JPH02274712A - Macromonomer, its synthesis and graft copolymer prepared by using same - Google Patents
Macromonomer, its synthesis and graft copolymer prepared by using sameInfo
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- JPH02274712A JPH02274712A JP1096500A JP9650089A JPH02274712A JP H02274712 A JPH02274712 A JP H02274712A JP 1096500 A JP1096500 A JP 1096500A JP 9650089 A JP9650089 A JP 9650089A JP H02274712 A JPH02274712 A JP H02274712A
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- 229920000578 graft copolymer Polymers 0.000 title claims description 15
- 230000015572 biosynthetic process Effects 0.000 title claims 2
- 238000003786 synthesis reaction Methods 0.000 title claims 2
- -1 oxazoline compound Chemical class 0.000 claims abstract description 39
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 125000002091 cationic group Chemical group 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 238000010550 living polymerization reaction Methods 0.000 claims abstract description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 7
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 30
- 125000003118 aryl group Chemical group 0.000 claims 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-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
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920003226 polyurethane urea Polymers 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 150000004895 1,3-oxazines Chemical class 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- KGWNRZLPXLBMPS-UHFFFAOYSA-N 2h-1,3-oxazine Chemical compound C1OC=CC=N1 KGWNRZLPXLBMPS-UHFFFAOYSA-N 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- HONIICLYMWZJFZ-UHFFFAOYSA-N azetidine Chemical compound C1CNC1 HONIICLYMWZJFZ-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- OYQYHJRSHHYEIG-UHFFFAOYSA-N ethyl carbamate;urea Chemical compound NC(N)=O.CCOC(N)=O OYQYHJRSHHYEIG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UVECLJDRPFNRRQ-UHFFFAOYSA-N ethyl trifluoromethanesulfonate Chemical compound CCOS(=O)(=O)C(F)(F)F UVECLJDRPFNRRQ-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000005267 main chain polymer Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000002243 precursor Substances 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
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VOVUARRWDCVURC-UHFFFAOYSA-N thiirane Chemical compound C1CS1 VOVUARRWDCVURC-UHFFFAOYSA-N 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polyethers (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明＋；ｉマクロモノマー及びマクロモノマーの合゛
成方法並びにこのマクロモノマーを用いたグラフト共重
合体ポリマーに関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention +; i relates to a macromonomer, a method for synthesizing the macromonomer, and a graft copolymer using the macromonomer.
〈従来の技術〉
従来より、各種エラストマーにより高次の機能や性能を
付与する乙とが種々検討されている。<Conventional Technology> Various methods of imparting higher-order functions and performance to various elastomers have been studied.
乙の一例を以下に述べる。An example of B is described below.
例えば、チオリンゴ酸やγ−チオグリセリンを連鎖移動
剤に用いてビニルモノマーを重合させ、片末端にカルボ
キシル基あるいは水酸基をそれぞれ２個有するマクロモ
ノマーを合成する乙とが提案されている（Ｐｏｌｙｍｅ
ｒ Ｂｕｌｌｅｔｉｎ５、３６１． （１９８１）、同
８．２３９（１９８１）。For example, it has been proposed to polymerize a vinyl monomer using thiomalic acid or γ-thioglycerin as a chain transfer agent to synthesize a macromonomer having two carboxyl groups or two hydroxyl groups at one end (Polyme
r Bulletin 5, 361. (1981), 8.239 (1981).
乙の手法を用いて、ＭＭＡ （メチルメタクリレート）
の片末端に２個のカルボキシル基を導入したマクロモノ
マーを得た後、芳香族アミンを添加して、縮合反応を行
うことにより、ＰＭＭＡをグラフト鎖として有する芳香
族ポリアミドを得た。Using Otsu's method, MMA (methyl methacrylate)
After obtaining a macromonomer in which two carboxyl groups were introduced at one end, an aromatic amine was added and a condensation reaction was performed to obtain an aromatic polyamide having PMMA as a graft chain.
こうして得られた芳香族ポリアミドは、グラフト鎖中に
ＰＭＭＡを有しているため、機械的強度に優れている。The aromatic polyamide thus obtained has PMMA in the graft chain and therefore has excellent mechanical strength.
〈発明が解決しようとする課題〉
しかしながら、前述した従来のマクロモノマーを得る方
法は、ビニルモノマーしか使えないという問題がある。<Problems to be Solved by the Invention> However, the above-described conventional method for obtaining macromonomers has a problem in that only vinyl monomers can be used.
