JPH03277631A - A method for producing a new polymeric quaternary salt - Google Patents

A method for producing a new polymeric quaternary salt

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Publication number
JPH03277631A
JPH03277631A JP2229917A JP22991790A JPH03277631A JP H03277631 A JPH03277631 A JP H03277631A JP 2229917 A JP2229917 A JP 2229917A JP 22991790 A JP22991790 A JP 22991790A JP H03277631 A JPH03277631 A JP H03277631A
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JP
Japan
Prior art keywords
formula
quaternary salt
polymeric quaternary
resin
salt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP2229917A
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Japanese (ja)
Other versions
JPH0424364B2 (en
Inventor
Hideo Toda
秀夫 戸田
Kunio Kihara
木原　圀男
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Mitsubishi Chemical Corp
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Mitsubishi Petrochemical Co Ltd
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Priority to JP2229917A priority Critical patent/JPH03277631A/en
Publication of JPH03277631A publication Critical patent/JPH03277631A/en
Publication of JPH0424364B2 publication Critical patent/JPH0424364B2/ja
Granted legal-status Critical Current

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

PURPOSE:To obtain a polymeric quaternary salt having an imidazolium salt in the main chain, being odorless and not emitting any unpleasant odor even in applications where heating is required by reacting an imidazole with a halomethyloxirane compound. CONSTITUTION:An imidazole of formula I (wherein R1 is H, 1-17C alkyl or 6-8C aryl; R2 and R3 are each H or 1-3C alkyl), e.g. imidazole or 2-ethyl-4- methylimidazole, is reacted with a halomethyloxirane compound of formula II (wherein R4 is H or CH3; and X is halogen), e.g. epichlorohydrin, in an aqueous solvent to obtain a polymeric quaternary salt of formula III (wherein R1, R2, R3, R4 and X are as defined above; and n is 2-5000), e.g. a polymeric quaternary salt of formula IV. The polymeric quaternary salt having an imidazolium salt in the main chain is odorless, does not emit any unpleasant odor even in applications where heating is required and has possibilities of use as a modifier for synthetic resins, a textile aftertreatment agent, a paper processing agent, a flocculant, an antistatic agent, an assistant for detergents, cosmetics, etc., an antiseptic or a medicine such as a cholesterol depressant.

Description

【発明の詳細な説明】 産ｌ上坐剋里公団 本発明は、新規な高分子四級塩の製造方法に関するもの
であり、更に詳しくはイミダゾリウム塩を主鎖に有する
新規な高分子四級塩の製造方法に関するものである。Detailed Description of the Invention The present invention relates to a method for producing a novel quaternary polymer salt, and more specifically relates to a method for producing a novel quaternary polymer salt having an imidazolium salt in its main chain. This invention relates to a method for producing salt.

本発明の方法により製造される新規な高分子四級塩は、
合成樹脂の改質剤、織物後処理剤、紙処理剤、凝集剤、
帯電防止剤、洗剤・化粧品・シャンプー等の助剤、防腐
剤、抗菌剤・コレステロール低下剤等の医薬としての応
用等が期待されるものである。The novel polymeric quaternary salt produced by the method of the present invention is
Synthetic resin modifier, textile post-treatment agent, paper treatment agent, flocculant,
It is expected to be applied as an antistatic agent, an auxiliary agent for detergents, cosmetics, shampoos, etc., a preservative, an antibacterial agent, a cholesterol-lowering agent, and other pharmaceuticals.

の　　　　　　　°　しよ゛と　る 従来、高分子四級塩としてアンモニウム塩、ピリジニウ
ム塩を有する高分子等が知られている。Conventionally, polymers having ammonium salts and pyridinium salts are known as polymer quaternary salts.

しかし、この種の高分子四級塩は高分子の熱安定性が劣
るため、使用時、特に加熱される場合において著しく不
快なアミン臭を発し、作業環境を悪化させたり、あるい
は改良すべき材料の品質を低下させる等の欠点を有して
いた。However, this type of polymeric quaternary salt has poor thermal stability, so when used, especially when heated, it emits an extremely unpleasant amine odor, which worsens the working environment or creates materials that should be improved. It had drawbacks such as deterioration of quality.

本発明者らは、この様な従来品の欠点を克服すべく鋭意
研究を重ね本発明を完成した。The present inventors completed the present invention through extensive research in order to overcome these drawbacks of conventional products.

