、R3は水素原子又はメチル基、Ｍは水素
原子又はアルカリ金属原子を示す。〕で表わされ
るビニルモノマー（）に塩素化剤を反応させ酸
塩化物とした後、式
〔式中、R1、R2は同じか異なるアルキル基を示
す。〕
で表わされるアミノアルコール系化合物を反応さ
せて生成する酸アミド化合物を上記塩素化剤の存
在下で縮合、閉環して得られる該ビニルモノマー
（）の４，４−置換オキサゾリニル基置換体を
アニオン重合開始剤の存在下で重合することから
なる上記ポリマー（）の製造方法を要旨とす
る。
上記ビニルモノマー（）の具体例としては、
４−ビニル安息香酸、４−ビニル安息香酸リチウ
ム塩、４−ビニル安息香酸ナトリウム塩、４−ビ
ニル安息香酸カリウム塩、４−ビニル安息香酸セ
シウム塩、４−カルボキシ−α−メチルスチレ
ン、４−カルボキシ−α−メチルスチレンリチウ
ム塩、４−カルボキシ−α−メチルスチレンナト
リウム塩、４−カルボキシ−α−メチルスチレン
カリウム塩、４−カルボキシ−α−メチルスチレ
ンセシウム塩等が挙げられる。
ビニルモノマー（）からビニルモノマー
（）の酸塩化物を得る際に用いられる塩素化剤
としては、塩化チオニル、五塩化リン、三塩化リ
ン、塩化ホスホリル等が列挙されるが、好ましく
は塩化チオニルである。
ビニルモノマー（）と塩素化剤の反応は０〜
40℃で１〜10時間行われる。両者の接触は通常無
溶媒で行われるが、必要に応じてベンゼン、塩化
メチレン、クロロホルム、四塩化炭素等の溶媒の
存在下で行つてもよく、また窒素ガス等の不活性
ガス雰囲気下で行つてもよい。両者の接触割合
は、通常、ビニルモノマー（）に対して塩素化
剤が１倍モル以上、望ましくは２〜３倍モルであ
る。
前記アミノアルコール系化合物の式中のR1及
びR2は、メチル、エチル、ｎ−プロピル、iso−
プロピル、ｎ−ブチル、iso−ブチル、ｔ−ブチ
ル、ｎ−ペンチル、ｎ−ヘキシル等の低級アルキ
ル基であり、R1とR2は同じでも異つてもよい。
ビニルモノマー（）の酸塩化物とアミノアルコ
ール系化合物の反応は、エーテル、塩化メチレ
ン、クロロホルム等の溶媒、望ましくは塩化メチ
レンの存在下、０〜10℃で１〜10時間行われる。
前記アミノアルコール系化合物は、ビニルモノマ
ー（）の酸塩化物に対して１倍モル以上、望ま
しくは２〜３倍モル用いられる。
ビニルモノマー（）の酸塩化物と前記アミノ
アルコール系化合物を反応させた後、縮合、閉環
によりオキサゾリン環を形成させるために用いら
れる塩素化剤は、塩化チオニル、五塩化リン、三
塩化リン、塩化ホスホリル等が挙げられるが、望
ましくは塩化チオニルである。塩素化剤は、ビニ
ルモノマー（）の酸塩化物に対して１倍モル以
上、望ましくは３〜５倍モル加え、反応は０〜10
℃で１〜10時間行われ、必要に応じて塩化メチレ
ン、クロロホルム等の溶媒の存在下で行つてもよ
い。
かくすることにより、ビニルモノマーー（）
のカルボキシル基は、４，４−置換オキサゾリニ
ル基と置換され、ビニルモノマー（）の置換体
となるが、該置換体はアニオン重合開始剤を用い
てアニオン重合することにより、該置換体のリビ
ングポリマー（）が得られる。
本発明で用いる適当なアニオン重合開始剤とし
ては、ｎ−ブチルリチウム、ナフタレンリチウム
塩、ナフタレンナトリウム塩、ナフタレンカリウ
ム塩、（α−メチルスチレンオリゴマー）リチウ
ム塩、（α−メチルスチレンオリゴマー）ナトリ
ウム塩、（α−メチルスチレンオリゴマー）カリ
ウム塩、クミルカリウム塩等を挙げることができ
る。
アニオン重合は、−100℃〜室温で行われるが、
望ましくは−30℃以下の低温、特に望ましくは−
50〜−100℃の低温で0.1〜24時間行われる。重合
反応は無溶媒で行つてもよいが、望ましくは溶媒
の存在下で行われる。適当な溶媒としてはテトラ
ヒドロフラン、ヘキサン、トルエン、シクロヘキ
サン、ペンタン、ベンゼン等が列挙され、これら
は二種以上を混合して用いてもよい。また、重合
系は、重合反応を妨害する水分、酸素のない不活
性ガス雰囲気あるいは減圧下、特に望ましくは高
真空下に保つことが必要とされる。
リビングポリマー（）の分子量は、該置換
体／アニオン重合開始剤の比を変えることによつ
て制御することができ、その比を大きくすること
によつて分子量を高くすることができる。
かくして得られたリビングポリマー（）は、
通常約500〜約500000、好ましくは約2000〜約
200000、特に好ましくは約5000〜約100000の数平
均分子量を持ち、重量平均分子量／数平均分子量
の比が１に近い極めて狭い分子量分布を有してい
る。
〔発明の効果〕
本発明のリビングポリマー（）は、メタノー
ルなどで処理し、ついで塩酸、硫酸等の鉱酸と接
触させた後、更に水酸化ナトリウム、水酸化カリ
ウム等の塩基の存在下でケン化することにより、
保護基である４，４−置換オキサゾリニル基が脱
離し、ビニルモノマー（）のポリマーを製造す
ることができる。この方法によれば、公知のビニ
ルモノマー（）のラジカル重合法によるビニル
モノマー（）のポリマー製造法に比べ、分子量
の制御が容易であり、任意の分子量でかつ極めて
狭い分子量分布を有するポリマーを容易に製造で
きるという特徴を有する。
かくして得られる保護基を外したポリマーは、
それ自体、熱可塑性樹脂と機能性樹脂の両方の性