また重合反応はラジカル重合のため、重合の制御が容易
に出来ず、分子量範囲が広くなる結果、得られたポリマ
ーの物性値の再現性が悪いという問題がある。Further, since the polymerization reaction is a radical polymerization, the polymerization cannot be easily controlled, and as a result, the molecular weight range becomes wide, resulting in a problem that the reproducibility of the physical property values of the obtained polymer is poor.
本発明は、以上述べた事情に鑑み、分子量の制御が容易
な新規マクロモノマー及びこのマクロモノマーの合成方
法、並びに乙のマクロモノマーを用いた新規グラフト共
重合体ポリマーを提供することを目的とする。In view of the above-mentioned circumstances, the present invention aims to provide a new macromonomer whose molecular weight can be easily controlled, a method for synthesizing this macromonomer, and a new graft copolymer using the macromonomer B. .
く課題を解決するための手段〉
前記目的を達成するために本発明者らは鋭意研究を重ね
た結果、カチオンリビング重合するモノマーのリビング
生長末端を、例えばジェタノールアミン等の末端停止剤
を用いて重合を停止して、新規なマクロモノマーを合成
すると共に、リビング重合したモノマーに由来する重合
体鎖をグラフト鎖として導入し、機能性を付加した新規
グラフト共重合体ポリマーを得ることを知見し、本発明
を完成させた。Means for Solving the Problems In order to achieve the above object, the present inventors have conducted extensive research and found that the living growing end of a monomer that undergoes cationic living polymerization is terminated using a terminal capping agent such as jetanolamine. They found that they could synthesize a new macromonomer by stopping the polymerization, and also introduce a polymer chain derived from the living polymerized monomer as a graft chain to obtain a new graft copolymer polymer with added functionality. , completed the present invention.
かかる知見に基づく本発明のマクロモノマーの構成ば、 一般式［１１ で表されることを特徴とする。The structure of the macromonomer of the present invention based on such knowledge is as follows: General formula [11 It is characterized by being expressed as.
但し、式中、
Ｒ１は水素、アルキル基、アラルキル基を表し、
Ａは２−オキサゾリン化合物、１，３−オキサジン化合
物、環状イミン化合物、テトラヒドロフラン化合物、不
飽和エーテル化合物、芳香族ビニル系化合物、カルバゾ
ール化合物、含硫黄複素環化合物から由来する分子量５
０〜１０万の単独又は共重合体を表し、
で表し、
ＹはＲ２Ｙ’、 Ａ ｒ Ｙ’で表し、重合を停止させ
る停止剤を反応させ、マクロモノマーを合成することを
特徴とする。However, in the formula, R1 represents hydrogen, an alkyl group, or an aralkyl group, and A represents a 2-oxazoline compound, a 1,3-oxazine compound, a cyclic imine compound, a tetrahydrofuran compound, an unsaturated ether compound, an aromatic vinyl compound, or a carbazole. Molecular weight 5 derived from compound, sulfur-containing heterocyclic compound
It represents a single or copolymer of 0 to 100,000, and is represented by: Y is represented by R2Y' or A r Y', and is characterized in that a macromonomer is synthesized by reacting with a terminator that terminates polymerization.
更に、このマクロモノマーを用いたグラフト共重合体ポ
リマーの構成は、
一般式（社）
±
Ｙ＃
ＺはＲＺ’、 ＡｒＺ’で表し、
このマクロモノマーの合成方法の構成は、カチオンリビ
ング重合するモノマーを用いてカチオンリビング重合し
、次いでカチオンリビング生長末端と反応してカヂオン
リビングｆ′−
で表されることを特徴とするグラフト共重合体ポリマー
但し、式中、
Ｒ１は水素、アルキル基、アラルキル基を表し、
Ａは２−オキサゾリン化合物、１，３−オキサジン化合
物、環状イミン化合物、テトラヒドロフラン化合物、不
飽和エーテル化金物、芳香族ビニル系化合物、カルバゾ
ール化合物、含硫黄複素環化合物から由来する分子量５
０〜１０万の単独又は共重合体を表し、
Ｂはジ又はポリカルボン酸類、ジ又はポリオール類、ジ
又はポリイソシアネート類。Furthermore, the composition of the graft copolymer using this macromonomer is as follows: General formula ± Y# Z is represented by RZ', ArZ', and the composition of the method for synthesizing this macromonomer is as follows: A graft copolymer polymer characterized by cationic living polymerization using cationic living polymers and then reacting with cationic living propagating terminals to form a cationic living polymer represented by cationic living f'-. represents a group, and A has a molecular weight of 5 derived from a 2-oxazoline compound, a 1,3-oxazine compound, a cyclic imine compound, a tetrahydrofuran compound, an unsaturated etherified metal, an aromatic vinyl compound, a carbazole compound, a sulfur-containing heterocyclic compound
B represents a single or copolymer of 0 to 100,000, and B is di- or polycarboxylic acids, di- or polyols, or di- or polyisocyanates.