本発明は、高分子四級塩の無臭化および耐熱性の改良を
はかり、重合体に臭気がなく、かつ加熱を必要とする使
用時においても不快臭のない新規な高分子四級塩の製造
方法を提供するものである。The present invention aims to make the polymer quaternary salt odorless and improve its heat resistance, and to produce a novel polymer quaternary salt that has no odor in the polymer and does not have an unpleasant odor even when used when heating is required. The present invention provides a method.

主■皇盈戒 本発明は、下記式Ｎ） Ｒ＋　　　　　　　　　　　　　　　Ｒ１（式中、Ｒ１
は水素原子、０１〜３．のアルキル基または０６〜．の
アリール基を、Ｒ２およびＲ３は同一または異なる置換
基で水素原子またはＣｌ〜３のアルキル基を、Ｒ４は水
素原子またはメチル基を、Ｘはハロゲン原子を、ｎは２
以上の整数をそれぞれ表わす） で示される新規な高分子四級塩の製造方法を提供するも
のである。The present invention is based on the following formula N) R+ R1 (in the formula, R1
is a hydrogen atom, 01-3. an alkyl group or 06-. R2 and R3 are the same or different substituents and represent a hydrogen atom or an alkyl group of Cl~3, R4 represents a hydrogen atom or a methyl group, X represents a halogen atom, and n represents 2
The present invention provides a method for producing a novel quaternary polymer salt represented by the following integers:

本発明の方法により製造される高分子四級塩の前記式（
１）中で用いられるＲ１は水素原子、メチル、エチル、
プロピル、ヘキシル、ウンデシル、ヘプタデシル基等の
ＣＩ””Ｉ７のアルキル基またはフェニル、トリル、キ
シリル基等のＣ８〜８のアリール基、ＲｚおよびＲ３は
同一または異なる置換基で水素原子またはメチル、エチ
ル、プロピル基等のＣ１〜３のアルキル基、Ｒ４は水素
原子またはメチル基、Ｘは塩素、臭素等のハロゲン原子
から選んで用いられる。これらの中でも特に好ましい高
分子四級塩の具体例は、次記の構造を有するものである
。The above formula (
1) R1 used in is a hydrogen atom, methyl, ethyl,
CI""I7 alkyl group such as propyl, hexyl, undecyl, heptadecyl group or C8-8 aryl group such as phenyl, tolyl, xylyl group, Rz and R3 are the same or different substituents and are a hydrogen atom or methyl, ethyl, A C1-3 alkyl group such as a propyl group, R4 is a hydrogen atom or a methyl group, and X is selected from a halogen atom such as chlorine or bromine. Among these, specific examples of particularly preferred polymeric quaternary salts have the following structure.

これらの置換基で特定される高分子四級塩の分子量は水
溶性である限り特に制限はないが、好ましくはｎが２以
上、好ましくは２〜５０００の高分子四級塩である。The molecular weight of the polymeric quaternary salt specified by these substituents is not particularly limited as long as it is water-soluble, but it is preferably a polymeric quaternary salt in which n is 2 or more, preferably 2 to 5,000.

本発明の高分子四級塩の製造方法は、下記式（） （式中、Ｒ＋　は水素原子、Ｃ１〜ｌ、のアルキル基ま
たは０６〜８のアリール基を、Ｒ２およびＲ３は同一ま
たは異なる置換基で水素原子またはＣ〜３のアルキル基
をそれぞれ表わす） で示されるイミダゾール類を下記式（ＩＩ［）４ υ （式中、Ｒ４は水素原子またはメチル基を、Ｘはハロゲ
ン原子をそれぞれ表わす） で示されるハロメチルオキシラン化合物と反応させる方
法である。The method for producing a polymer quaternary salt of the present invention is carried out by the following formula () (wherein, R+ is a hydrogen atom, C1-1 alkyl group or 06-8 aryl group, R2 and R3 are the same or different substituted The imidazoles represented by the following formula (II[)4 υ (wherein, R4 represents a hydrogen atom or a methyl group, and X represents a halogen atom) This is a method of reacting with a halomethyloxirane compound shown in

