JPH0128053B2 - - Google Patents
Info
- Publication number
- JPH0128053B2 JPH0128053B2 JP56003739A JP373981A JPH0128053B2 JP H0128053 B2 JPH0128053 B2 JP H0128053B2 JP 56003739 A JP56003739 A JP 56003739A JP 373981 A JP373981 A JP 373981A JP H0128053 B2 JPH0128053 B2 JP H0128053B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- polymer according
- producing
- polymer
- methyl
- 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
Links
- 229920000642 polymer Polymers 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 6
- 125000004076 pyridyl group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 125000002883 imidazolyl group Chemical group 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- -1 acyl peroxides Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SDYRIBONPHEWCT-UHFFFAOYSA-N n,n-dimethyl-2-phenylethenamine Chemical compound CN(C)C=CC1=CC=CC=C1 SDYRIBONPHEWCT-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、塩基性を有する新規な重合体および
その製造法に関する。
塩基性を有する重合体は、その塩基性を利用し
て種々の用途に利用されている。例えば、塩基性
を有する三次元架橋ポリマーはカチオン交換樹脂
として広く利用されており、ジメチルアミノスチ
レン、アミノスチレン、ビニルピリジン等の三次
元重合体はその代表例といえよう。また塩基性を
有する線状高分子も抽剤などとして広く利用され
ている。
本発明者らは、塩基性を有する高分子化合物に
ついて種々の検討を加えた結果、下記に示す新規
な塩基性重合体を見い出すに至つた。
本発明に係る新規な重合体は、下記の構造式
（）で示される線状重合体である。
（式中、ＡおよびＢは水素、炭素数１から17のア
ルキル基、アリール基、アラルキル基、ピリジル
基またはニトロ基、ｎは２以上の整数を表わす。）
本発明の重合体は、下記の構造式（）で示さ
れる単量体を重合させることによつて製造するこ
とができる。
（式中、ＡおよびＢは水素、炭素数１から17のア
ルキル基、アリール基、アラルキル基、ピリジル
基またはニトロ基を表わす。）
ベンゼン核に関する二つの置換基の位置はオル
ト、メタ、パラのいずれの位置でもよいが、メタ
またはパラあるいはこれらの両者の位置が好まし
い。
構造式（）で示される単量体は、例えば、ハ
ロゲノメチルスチレンとイミダゾールまたはその
誘導体から得ることができる。
（式中、ＡおよびＢは前述と同じ。）
具体的な例としては、
１−（メタ−スチリル）メチル−２−エチル−
４(5)−メチルイミダゾール、１−（パラ−スチリ
ル）メチル−２−エチル−４(5)−メチルイミダゾ
ール、１−（メタ−スチリル）メチル−２−ベン
ジル−４(5)−メチルイミダゾール、１−（パラ−
スチリル）メチル−２−ベンジル−４(5)−メチル
イミダゾール、１−（メタ−スチリル）メチル−
２−ピリジル−４(5)−メチルイミダゾール、１−
（パラ−スチリル）メチル−２−ピリジル−４(5)
−メチルイミダゾール、１−（メタ−スチリル）
メチルイミダゾール、１−（パラ−スチリル）メ
チルイミダゾール、１−（メタ−スチリル）メチ
ル−２−メチルイミダゾール、１−（パラ−スチ
リル）メチル−２−メチルイミダゾール、１−
（パラ−スチリル）メチル−２−ウンデシルイミ
ダゾール、１−（メタ−スチリル）メチル−２−
ヘプタデシルイミダゾール、１−（パラ−スチリ
ル）メチル−２−フエニルイミダゾール、１−
（パラ−スチリル）メチル−５−ニトロイミダゾ
ールなどがある。
本発明における重合体を構造式（）の単量体
を用いて製造する場合の重合方法は特に制限はな
く、加熱による重合でも充分可能であるが、重合
開始剤を利用することが好ましい場合が多い。重
合開始剤として用いられるのは、過酸化ベンゾイ
ル、過酸化ラウロイル等の過酸化アシル類、アゾ
ビスイソブチロニトリル、２，2′−アゾビス
（２，４−ジメチルマレロニトリル）等のアゾニ
トリル類、過酸化ジターシヤリーブチル、過酸化
ジクミル、メチルエチルケトンパーオキシド等の
過酸化物、クメンヒドロペルオキシド、ターシヤ
リーヒドロペルオキシド等のヒドロペルオキシド
類である。
本発明における重合体は、不活性液体の存在下
で重合を行つて製造することも可能である。不活
性液体としては、ノルマル−ペンタン、ノルマル
−ヘキサン、ノルマル−ヘプタン、ノルマル−オ
クタンを始めとする脂肪族炭化水素類、メタノー
ル、エタノール、イソプロピルアルコールなどの
アルコール類、アセトン、メチルエチルケトン、
ジエチルケトンなどのケトン類、ジエチルエーテ
ル、メチルエチルエーテル、ジブチルエーテル、
ジオキサン、テトラヒドロフラン等のエーテル
類、ベンゼン、トルエン、キシレン等の芳香族炭
化水素類、ギ酸エチル、酢酸エチル、酢酸ブチル
等のエステル類、ジメチルホルムアミド、ジメチ
ルアセトアミドを始めとするアミド類、クロロホ
ルム、塩化メチレン、ジクロルエタン等の脂肪族
ハロゲン化物、クロルベンゼンを始めとする芳香
族ハロゲン化物、およびジメチルスルホキシド等
の極性液体も用いることができる。これらの液体
は単独ないしは二つ以上の液体の混合物として用
いることもできる。
反応の温度に制限はないが、20℃から120℃程
度が好ましく、さらに好ましくは60℃から100℃
程度である。
本発明における重合体は、金属の抽剤として用
いたり、塗料材料などとして用いられることがわ
かつた。また意外なことに、この陰イオン性重合
体は、他の既知の陰イオン性重合体に比べ、アル
キルスルホン酸等の有機アニオンに対し適当な親
和性を有した。
以下に本発明の実施例を示すが、これらは本発
明を制限するものではない。
実施例 １
50mlのアンプル管に10ｇのイミダゾメチルスチ
レン（ｍ体60％、ｐ体40％の混合物）を20mlのメ
タノールに溶解されて入れた。これに0.1ｇのア
ゾビスイソブチロニトリル（AIBN）を加え、よ