ジ又はポリ酸無水物類、ジ又はポリグリシジルエーテル
類、ジ又はポリグリシジルエステル類、ジ又はポリアミ
ン類等のＹＮ及びＺ”と重付加又は重縮合することがて
きるモノマーに由来するユニットを表し、
で表し、
ｎ は１〜１００を表し、
ｎ は１〜１０００を表す。Represents a unit derived from a monomer that can be polyadded or polycondensed with YN and Z'' such as di- or polyacid anhydrides, di- or polyglycidyl ethers, di- or polyglycidyl esters, or di- or polyamines. , where n represents 1 to 100, and n represents 1 to 1000.
以下、本発明の構成を詳細に説明する。Hereinafter, the configuration of the present invention will be explained in detail.
本発明にかかる一般式（Ｉ＋で表されるマクロモノマー
を合成するための重合体ユニットＡを生成するには、カ
チオンリビング重合を行うモノマーであればいずれでも
用いることができる。具体的には２−オキサゾリン（重
合物： ポリ （Ｎ−アシルエチレンイミン））等の２
−オキサゾリン化合物、１，３オキサジン（重合物：
ポリ （Ｎ−アシルプロピレンイミン）等の１，３−オ
キサジン系化合物、エチレンイミン、トリメチレンイミ
ン（重合物：ポリエチレンイミン、ポリトリメチレンイ
ミン）等の環状イミン化合物、テトラヒドロフラン（重
合物：ポリオキシテトラメチレン）等のテトラヒドロフ
ラン系化合物、ビニルエーテル（ｌｌ物：ポリビニルエ
ーテル）等の不飽和エーテル化合物、スチレン（重合物
：ポリスチレン）等の芳香族ビニル系化合物、Ｎビニル
カルバゾール（重合ｍ、ポリＮ−ビニルカルバゾール）
等のカルバゾール化合物、エチレンスルフィド（Ｍ合物
： ポリ （エチレンスルフィド））等の含硫黄複素環
化合物等の単独又は共重合物を挙げることができる。To produce the polymer unit A for synthesizing the macromonomer represented by the general formula (I+) according to the present invention, any monomer that undergoes cationic living polymerization can be used. Specifically, 2 -oxazoline (polymer: poly(N-acylethyleneimine)), etc. 2
-Oxazoline compound, 1,3 oxazine (polymer:
1,3-oxazine compounds such as poly (N-acylpropylene imine), cyclic imine compounds such as ethyleneimine, trimethylene imine (polymer: polyethylene imine, polytrimethylene imine), tetrahydrofuran (polymer: polyoxytetra tetrahydrofuran compounds such as methylene), unsaturated ether compounds such as vinyl ether (polyvinyl ether), aromatic vinyl compounds such as styrene (polymerized polystyrene), N-vinylcarbazole (polymerization m, polyN-vinylcarbazole) )
Examples thereof include carbazole compounds such as, sulfur-containing heterocyclic compounds such as ethylene sulfide (M compound: poly(ethylene sulfide)), and the like alone or in copolymers.
また、一般式ｆＩｌてＲ１とは、上記カチオンリビング
重合を開始させる能力を有する開始基であればよく、例
えば水素、メチル基、エチル基、プロピル基、ブチル基
、ヘキシル基。Further, R1 in the general formula fl may be any initiating group capable of initiating the above-mentioned cationic living polymerization, such as hydrogen, methyl group, ethyl group, propyl group, butyl group, and hexyl group.
シクロヘキシル基、ドデシル基のようなアルキル基、ベ
ンジル基のようなアラルキル基を挙げることができる。Examples include a cyclohexyl group, an alkyl group such as a dodecyl group, and an aralkyl group such as a benzyl group.
乙のマクロモノマーの重合度は１〜１，０００の範囲（
分子量で約５０〜１０万程度）であればよい。The degree of polymerization of the macromonomer B is in the range of 1 to 1,000 (
The molecular weight may be approximately 500,000 to 100,000.