質を有する特異な樹脂として種々の工業的用途に
利用でき、その反応性置換基を他の反応性基と置
換した新たな機能性樹脂の合成原料としても有用
である。
以下、本発明を実施例により具体的に説明する
が、本発明はこれらに限定されるものではない。
〔実施例〕
（アニオン重合に用いる重合装置）
アニオン重合に用いるアニオン重合開始剤溶
液、モノマー溶液、１−オクタノール標準溶液は
凍結後、高真空ラインで脱気してブレークシール
を持つアンプルに封入した。
アニオン重合は、高真空ラインに接続されたフ
ラスコに、複数のアニオン重合開始剤溶液、モノ
マー溶液及び１−オクタノール標準溶液の入つた
上記アンプル並びに系内を洗浄した廃アニオン開
始剤溶液を取り出す枝管を接続した図面に示す装
置を用い、次の方法で行つた。
まず、フラスコ１を10-5mmHgに５時間保つて
脱気し、真空ライン７からＡ点で封じ切り、次い
で一つのアニオン重合開始剤溶液の入つたアンプ
ル３のシールを破り、フラスコ１を含む系内を充
分に洗浄し、枝管６に導いてその枝管６をＢ点で
封じ切つた。次に、フラスコ１を−78℃に冷却
し、−78℃に冷却された第２のアニオン重合開始
剤溶液の入つたアンプル２のシールを破り、アニ
オン開始剤をフラスコ１に導き、次いで−78℃に
冷却されたビニルモノマー（）の４，４−置換
オキサゾリニル基置換体をアンプル４から同様に
してフラスコ１に導入して10分間反応させた後、
１−オクタノール標準溶液の入つたアンプル５の
シールを破り、フラスコ１の内容物が呈するリビ
ングアニオン特有のやや黒みがかつた赤色が消色
するまで１−オクタノール標準溶液を少量ずつフ
ラスコ１に導入し、リビングアニオンの定量を行
つた。ポリマーは、後処理をした上で、キヤラク
タリゼーシヨンに供した。
（２−（４−ビニルフエニル）−４，４−ジメチ
ル−２−オキサゾリンの合成及び同定）
４−ビニル安息香酸（４−VB）に対して2.5倍
モルの塩化チオニルを０℃で加え、０〜10℃で５
時間、40℃で１時間反応させた後、生成物を減圧
蒸留して４−ビニルベンゾイルクロライド（４−
VBC）を得た。次に４−VBCに対して２培モル
の２−アミノ−２−メチル−１−プロパノールの
35重量％ジクロルメタン溶液を加え、０℃で２時
間反応させた後、生成した酸アミド化合物を再結
晶により分離し、次いで、該酸アミド化合物の
3.3倍モルの塩化チオニルを０℃で加え、０〜10
℃で１時間反応を行つた。得られた生成物を減圧
蒸留して、次式であらわされる２−（４−ビニル
フエニル）−４，４−ジメチル−２−オキサゾリ
ン（４−VOX）を４−VBに対して28％の収率で
得た。
この４−VOXは、84〜85℃／１mmHgの沸点を
有していた。４−VOXを 1H NMR（60MHz、
CCl4中、TMS基準）により分析し、そのケミカ
ルシフト値（下記）から、４−VOXは上記構造
を有するものであることが確認された。
1.31ppm（Ｓ；6H、−ＣＨ 3）、4.03ppm（Ｓ；
2H、−ＣＨ 2−）、5.30、5.80ppm（2d；2H、Ｊ＝
10、18Hz、ＣＨ 2＝CH）、6.79ppm（2d；1H、
CH2＝ＣＨ）、7.33〜8.00ppm（ｍ；4H、
Aromatic）
（４−VOXのリビングポリマーの合成及び同
定）
得られた４−VOXを第１表に示す各種のアニ
オン重合開始剤を用いて、テトラヒドロフラン
（以下、THFと略す。）中、−78℃、10分間の条件
で重合した。いずれの場合も、重合系はリビング
アニオン特有のやや黒みがかつた赤色を呈した。
リビングアニオンを定量するために、１−オクタ
ノール標準溶液を用いて高真空下で上記黒赤色が
消失するまで滴定を行つた結果、アニオン重合開
始剤のリビングアニオンと等モルのリビングアニ
オンが存在しており、リビングポリマーが生成し
ていることが確認された。
このリビングポリマーをメタノールで処理する
ことにより、ポリ〔２−（４−ビニルフエニル）−
４，４−ジメチル−２−オキサゾリン〕
（PVOX）が定量的に得られた。PVOXを 1H
NMR分析し、各シグナルのプロトン比から
PVOXは下記構造を有することが確認された。
また、PVOXのIRスペクトルは1650cm-1（−Ｃ＝
Ｎ−）、1610及び1510cm-1（ベンゼン環骨格）の特
性吸収を示し、下記構造を支持していた。
VPO（Vapor Pressure Osmometer）を用い
てPVOXの数平均分子量を測定し、４−VOX／
アニオン重合開始剤のモル比より計算した数平均
分子量と比較した結果を第１表に示す。両者はか
なり良く一致していることがわかる。
PVOXについて、THFを溶媒としてGPC（Gel
Permeation Chromatography）測定を行い、極
めて狭い分子量分布を持つポリマーであることが
確認された。
PVOXはTHF、ベンゼン、クロロホルム、ア
セトン、ジエチルエーテル、ジオキサン、Ｎ，Ｎ
−ジメチルホルムアミドに可溶、ヘキサン、エタ
ノール、メタノール、水に不溶であつた。
これらの分析結果から、４−VOXのアニオン
重合により得られたポリマーは、４−VOXの繰
り返し単位を持つリビングポリマーであることが
証明された。
（ポリ（４−ビニル安息香酸）の合成及び同
定）
PVOXを17容量％のTHFを含む３規定塩酸に
溶解して３％溶液とし、10時間還流した後中和し