く撹拌した後、アンプル管内を窒素パージして封
管した。これを80℃の水バスに約20時間浸漬し
た。封管を割り、内容物をヘキサンにあけて沈澱
を過した後、物をヘキサンで洗浄し、これを
乾燥して10.0ｇの白色生成物を得た。得られた生
成物の元素分析は以下のとおりである。
Ｃ：77.72（78.23）、Ｈ：6.68（6.57）、Ｎ：15.60
（15.20）
括弧内の数値は理論値を表わす。
また赤外吸収スペクトルにおける主たる吸収は
次のとおりであり、1630cm-1附近のＣ＝Ｃ二重結
合にもとづく吸収が消失し、重合体になつている
ことが確認できた。712、815、905、1030、1078、
1106、1275、1438、1501、1601、2950他（単位cm
-1）
得られたポリマーの25℃、2N塩酸中の極限粘
度〔η〕は0.60であつた。
このようにして得られたポリマー１ｇと塩化第
２鉄（分子式FeCl3・6H2O）0.676ｇ（2.5ミリモ
ル）を2Nの塩酸に溶解させて全容を50c.c.とした。
この溶液を50mlのクロロホルムで５回抽出操作を
行つた後、水相の鉄の濃度を測定したところ、２
ミリモル／であつた。一方、このポリマーを含
まない塩化第２鉄の同一の濃度の塩酸溶液につい
て、クロロホルム抽出を行つたところ、鉄の濃度
は50ミリモル／で、その濃度は抽出の前後でま
つたく変化しなかつた。これらのことから、この
ポリマーは金属の抽剤として使用することができ
ることがわかつた。
実施例 ２〜10
実施例１とほゞ同様の手法で構造式（）で表
わされる各種の線状重合体を合成した。その結果
を表１に一括して載せる。
The present invention relates to a novel basic polymer and a method for producing the same. Polymers having basicity are used for various purposes by taking advantage of their basicity. For example, three-dimensional crosslinked polymers having basicity are widely used as cation exchange resins, and three-dimensional polymers such as dimethylaminostyrene, aminostyrene, and vinylpyridine are representative examples. Furthermore, linear polymers having basicity are also widely used as extraction agents. The present inventors conducted various studies on basic polymer compounds, and as a result, discovered the novel basic polymer shown below. The novel polymer according to the present invention is a linear polymer represented by the following structural formula (). (In the formula, A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group, and n represents an integer of 2 or more.) It can be produced by polymerizing a monomer represented by the structural formula (). (In the formula, A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group.) The positions of the two substituents on the benzene nucleus are ortho, meta, and para. Although it may be in any position, meta or para or both positions are preferred. The monomer represented by the structural formula () can be obtained from, for example, halogenomethylstyrene and imidazole or a derivative thereof. (In the formula, A and B are the same as above.) Specific examples include 1-(meth-styryl)methyl-2-ethyl-
4(5)-methylimidazole, 1-(para-styryl)methyl-2-ethyl-4(5)-methylimidazole, 1-(meth-styryl)methyl-2-benzyl-4(5)-methylimidazole, 1-(para-
styryl)methyl-2-benzyl-4(5)-methylimidazole, 1-(meth-styryl)methyl-
2-pyridyl-4(5)-methylimidazole, 1-
(para-styryl)methyl-2-pyridyl-4(5)
-methylimidazole, 1-(meth-styryl)
Methylimidazole, 1-(para-styryl)methylimidazole, 1-(meth-styryl)methyl-2-methylimidazole, 1-(para-styryl)methyl-2-methylimidazole, 1-
(para-styryl)methyl-2-undecylimidazole, 1-(meth-styryl)methyl-2-
Heptadecylimidazole, 1-(para-styryl)methyl-2-phenylimidazole, 1-