上記カチオンリビング重合を停止させる重合停止剤Ｘと
は、カチオンリビング生長末端と反応して末端をキャッ
ピングすることにより、重合を停止し得るものであれば
、いずれを用いてもよく、例えば、
を挙げる乙とができる。The polymerization terminator X that terminates the cationic living polymerization may be any agent as long as it can terminate the polymerization by reacting with the cationic living propagating terminal and capping the terminal, such as: I can do it.
またＹ、Ｚとは上記Ｘに置換され、重縮合。Further, Y and Z are substituted with the above X and are polycondensed.
重付加を行う官能基及びその官能基の前駆体であり、Ｙ
、Ｚが同じでも異っていてもよい。A functional group that performs polyaddition and a precursor of that functional group, Y
, Z may be the same or different.
具体的にはＹは、Ｒ２Ｙ’ ｐ ＡｒＹ’で表すことが
できＺはＲ２Ｚ’、 ＡｒＺ’て表すことができる。Specifically, Y can be represented as R2Y' p ArY', and Z can be represented as R2Z', ArZ'.
具体的な停止剤Ｘとしては、 を用いるのが望ましい。As a specific terminator X, It is preferable to use
このようにカチオンリビング重合するモノマーを利用し
て得られた一般式（Ｉｌで表わされるマクロモノマーを
用い、下記に示すように鎖長延長剤（ｃｈａｉｎ ｃｘ
ｔｅｎｄｅｒ）及びモノマーを添加することにより、一
般式（５）で表すグラフト共重合体を得る乙とができる
。Using a macromonomer represented by the general formula (Il) obtained using a monomer that undergoes cationic living polymerization, a chain extender (chain cx
(tender) and a monomer, a graft copolymer represented by general formula (5) can be obtained.
この反応工程を下記に示す。This reaction process is shown below.
■
上・・
七・・
このように得られる一般式（社）で示されるグラフト共
重合体ポリマーはカチオンリビング重合したモノマーか
ら由来する重合体鎖をグラフト鎖として導入することに
より、このグラフト鎖の機能性を付加した新規なもので
ある。■ Top... Seven... The graft copolymer polymer represented by the general formula (Company) obtained in this way is obtained by introducing a polymer chain derived from a cationically living polymerized monomer as a graft chain. This is a new product with added functionality.
このようにマクロモノマーを構成するＹ及びＺを、任意
に変えることにより、例えば機能性が付加されたポリウ
レタン、ポリウレア。By arbitrarily changing Y and Z constituting the macromonomer in this way, for example, polyurethane and polyurea are added with functionality.
ポリアミド、ポリエステル等種々のグラフト共重合体を
製造する乙とができ、これにより主鎖にカチオンリビン
グ重合体鎖をグラフト鎖として導入し、主鎖自身の性質
を損うことなく、更にこのカチオンリビング重合体鎖の
機能性を付加したポリマーを得る乙とができる。It is possible to produce various graft copolymers such as polyamides and polyesters, by introducing a cationic living polymer chain into the main chain as a graft chain, without impairing the properties of the main chain itself. It is possible to obtain a polymer with added functionality of the polymer chain.
く実 施 例〉
以下本発明の特徴をさらによく理解するために実施例と
共に説明するが、これは本発明をこれら特定の実施例に
限定することを目的とするものではない。すなわち、特
許請求の範囲に定義される本発明の範囲のすべての変形
、改造、および類似物を包含するものである。したがっ
て、好適な実施例を含む以下の例は本発明を実施する際
に役立つものであり、特定例は本発明の好適な実施例の
例示のみを目的とし、最も有用であると考えられ、配合
の説明ならびに本発明の原理および概念を容易に理解す
るｔこめのものとして示されたものである。EXAMPLES> In order to better understand the characteristics of the present invention, the present invention will be described below along with examples, but this is not intended to limit the present invention to these specific examples. That is, it is intended to cover all changes, modifications, and analogs within the scope of the invention as defined in the claims. Accordingly, the following examples, including the preferred embodiments, are provided to assist in practicing the invention; the specific examples are for the sole purpose of illustrating the preferred embodiments of the invention; This has been presented to provide an easy understanding of the description and principles and concepts of the invention.