た。次に溶媒を減圧下で留去し、その乾固物を20
重量％の水酸化ナトリウムを含むメタノール−水
（１：１）混液に溶解して３％溶液とし、６時間
還流することにより保護基の４，４−置換オキサ
ゾリニル基は脱離し、ポリ（４−ビニル安息香
酸）（PVB）が得られた。PVBの 1H NMR分析
から、オキサゾリン環に置換したメチル基の特性
シグナルは認められなかつた。また、PVBのIR
スペクトルは2500−3300cm-1（−OH）、1700cm-1
（Ｃ＝Ｏ）、の特性吸収を示し、オキサゾリン環
に基づく吸収は認められなかつた。従つて、
PVBは
の構造式を持つことが確認された。
PVBはTHF、メタノール、エタノール、Ｎ，
Ｎ−ジメチルホルムアミド、ジメチルスルホキシ
ドに可溶、ヘキサン、ベンゼン、アセトン、ジオ
キサン、水に不溶であつた。
又、得られたPVBをベンゼン溶液中でジアゾ
メタンによりメチル化し、メチル化PVBを得、
これを用いてTHFを溶媒としてGPC測定を行い、
極めて狭い分子量分布を持つポリマーであること
を確認した。
【表】DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a living polymer of an aromatic vinyl compound and a method for producing the same. [Prior Art] Anion living polymers of vinyl monomers having reactive groups in their molecules cannot be directly obtained because of the active hydrogen and carbonyl carbon in the reactive groups. The present inventors first protected the reactive group of an aromatic vinyl monomer having a reactive group such as a hydroxyl group, an amino group, or a formyl group with a substituent group, and then allowed an anionic polymerization initiator to act thereon. found that anionic living polymers of aromatic vinyl monomers having protected reactive groups could be obtained by [JP-A-59-53509; Proceedings of Polymers,
Volume 34, No. 2, Page 195 (1985)]. [Problems to be Solved by the Invention] The object of the present invention is to synthesize an anionic living polymer of an aromatic vinyl monomer having a carboxyl group with the carboxyl group protected. [Means for Solving the Problems] As a result of extensive research, the present inventors have discovered that the carboxyl group of the aromatic vinyl monomer can be protected by converting it into a substituent consisting of a 4,4-substituted oxazoline skeleton. The present invention was completed by discovering that a living polymer having repeating units of an aromatic vinyl monomer having a 4,4-substituted oxazolinyl group was produced by the above method. That is, the present invention has the general formula [In the formula, R 1 and R 2 are the same or different alkyl groups, R 3