(para-styryl)methyl-5-nitroimidazole and the like. When producing the polymer of the present invention using a monomer of structural formula (), there is no particular restriction on the polymerization method, and polymerization by heating is sufficient, but it may be preferable to use a polymerization initiator. many. The polymerization initiators used include acyl peroxides such as benzoyl peroxide and lauroyl peroxide, azonitrile such as azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylmaleronitrile), These include peroxides such as ditertiary butyl peroxide, dicumyl peroxide, and methyl ethyl ketone peroxide, and hydroperoxides such as cumene hydroperoxide and tertiary hydroperoxide. The polymer in the present invention can also be produced by polymerizing in the presence of an inert liquid. Inert liquids include aliphatic hydrocarbons such as normal pentane, normal hexane, normal heptane, and normal octane, alcohols such as methanol, ethanol, and isopropyl alcohol, acetone, methyl ethyl ketone,
Ketones such as diethyl ketone, diethyl ether, methyl ethyl ether, dibutyl ether,
Ethers such as dioxane and tetrahydrofuran, aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl formate, ethyl acetate and butyl acetate, amides such as dimethylformamide and dimethylacetamide, chloroform and methylene chloride. , aliphatic halides such as dichloroethane, aromatic halides such as chlorobenzene, and polar liquids such as dimethyl sulfoxide can also be used. These liquids can be used alone or as a mixture of two or more liquids. There is no limit to the reaction temperature, but it is preferably about 20°C to 120°C, more preferably 60°C to 100°C.
That's about it. It has been found that the polymer of the present invention can be used as a metal extraction agent, a paint material, and the like. Also surprisingly, this anionic polymer had a suitable affinity for organic anions such as alkyl sulfonic acids compared to other known anionic polymers. Examples of the present invention are shown below, but these are not intended to limit the present invention. Example 1 10 g of imidazomethylstyrene (a mixture of 60% m-isomer and 40% p-isomer) was dissolved in 20 ml of methanol and placed in a 50 ml ampoule tube. After adding 0.1 g of azobisisobutyronitrile (AIBN) and stirring well, the inside of the ampoule tube was purged with nitrogen and the tube was sealed. This was immersed in a water bath at 80°C for about 20 hours. The sealed tube was broken, and the contents were poured into hexane to filter out the precipitate. The material was then washed with hexane and dried to obtain 10.0 g of a white product. The elemental analysis of the obtained product is as follows. C: 77.72 (78.23), H: 6.68 (6.57), N: 15.60
(15.20) The numbers in parentheses represent theoretical values. The main absorption in the infrared absorption spectrum was as follows, and it was confirmed that the absorption based on the C═C double bond around 1630 cm −1 disappeared, indicating that the product had become a polymer. 712, 815, 905, 1030, 1078,
1106, 1275, 1438, 1501, 1601, 2950, etc. (unit: cm)
-1 ) The intrinsic viscosity [η] of the obtained polymer in 2N hydrochloric acid at 25°C was 0.60. 1 g of the polymer thus obtained and 0.676 g (2.5 mmol) of ferric chloride (molecular formula: FeCl 3 .6H 2 O) were dissolved in 2N hydrochloric acid to give a total volume of 50 c.c.