実施例１
乾燥窒素雰囲気下にて、１００ｍ１のガラス製容器にア
セトニトリル３０ｒｒｌ、２−メチル−２−オキサゾリ
ン〔よ］ （１７，０ら、２００ｍｍｏ１）、開始剤と
してｐ−トルエンスルホン酸メチルエステル（１，８６
ｇ、 １０ｍｍｏ１）を仕込み、８０℃で２４時間加熱
した。Example 1 In a dry nitrogen atmosphere, 30 rrl of acetonitrile, 2-methyl-2-oxazoline (17,0, 200 mmol), and p-toluenesulfonic acid methyl ester (1 ml) as an initiator were placed in a 100 ml glass container. ,86
g, 10 mmol 1) and heated at 80° C. for 24 hours.
室温にもどした後、ジェタノールアミン（３，１５ｇ、
３０ ｍｍｏＪ ）を加え、７０℃で２時間加熱し
、２−１ルキルー２−オキサゾリンの生長末端〔之〕を
キャッピングし、重合を停止した。After returning to room temperature, jetanolamine (3.15g,
30 mmoJ) was added and heated at 70° C. for 2 hours to cap the growing end of 2-1-lukyl-2-oxazoline and terminate polymerization.
この反応物をイオン交換処理しくイオン交換樹脂［アン
バリストＡ−２１Ｊ（商品名）。This reaction product was subjected to ion exchange treatment using an ion exchange resin [Amberlyst A-21J (trade name).
オルガノ＃りた後、ジエチルエーテルＩＩにより再沈殿
を行い、白色粉末の末端にグリコールを有するマクロマ
ー〔之）１７．Ｏｇを得た（収率９３％）。After organolysis, reprecipitation is performed with diethyl ether II to obtain a white powder containing a macromer with glycol at the end.17. Og was obtained (yield 93%).
乙の反応を下記に示す。The reaction of Party B is shown below.
〔之〕
〔之〕
乙の得られた白色粉末品は、次のスペクトルデータによ
り、末端にグリコールを有するマクロマー〔之〕と確認
された。[No.] [No.] The obtained white powder product B was confirmed to be a macromer having a glycol at the end according to the following spectral data.
赤外吸収スペクトル： 第１図参照。Infrared absorption spectrum: See Figure 1.
核磁気スペクトル：
２．０ｐｐｍ （Ｓ、 ＣＨ３Ｃ＝Ｏ）３．０ｐｐｍ
（Ｓ、ＣＨ，Ｎ ）
Ｇ ＰＣ：
Ｍｗ／Ｍｗ ＝ １．１８
ＶＰＯ：
Ｍｎ＝１９００
水酸基価７５７．９
実施例２
乾燥窒素雰囲気下にて、５０ｍ１のガラス製容器に塩化
メチレン１３．１ｍＪ、テトラヒドロフラン〔走］ （
５，９６ｇ 、 ８２．６ ｍ ｍｏｊ！ ）、に、０
℃で開始剤としてトリフルオロメタンスルホン酸エチル
エステル（０，１０８ｇ、 ０．６０６ｍｍｏＪ）を加
え、１時間、０℃に保つｔこ。Nuclear magnetic spectrum: 2.0ppm (S, CH3C=O) 3.0ppm
(S, CH, N) G PC: Mw/Mw = 1.18 VPO: Mn = 1900 Hydroxyl value 757.9 Example 2 In a dry nitrogen atmosphere, 13.1 mJ of methylene chloride and tetrahydrofuran were placed in a 50 ml glass container. [Run] (
5,96g, 82.6m moj! ), to, 0
Add trifluoromethanesulfonic acid ethyl ester (0.108 g, 0.606 mmoJ) as an initiator at 0°C and keep at 0°C for 1 hour.
７８℃に冷却後、２−メチル−２−オキサゾリン〔よ］
（０，５０３，５，９１ｍｍｏＪ）を加え、１時間、
−７８℃に保った。その後、ゆっくりと室温にもどし、
６０℃で２０時間加熱した。After cooling to 78°C, 2-methyl-2-oxazoline
(0,503,5,91 mmoJ) was added for 1 hour.
It was kept at -78°C. Then, slowly return to room temperature,
It was heated at 60°C for 20 hours.
室温にもどした後、ジェタノールアミン（０，１９１ｇ
、１．８２ｍｍｏＩりを加え、７０℃で２時間加熱し、
２−アルキル−２−オキサゾリンの生長末端〔之′〕を
キャッピングし、重合を停止した。After returning to room temperature, jetanolamine (0,191g
, 1.82 mmol was added and heated at 70°C for 2 hours.
The growing end of the 2-alkyl-2-oxazoline was capped to terminate polymerization.
乙の反応物をイオン交換処理しくイオン交換樹脂「アン
バリストＡ−２１Ｊ（商品名）。The reactant in Part B was treated with ion exchange using an ion exchange resin "Amberlyst A-21J (trade name)".