represents a hydrogen atom or a methyl group, and n represents an integer of 2 or more. ] A new living polymer () having a repeating unit of the general formula [In the formula, R 3 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom or an alkali metal atom. ] After reacting the vinyl monomer ( ) with a chlorinating agent to form an acid chloride, the formula [In the formula, R 1 and R 2 represent the same or different alkyl groups. ] The 4,4-substituted oxazolinyl group substituted product of the vinyl monomer () obtained by condensing and ring-closing the acid amide compound produced by reacting the amino alcohol compound represented by the above in the presence of the chlorinating agent is converted into an anion. The gist of the present invention is a method for producing the above polymer (2), which comprises polymerizing in the presence of a polymerization initiator. Specific examples of the above vinyl monomer () include:
4-vinylbenzoic acid, 4-vinylbenzoic acid lithium salt, 4-vinylbenzoic acid sodium salt, 4-vinylbenzoic acid potassium salt, 4-vinylbenzoic acid cesium salt, 4-carboxy-α-methylstyrene, 4-carboxy -α-methylstyrene lithium salt, 4-carboxy-α-methylstyrene sodium salt, 4-carboxy-α-methylstyrene potassium salt, 4-carboxy-α-methylstyrene cesium salt, and the like. The chlorinating agent used to obtain the acid chloride of the vinyl monomer () from the vinyl monomer () includes thionyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphoryl chloride, etc., but thionyl chloride is preferable. be. The reaction between vinyl monomer () and chlorinating agent is 0~
It is carried out for 1 to 10 hours at 40°C. Contact between the two is usually carried out without a solvent, but if necessary, it may be carried out in the presence of a solvent such as benzene, methylene chloride, chloroform, carbon tetrachloride, etc., or in an inert gas atmosphere such as nitrogen gas. It's good to wear. The contact ratio between the two is usually at least 1 mole of the chlorinating agent, preferably 2 to 3 times the mole of the vinyl monomer (). R 1 and R 2 in the formula of the amino alcohol compound are methyl, ethyl, n-propyl, iso-
It is a lower alkyl group such as propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, n-hexyl, etc., and R 1 and R 2 may be the same or different.
The reaction between the acid chloride of the vinyl monomer () and the aminoalcohol compound is carried out at 0 to 10°C for 1 to 10 hours in the presence of a solvent such as ether, methylene chloride, or chloroform, preferably methylene chloride.