After extracting this solution five times with 50 ml of chloroform, the iron concentration in the aqueous phase was measured.
It was millimoles/mm. On the other hand, when chloroform extraction was performed on a hydrochloric acid solution of the same concentration of ferric chloride that did not contain this polymer, the iron concentration was 50 mmol/min, and the concentration did not change at all before and after the extraction. These results indicate that this polymer can be used as an extractant for metals. Examples 2 to 10 Various linear polymers represented by the structural formula () were synthesized in substantially the same manner as in Example 1. The results are summarized in Table 1.
【表】【table】
【表】
Ｂ；ヘキサンから再沈して回収
※4) (Ｈ)2N塩酸中
(Ｄ)DMSO中
[Table] B: Recovered by reprecipitation from hexane *4) (H) In 2N hydrochloric acid
(D) In DMSO
Claims (1)
ルキル基、アリール基、アラルキル基、ピリジル
基またはニトロ基、ｎは２以上の整数を表わす。） ２ ベンゼン核に関する二つの置換基の位置がメ
タまたはパラまたはそれらの混合物である特許請
求の範囲第１項記載の重合体。 ３ ＡおよびＢが水素、メチル基、エチル基、フ
エニル基、ベンジル基、ニトロ基またはピリジル
基である特許請求の範囲第１項または第２項記載
の重合体。 ４ ＡおよびＢのいずれかが、イミダゾール環の
２の位置である特許請求の範囲第１項ないし第３
項記載の重合体。 ５ 下記の構造式（）で示される化合物を重合
させることを特徴とする新規な塩基性重合体の製
造法。 （式中、ＡおよびＢは水素、炭素数１から17のア
ルキル基、アリール基、アラルキル基、ピリジル
基またはニトロ基を表わす。） ６ ベンゼン核に関する二つの置換基の位置がメ
タまたはパラまたはそれらの混合物である特許請
求の範囲第５項記載の重合体の製造法。 ７ ＡおよびＢが水素、メチル基、エチル基、フ
エニル基、ベンジル基、ニトロ基またはピリジル
基である特許請求の範囲第５項または第６項記載
の重合体の製造法。 ８ ＡおよびＢのいずれかがイミダゾール環の２
の位置である特許請求の範囲第５項ないし第７項
記載の重合体の製造法。 ９ 重合開始剤を添加させて重合を行なう特許請
求の範囲第５項ないし第８項記載の重合体の製造
法。 １０ 不活性液体の存在下に重合を行なう特許請
求の範囲第５項ないし第８項記載の重合体の製造
法。[Claims] 1. A linear polymer represented by the following structural formula (). (In the formula, A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group, and n represents an integer of 2 or more.) 2. Two substituents related to the benzene nucleus A polymer according to claim 1, wherein the position is meta or para or a mixture thereof. 3. The polymer according to claim 1 or 2, wherein A and B are hydrogen, methyl group, ethyl group, phenyl group, benzyl group, nitro group, or pyridyl group. 4 Claims 1 to 3, in which either A or B is at the 2 position of the imidazole ring
Polymers described in Section. 5. A method for producing a novel basic polymer, which comprises polymerizing a compound represented by the following structural formula (). (In the formula, A and B represent hydrogen, an alkyl group having 1 to 17 carbon atoms, an aryl group, an aralkyl group, a pyridyl group, or a nitro group.) 6 The positions of the two substituents on the benzene nucleus are meta, para, or A method for producing the polymer according to claim 5, which is a mixture of. 7. The method for producing a polymer according to claim 5 or 6, wherein A and B are hydrogen, methyl group, ethyl group, phenyl group, benzyl group, nitro group, or pyridyl group. 8 Either A or B is an imidazole ring 2
A method for producing a polymer according to any one of claims 5 to 7, wherein the method is as follows. 9. A method for producing a polymer according to claims 5 to 8, wherein polymerization is carried out by adding a polymerization initiator. 10. A method for producing a polymer according to claims 5 to 8, wherein the polymerization is carried out in the presence of an inert liquid.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56003739A JPS57117509A (en) | 1981-01-16 | 1981-01-16 | Novel basic polymer and its preparation |