オルガノ製）た後、ヘキサン１００ｍ１により再沈殿を
行い、白色粉末の末端にグリコールを有するマクロマー
（Ａｌ１．６１ｇを得たこの反応を下記に示す。(manufactured by Organo), reprecipitation was performed with 100 ml of hexane to obtain 1.61 g of a macromer (Al) having glycol at the end of a white powder. This reaction is shown below.
Ｏ
〔よ〕
〔ｚ′〕
〔乏〕
この得られた白色粉末品は、次のスペクトルデータによ
り、末端にグリコールを有するマクロマー〔乏〕と確認
された。O [Yo] [Z'] [Poor] The obtained white powder product was confirmed to be a macromer having glycol at the end (poor) based on the following spectral data.
赤外吸収スペクトル：
３４００ｃｍ ’ （シ０−Ｈ）
１６００ｃｍ ’ （νｃ＝ｏ）
核磁気スペクトル：
１．０〜１．４ｐｐｍ （ｍ、 ＣＨ３ＣＨ２−０）
１、５〜２．０ ｐ ｐｍ （ｂ ｒ、 −ＣＨ２ＣＨ
２０）２、０〜２．１ ｐ ｐｍ （Ｓ、 ＣＨ３Ｃ
＝Ｏ）２．５〜２．７ｐｐｍ
（ｍ。Infrared absorption spectrum: 3400cm' (CH0-H) 1600cm' (νc=o) Nuclear magnetic spectrum: 1.0-1.4ppm (m, CH3CH2-0)
1,5-2.0 ppm (br, -CH2CH
20) 2,0-2.1 ppm (S, CH3C
=O)2.5-2.7ppm (m.
ＧＰＣ：
Ｍｗ／Ｍｗ −−１，２０
ＶＰＯ：
Ｍ ｎ −＝ １１００
水酸基価＝１１４
ＣＨＮ）
リウレタンウレアＬＬ）２．５ｇを得た（収率９６％）
。GPC: Mw/Mw −-1,20 VPO: M n −=1100 Hydroxyl value=114 CHN) 2.5 g of urethane urea LL) was obtained (yield 96%)
.
この反応を下記に示す。This reaction is shown below.
実施例３
上記実施例１て得られたマクロマー〔之〕（１，９ｇ、
１ｍｍｏＪ）を用い、４，４′−ジフェニルメタジイ
ソシアネ−ｈ （０，５０ｇ、 ２ｍｍｏｊ’）を添加
して８０℃で８時間反応させて、両末端にイソシアネー
ト基をもつプレポリマー〔瓦〕２．４ｇを得た（収率１
００％）。Example 3 Macromer obtained in Example 1 above (1.9 g,
1 mmoJ), 4,4'-diphenylmetadiisocyanate-h (0.50 g, 2 mmoj') was added and reacted at 80°C for 8 hours to form a prepolymer [roof tile] 2 having isocyanate groups at both ends. .4g was obtained (yield 1
00%).
この得られたプレポリマー〔庭〕に鎖長延長剤として４
，４′−ジアミノジフェニルエーテル（０，２ｇ、 １
ｍｍｏｌ ）を反応させ、ポリ（２詞キサゾリン）鎖
をグラフト鎖に有するボノ
ゴトうこ
この得られたポリマーは、次のスペクトルデータにより
、ポリウレタンウレアのグラフト共重合体ポリマーと確
認された。This obtained prepolymer was added to 4 as a chain extender.
,4'-diaminodiphenyl ether (0.2g, 1
The resulting polymer having a poly(xazoline) chain in the graft chain was confirmed to be a graft copolymer of polyurethane urea based on the following spectral data.
赤外吸収スペクトル： 第２図参照。Infrared absorption spectrum: See Figure 2.
ＧＰＣ：
Ｍｗ ＝ ９．０００
またこの得られたグラフト共重合体用ポリマーは親水性
を有しており、水濡れ性が高く、且つ帯電防止性も高い
ことが確認された。GPC: Mw = 9.000 It was also confirmed that the obtained polymer for graft copolymer had hydrophilicity, high water wettability, and high antistatic property.