The amino alcohol compound is used in an amount of 1 mole or more, preferably 2 to 3 moles, relative to the acid chloride of the vinyl monomer (). The chlorinating agents used to form an oxazoline ring by condensation and ring closure after reacting the acid chloride of the vinyl monomer () with the amino alcohol compound are thionyl chloride, phosphorus pentachloride, phosphorus trichloride, chloride Examples include phosphoryl, and thionyl chloride is preferred. The chlorinating agent is added at least 1 mole, preferably 3 to 5 times the mole of the acid chloride of the vinyl monomer (), and the reaction is carried out at a concentration of 0 to 10 moles.
The reaction is carried out at a temperature of 1 to 10 hours, and may be carried out in the presence of a solvent such as methylene chloride or chloroform, if necessary. By doing so, the vinyl monomer ()
The carboxyl group of is substituted with a 4,4-substituted oxazolinyl group to become a substituted product of the vinyl monomer (), and the substituted product is anionically polymerized using an anionic polymerization initiator to form a living polymer of the substituted product. () is obtained. Suitable anionic polymerization initiators used in the present invention include n-butyllithium, naphthalene lithium salt, naphthalene sodium salt, naphthalene potassium salt, (α-methylstyrene oligomer) lithium salt, (α-methylstyrene oligomer) sodium salt, (α-methylstyrene oligomer) potassium salt, cumyl potassium salt, etc. can be mentioned. Anionic polymerization is carried out at -100°C to room temperature,
Desirably at a low temperature of -30°C or lower, particularly preferably -
It is carried out at a low temperature of 50 to -100°C for 0.1 to 24 hours. The polymerization reaction may be carried out without a solvent, but is preferably carried out in the presence of a solvent. Suitable solvents include tetrahydrofuran, hexane, toluene, cyclohexane, pentane, benzene and the like, and two or more of these may be used in combination. Furthermore, the polymerization system needs to be maintained in an inert gas atmosphere free of moisture and oxygen that would interfere with the polymerization reaction, or under reduced pressure, particularly preferably under high vacuum. The molecular weight of the living polymer () can be controlled by changing the ratio of the substituent/anionic polymerization initiator, and the molecular weight can be increased by increasing the ratio. The living polymer () thus obtained is
Usually about 500 to about 500,000, preferably about 2000 to about
It has a number average molecular weight of 200,000, particularly preferably from about 5,000 to about 100,000, and has an extremely narrow molecular weight distribution with a weight average molecular weight/number average molecular weight ratio close to 1. [Effects of the Invention] The living polymer () of the present invention is treated with methanol etc., then brought into contact with a mineral acid such as hydrochloric acid or sulfuric acid, and then quenched in the presence of a base such as sodium hydroxide or potassium hydroxide. By becoming
The 4,4-substituted oxazolinyl group, which is a protective group, is removed, and a polymer of vinyl monomer () can be produced. According to this method, it is easier to control the molecular weight than the known method of producing a polymer of vinyl monomer (2) using a radical polymerization method of vinyl monomer (2), and it is easy to produce a polymer having an arbitrary molecular weight and an extremely narrow molecular weight distribution. It has the characteristic that it can be manufactured in The thus obtained deprotected polymer is
As a unique resin that has the properties of both a thermoplastic resin and a functional resin, it can be used for various industrial purposes, and the synthesis of new functional resins in which its reactive substituents are replaced with other reactive groups. It is also useful as a raw material. EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto. [Example] (Polymerization apparatus used for anionic polymerization) The anionic polymerization initiator solution, monomer solution, and 1-octanol standard solution used for anionic polymerization were frozen, degassed in a high vacuum line, and sealed in an ampoule with a break seal. . In anionic polymerization, a flask connected to a high vacuum line is filled with the above ampoules containing multiple anionic polymerization initiator solutions, a monomer solution, and a 1-octanol standard solution, and a branch pipe that takes out the waste anionic initiator solution after cleaning the system. The experiment was carried out using the equipment shown in the drawing, which is connected to the following method. First, flask 1 is kept at 10 -5 mmHg for 5 hours to degas it, and the vacuum line 7 is sealed off at point A. Then, the seal of ampoule 3 containing one anionic polymerization initiator solution is broken, and flask 1 is contained. The inside of the system was thoroughly washed and led to a branch pipe 6, which was sealed off at point B. Next, flask 1 was cooled to -78°C, the seal of ampoule 2 containing the second anionic polymerization initiator solution cooled to -78°C was broken, the anionic initiator was introduced into flask 1, and then -78°C The 4,4-substituted oxazolinyl group-substituted vinyl monomer () cooled to ℃ was similarly introduced into flask 1 from ampoule 4 and reacted for 10 minutes.