| US06/335,943 US4430445A (en) | 1979-07-19 | 1981-12-30 | Novel basic imidazolylmethylstyrene compound, its polymer, a process for the preparation thereof and a use as ion exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56003739A JPS57117509A (en) | 1981-01-16 | 1981-01-16 | Novel basic polymer and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57117509A JPS57117509A (en) | 1982-07-22 |
| JPH0128053B2 true JPH0128053B2 (en) | 1989-05-31 |
Family
ID=11565583
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56003739A Granted JPS57117509A (en) | 1979-07-19 | 1981-01-16 | Novel basic polymer and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57117509A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005230692A (en) * | 2004-02-19 | 2005-09-02 | Kurita Water Ind Ltd | Poly ion complex membrane and water treatment device |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180822A (en) * | 1988-09-21 | 1993-01-19 | Reilly Industries, Inc. | Highly selective chelating resins and monomers for their preparation |
-
1981
- 1981-01-16 JP JP56003739A patent/JPS57117509A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005230692A (en) * | 2004-02-19 | 2005-09-02 | Kurita Water Ind Ltd | Poly ion complex membrane and water treatment device |
| JP4547932B2 (en) * | 2004-02-19 | 2010-09-22 | 栗田工業株式会社 | Polyion complex membrane and water treatment device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57117509A (en) | 1982-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5773538A (en) | Process for polymerization of olefinic monomers | |
| JPH11513429A (en) | Control of polymer molecular weight and end group functionality | |
| Carlin et al. | The Polymerization of p-Chlorostyrene in the Presence of Polymethylacrylate | |
| EP0917542A1 (en) | Process for polymerization of olefinic monomers | |
| JPH0128053B2 (en) | ||
| Matsoyan | Cyclic polymerization and copolymerization of divinyl acetals | |
| EP0126231B1 (en) | Vinylphenyl benzimidazole derivatives, their polymers, their preparation and use | |
| US2694693A (en) | Process for preparing polymers of vinyl hydroquinone employing azo-bis-isobutyronitrile as catalyst | |
| JPH059448B2 (en) | ||
| US2844545A (en) | Method for the polymerization of olefin oxides with ferric compounds | |
| Filiz Şenkal et al. | Atom transfer radical polymerization through N‐chlorosulfonamides | |
| JPH0128052B2 (en) | ||
| JPH0513161B2 (en) | ||
| Kinoshita et al. | Vinyl polymerization. 235. Free radicals in the polymerization of vinyl monomers initiated by Gomberg's and its relatad reactions | |
| JPS62292810A (en) | Functional polymer having ethynyl group and its production | |
| JPS648007B2 (en) | ||
| US3686306A (en) | Halogen-substituted derivatives of n-3-oxohydrocarbonsubstituted acrylamides | |
| CA1272205A (en) | Substituted o-phthalaldehydes | |
| US3044997A (en) | Esters of hyponitrous acid and their use as polymerization catalysts | |
| JPH0459328B2 (en) | ||
| JPH0322885B2 (en) | ||
| GB2125416A (en) | Imidazoylmethyl styrene polymers; use thereof as ion exchange resins | |
| JPH0513163B2 (en) | ||
| Nakaya et al. | Vinyl polymerization 270. Polymerization of methyl methacrylate initiated by azibenzil | |
| JPH01313478A (en) | Novel porphyrin compound |