〈発明の効果〉
以上、実施例と共に詳しく述べたように、本発明によれ
ばカチオンリビング重合するモノマーのリビング生長末
端をキャッピングして任意に重合度が規制される新規な
マクロモノマーを得ることができると同時に、このマク
ロモノマーを利用して種々の新規なグラフト共重合体ポ
リマーを得ることができる。またこのグラフト共重合体
ポリマーは、リビング重合したモノマーから由来する重
合体鎖をグラフト鎖として導入させている乙とにより、
主鎖のポリマー自身の性質を損うことなく、更に機能性
を付加したものとなる。<Effects of the Invention> As described above in detail along with Examples, according to the present invention, it is possible to obtain a novel macromonomer whose degree of polymerization can be arbitrarily regulated by capping the living growing end of a monomer that undergoes cationic living polymerization. At the same time, various novel graft copolymers can be obtained using this macromonomer. In addition, this graft copolymer polymer has a polymer chain derived from a living polymerized monomer introduced as a graft chain.
Further functionality is added without impairing the properties of the main chain polymer itself.
第１図は実施例１で得られたマクロモノマーの赤外吸収
スペクトル、第２図は実施例３で得られたグラフト共重
合体ポリマーの赤外吸収スペクトルである。FIG. 1 shows an infrared absorption spectrum of the macromonomer obtained in Example 1, and FIG. 2 shows an infrared absorption spectrum of the graft copolymer obtained in Example 3.
Claims (1)
物、環状イミン化合物、テトラヒドロフラン化合物、不
飽和エーテル化合物。 芳香族ビニル系化合物、カルバゾール化合物、含硫黄複
素環化合物から由来する分子量５０〜１０万の単独又は
共重合体を表し、 Ｘは▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼、▲数式、化学式、表等がありま
す▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 で表し、 ＹはＲ＿２Ｙ′、ＡｒＹ′で表し、 〔Ｒ＿２：▲数式、化学式、表等があります▼、 Ａｒ：▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、 Ｙ′：−ＯＨ、−ＮＨ＿２、▲数式、化学式、表等があ
ります▼、 −Ｉ、−Ｂｒ、−Ｃｌ、−ＳＨ、−ＣＯＯＲ＿３、−Ｏ
ＳＯ＿２Ｒ＿３（Ｒ＿３：Ｈ、アルキル基、アリール基
、 トリメチルシリル基）〕 ＺはＲ＿２Ｚ′、ＡｒＺ′で表し、 〔Ｒ＿２：▲数式、化学式、表等があります▼、 Ａｒ：▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、 Ｚ′：−Ｈ、−ＯＨ、−ＮＨ＿２、▲数式、化学式、表
等があります▼、−Ｉ、−Ｂｒ、−Ｃｌ、−ＳＨ、−Ｃ
ＯＯＲ＿３、−ＯＳＯ＿２Ｒ＿３（Ｒ＿３：Ｈ、アルキ
ル基、アリール基、 トリメチルシリル基）〕 ｎ＿１は１〜１０００を表す。 ２）カチオンリビング重合するモノマーを用いてカチオ
ンリビング重合し、次いでカチオンリビング生長末端と
反応してカチオンリビング重合を停止させる停止剤を反
応させ、マクロモノマーを合成することを特徴とするマ
クロモノマーの合成方法。 ３）一般式（II） ▲数式、化学式、表等があります▼・・・（II） で表されることを特徴とするグラフト共重合体ポリマー
。 但し、式中、 Ｒ＿１は水素、アルキル基、アラルキル基を表し、 Ａは２−オキサゾリン化合物、１，３−オ キサジン化合物、環状イミン化合物、テト ラヒドロフラン化合物、不飽和エーテル化 合物、芳香族ビニル系化合物、カルバゾー ル化合物、含硫黄複素環化合物から由来す る分子量５０〜１０万の単独又は共重合体 を表し、 ＢはＹ″及びＺ″と重付加又は重縮合することができる
モノマーに由来するユニットを 表し、 Ｘは▲数式、化学式、表等があります▼、▲数式、化学
式、表等があります▼、▲数式、化学式、表等がありま
す▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼、 ▲数式、化学式、表等があります▼、▲数式、化学式、
表等があります▼ で表し、 Ｙ″はＲ＿２Ｙ′″、ＡｒＹ′″で表し、 〔Ｒ＿２：▲数式、化学式、表等があります▼、 Ａｒ：▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、 Ｙ′″：−Ｏ、−ＮＨ、▲数式、化学式、表等がありま
す▼、 −Ｓ、−ＣＯＯ、−ＯＳＯ＿２〕 Ｚ″はＲ＿２Ｚ′″、ＡｒＺ′″で表し、 〔Ｒ＿２：▲数式、化学式、表等があります▼、 Ａｒ：▲数式、化学式、表等があります▼、▲数式、化
学式、表等があります▼、 Ｚ′″：−Ｏ、−ＮＨ、▲数式、化学式、表等がありま
す▼、 −Ｓ、−ＣＯＯ、−ＯＳＯ＿２〕 ｎ＿１は１〜１００を表し、 ｎ＿２は１〜１０００を表す。[Claims] 1) A macromonomer characterized by being represented by the general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I). However, in the formula, R_1 represents hydrogen, an alkyl group, or an aralkyl group, and A is a 2-oxazoline compound, a 1,3-oxazine compound, a cyclic imine compound, a tetrahydrofuran compound, or an unsaturated ether compound. Represents a single or copolymer with a molecular weight of 500,000 to 100,000 derived from an aromatic vinyl compound, a carbazole compound, or a sulfur-containing heterocyclic compound. There are ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, Y is represented by R_2Y', ArY', [R_2: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas , there are tables, etc. ▼, Y': -OH, -NH_2, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -I, -Br, -Cl, -SH, -COOR_3, -O
SO_2R_3 (R_3: H, alkyl group, aryl group, trimethylsilyl group)] Z is represented by R_2Z', ArZ', [R_2: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, Z': -H, -OH, -NH_2, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -I, -Br, -Cl, -SH, - C