Break the seal of ampoule 5 containing the 1-octanol standard solution and introduce the 1-octanol standard solution into flask 1 little by little until the slightly dark red characteristic of living anions exhibited by the contents of flask 1 disappears. , the living anions were quantified. The polymer was post-treated and then subjected to characterization. (Synthesis and identification of 2-(4-vinylphenyl)-4,4-dimethyl-2-oxazoline) Add 2.5 times the mole of thionyl chloride to 4-vinylbenzoic acid (4-VB) at 0°C. 5 at 10℃
After reacting for 1 hour at 40°C, the product was distilled under reduced pressure to produce 4-vinylbenzoyl chloride (4-vinylbenzoyl chloride).
VBC) was obtained. Next, 2 moles of 2-amino-2-methyl-1-propanol was added to 4-VBC.
After adding a 35% by weight dichloromethane solution and reacting at 0°C for 2 hours, the generated acid amide compound was separated by recrystallization.
Add 3.3 times the mole of thionyl chloride at 0℃,
The reaction was carried out at ℃ for 1 hour. The obtained product was distilled under reduced pressure to obtain 2-(4-vinylphenyl)-4,4-dimethyl-2-oxazoline (4-VOX) represented by the following formula at a yield of 28% based on 4-VB. I got it from This 4-VOX had a boiling point of 84-85°C/1 mmHg. 4-VOX by 1H NMR (60MHz,
It was confirmed from the chemical shift value (see below) that 4-VOX has the above structure. 1.31ppm (S; 6H, -CH3 ) , 4.03ppm (S;
2H, -CH2- ), 5.30, 5.80ppm ( 2d ; 2H, J=
10, 18Hz, CH2 =CH) , 6.79ppm (2d; 1H,
CH2 = CH ), 7.33-8.00ppm (m; 4H,
(Synthesis and identification of living polymer of 4-VOX) The obtained 4-VOX was incubated at -78°C in tetrahydrofuran (hereinafter abbreviated as THF) using various anionic polymerization initiators shown in Table 1. , polymerization was carried out for 10 minutes. In both cases, the polymerized system exhibited a slightly dark red color characteristic of living anions.
In order to quantify the living anion, titration was performed under high vacuum using a 1-octanol standard solution until the black-red color disappeared. As a result, it was found that there was an equimolar amount of the living anion with the living anion of the anionic polymerization initiator. It was confirmed that a living polymer was produced. By treating this living polymer with methanol, poly[2-(4-vinylphenyl)-
4,4-dimethyl-2-oxazoline]
(PVOX) was obtained quantitatively. PVOX 1H
NMR analysis and from the proton ratio of each signal
It was confirmed that PVOX has the following structure.
Also, the IR spectrum of PVOX is 1650cm -1 (-C=
N-), 1610 and 1510 cm -1 (benzene ring skeleton), and supported the following structure. The number average molecular weight of PVOX was measured using a VPO (Vapor Pressure Osmometer), and 4-VOX/
Table 1 shows the results of comparison with the number average molecular weight calculated from the molar ratio of the anionic polymerization initiator. It can be seen that the two agree quite well. Regarding PVOX, GPC (Gel
Permeation Chromatography) measurements were conducted and it was confirmed that the polymer had an extremely narrow molecular weight distribution. PVOX is THF, benzene, chloroform, acetone, diethyl ether, dioxane, N,N
-Soluble in dimethylformamide, insoluble in hexane, ethanol, methanol, and water. These analysis results proved that the polymer obtained by anionic polymerization of 4-VOX is a living polymer having repeating units of 4-VOX. (Synthesis and identification of poly(4-vinylbenzoic acid)) PVOX was dissolved in 3N hydrochloric acid containing 17% by volume of THF to make a 3% solution, which was refluxed for 10 hours and then neutralized. Next, the solvent was distilled off under reduced pressure, and the dried product was
The 4,4-substituted oxazolinyl group of the protecting group is removed by dissolving the solution in a methanol-water (1:1) mixture containing % by weight of sodium hydroxide to make a 3% solution and refluxing for 6 hours. Vinyl benzoic acid) (PVB) was obtained. From 1 H NMR analysis of PVB, no characteristic signal of the methyl group substituted on the oxazoline ring was observed. Also, PVB IR
The spectrum is 2500−3300cm -1 (-OH), 1700cm -1
(C=O), and no absorption based on the oxazoline ring was observed. Therefore,
PVB is It was confirmed that it has the structural formula. PVB is THF, methanol, ethanol, N,
It was soluble in N-dimethylformamide and dimethyl sulfoxide, and insoluble in hexane, benzene, acetone, dioxane, and water. In addition, the obtained PVB was methylated with diazomethane in a benzene solution to obtain methylated PVB,
Using this, we performed GPC measurements using THF as a solvent.