OOR_3, -OSO_2R_3 (R_3: H, alkyl group, aryl group, trimethylsilyl group)] n_1 represents 1 to 1000. 2) Synthesis of a macromonomer characterized by performing cationic living polymerization using a monomer that undergoes cationic living polymerization, and then reacting with a terminator that reacts with the cationic living growing end to terminate the cationic living polymerization to synthesize a macromonomer. Method. 3) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) A graft copolymer polymer characterized by being represented by the following. However, in the formula, R_1 represents hydrogen, an alkyl group, an aralkyl group, and A represents a 2-oxazoline compound, a 1,3-oxazine compound, a cyclic imine compound, a tetrahydrofuran compound, an unsaturated ether compound, an aromatic vinyl compound, a carbazole compound, represents a single or copolymer with a molecular weight of 500,000 to 100,000 derived from a sulfur-containing heterocyclic compound, B represents a unit derived from a monomer that can be polyadded or polycondensed with Y″ and Z″, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼ , Y″ is represented by R_2Y′″, ArY′″, [R_2: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas , chemical formulas, tables, etc. ▼, Y'″: -O, -NH, ▲ Numerical formulas, chemical formulas, tables, etc. ▼, -S, -COO, -OSO_2〕 Z″ is R_2Z′″, ArZ′″ Representation, [R_2: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Ar: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, Z′″: -O, -NH, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -S, -COO, -OSO_2] n_1 represents 1 to 100, n_2 represents 1 to 1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1096500A JPH02274712A (en) | 1989-04-18 | 1989-04-18 | Macromonomer, its synthesis and graft copolymer prepared by using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1096500A JPH02274712A (en) | 1989-04-18 | 1989-04-18 | Macromonomer, its synthesis and graft copolymer prepared by using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02274712A true JPH02274712A (en) | 1990-11-08 |
Family
ID=14166823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1096500A Pending JPH02274712A (en) | 1989-04-18 | 1989-04-18 | Macromonomer, its synthesis and graft copolymer prepared by using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02274712A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057174A1 (en) * | 1998-05-07 | 1999-11-11 | Nano Carrier Co. | Polyoxyethylene derivatives having optionally protected amino group at one end and process for producing the same |
| WO2001010934A1 (en) * | 1999-08-04 | 2001-02-15 | Nanocarrier Co., Ltd. | Block copolymer having polymer segment derived from oxazoline |
-
1989
- 1989-04-18 JP JP1096500A patent/JPH02274712A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999057174A1 (en) * | 1998-05-07 | 1999-11-11 | Nano Carrier Co. | Polyoxyethylene derivatives having optionally protected amino group at one end and process for producing the same |
| JP4581248B2 (en) * | 1998-05-07 | 2010-11-17 | 日油株式会社 | Polyoxyethylene derivative having amino group optionally protected at one end and method for producing the same |
| WO2001010934A1 (en) * | 1999-08-04 | 2001-02-15 | Nanocarrier Co., Ltd. | Block copolymer having polymer segment derived from oxazoline |
| US6974856B1 (en) | 1999-08-04 | 2005-12-13 | Nanocarrier Co., Ltd. | Block copolymers having polymer segment derived from oxazoline |
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