It was confirmed that this polymer has an extremely narrow molecular weight distribution. 【table】
第１図は本発明におけるアニオン重合を行う装
置の概略を示す。
１……フラスコ、２，３……アニオン重合開始
剤封入アンプル、４……モノマー封入アンプル、
５……１−オクタノール標準溶液封入アンプル、
６……枝管、７……真空ライン、８……コツク、
９……マグネツト。
FIG. 1 schematically shows an apparatus for carrying out anionic polymerization in the present invention. 1... Flask, 2, 3... Ampoule filled with anionic polymerization initiator, 4... Ampoule filled with monomer,
5...Ampoule containing 1-octanol standard solution,
6...Branch pipe, 7...Vacuum line, 8...Kotuku,
9...Magnet.
Claims (1)
は水素原子又はメチル基、ｎは２以上の整数を示
す。〕の繰り返し単位を持つ新規リビングポリマ
ー。 ２ 一般式 〔式中、R3は水素原子又はメチル基、Ｍは水素
原子又はアルカリ金属原子を示す。〕で表わされ
るビニルモノマーに塩素化剤を反応させ酸塩化物
とした後、式 〔式中、R1、R2は同じか異なるアルキル基を示
す。〕 で表わされるアミノアルコール系化合物を反応さ
せて生成する酸アミド化合物を、 上記塩素化剤の存在下で縮合、閉環して得られ
る該ビニルモノマーの４，４−置換オキサゾリニ
ル基置換体をアニオン重合開始剤の存在下で重合
することからなる、 一般式 〔式中、R1、R2は同一か異なるアルキル基、R3
は水素原子又はメチル基、ｎは２以上の整数を示
す。〕の繰り返し単位を持つ新規リビングポリマ
ーの製造方法。[Claims] 1. General formula [In the formula, R 1 and R 2 are the same or different alkyl groups, R 3
represents a hydrogen atom or a methyl group, and n represents an integer of 2 or more. ] A novel living polymer with repeating units. 2 General formula [In the formula, R 3 represents a hydrogen atom or a methyl group, and M represents a hydrogen atom or an alkali metal atom. ] After reacting the vinyl monomer represented by the formula with a chlorinating agent to form an acid chloride, the formula [In the formula, R 1 and R 2 represent the same or different alkyl groups. ] Anionic polymerization of the 4,4-substituted oxazolinyl group substituted product of the vinyl monomer obtained by condensing and ring-closing an acid amide compound produced by reacting the amino alcohol compound represented by the above in the presence of the chlorinating agent. The general formula consists of polymerization in the presence of an initiator. [In the formula, R 1 and R 2 are the same or different alkyl groups, R 3
represents a hydrogen atom or a methyl group, and n represents an integer of 2 or more. ] A method for producing a new living polymer having repeating units.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4535086A JPH0233046B2 (en) | 1986-03-04 | 1986-03-04 | SHINKIRIBINGUHORIMAAOYOBISONOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4535086A JPH0233046B2 (en) | 1986-03-04 | 1986-03-04 | SHINKIRIBINGUHORIMAAOYOBISONOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62205106A JPS62205106A (en) | 1987-09-09 |
| JPH0233046B2 true JPH0233046B2 (en) | 1990-07-25 |
Family
ID=12716828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4535086A Expired - Lifetime JPH0233046B2 (en) | 1986-03-04 | 1986-03-04 | SHINKIRIBINGUHORIMAAOYOBISONOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0233046B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432568B (en) * | 2016-09-29 | 2018-10-30 | 福州大学 | The preparation method of Yi Zhong Duo oxazolinyl chain extenders |
-
1986
- 1986-03-04 JP JP4535086A patent/JPH0233046B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62205106A (en) | 1987-09-09 |
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