上記製造方法に用いられる前記式（ｎ）で示されるイミ
ダゾール類としては、イミダゾール、２−エチルイミダ
ゾール、２−メチルイミダゾール２−プロピルイミダゾ
ール、２−フェニルイミダゾール、２−ウンデシルイミ
ダゾール、２−ヘプタデシルイミダゾール、２−エチル
−４−メチルイミダゾール、２，４−ジメチルイミダゾ
ール、２−フェニル−４−メチルイミダゾールなどが挙
げられる。また、前記式（ＩＩ［）で示されるハロメチ
ルオキシラン化合物としては、エピクロルヒドリン、β
−メチルエピクロルヒドリン、エピブロムヒドリンなど
が挙げられる。The imidazoles represented by the formula (n) used in the above production method include imidazole, 2-ethylimidazole, 2-methylimidazole, 2-propylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecyl Examples include imidazole, 2-ethyl-4-methylimidazole, 2,4-dimethylimidazole, and 2-phenyl-4-methylimidazole. Further, as the halomethyloxirane compound represented by the formula (II[), epichlorohydrin, β
-Methyl epichlorohydrin, epibromohydrin, etc.

反応溶媒としては、水が用いられ、このことにより高分
子量体を得ることができる。Water is used as the reaction solvent, and thereby a high molecular weight product can be obtained.

反応モル比は、イミダゾール１２１モルに対してハロメ
チルオキシラン化合物０．５〜２．０モルが用いられ特
に０．９〜１．１モルが好ましい。The reaction molar ratio is preferably 0.5 to 2.0 moles, and particularly preferably 0.9 to 1.1 moles, of the halomethyloxirane compound to 121 moles of imidazole.

反応温度は３０〜１５０°Ｃが用いられるが特に５０〜
１２０°Ｃが好ましい。３０℃未満では反応速度が遅く
、１２０℃を越えると副反応が起りやすいので好ましく
ない。The reaction temperature used is 30 to 150°C, but especially 50 to 150°C.
120°C is preferred. If it is less than 30°C, the reaction rate is slow, and if it exceeds 120°C, side reactions tend to occur, which is not preferable.

反応時間は２〜３０時間が適当である。A suitable reaction time is 2 to 30 hours.

反応方法は、溶媒として水を使用する場合、ハロメチル
オキシラン化合物をイミダゾール類の水溶液中に滴下す
るのが好ましいが、同時に仕込むこともできる。反応終
了後、得られた粘稠な反応液をエタノール、アセトン等
の本発明の方法により製造される高分子四級塩の貧溶媒
中に注ぐことにより白色粉末状の高分子四級塩を得るこ
とができる。In the reaction method, when water is used as a solvent, it is preferable to drop the halomethyloxirane compound into an aqueous solution of imidazoles, but they can also be added at the same time. After the reaction is completed, the resulting viscous reaction solution is poured into a poor solvent for the polymer quaternary salt produced by the method of the present invention, such as ethanol or acetone, to obtain a white powdery polymer quaternary salt. be able to.

１隻■ （製造例１） イミダゾール３０ｇ（０，４４１モル）を水６０ｍ１！
に溶かし３００１１の四ツロフラスコに入れた。1 ship ■ (Production example 1) 30g (0,441 mol) of imidazole in 60ml of water!
and put it in a 30011 Yotsuro flask.

次にエピクロルヒドリン４０．８ｇ（０，４４１モル）
を滴下ロートにより５０°Ｃで２時間かけて加えた後、
１００°Ｃに昇温しこの温度で１４時間反応を行なった
。得られた粘稠な反応液を２００ｍｆのエタノール中に
注ぎ重合体を析出させた。炉別後、洗浄を行ない減圧乾
燥により白色粉末樹脂（樹脂Ａとする）６８．６ｇを得
た。Next, 40.8 g (0,441 mol) of epichlorohydrin
was added using a dropping funnel at 50°C over 2 hours, and then
The temperature was raised to 100°C and the reaction was carried out at this temperature for 14 hours. The resulting viscous reaction solution was poured into 200 mf of ethanol to precipitate a polymer. After the furnace separation, 68.6 g of white powder resin (referred to as resin A) was obtained by washing and drying under reduced pressure.

得られた上記樹脂を分析して以下の結果を得た。The resulting resin was analyzed and the following results were obtained.

（１）赤外線吸収スペクトル特性吸収位置（ＫＢｒ法、
単位１−１） ３４００．２０４０．１６２０．１５６ｏ、１４４ｏ、
１３４ｏ、１１６ｏ、１１００．７６０．６３０ （２）プロトン核磁気共鳴スペクトル特性吸収位置（溶
媒：Ｄ２０、単位δ（ｐｐ＋ｗ）　）３、９〜４．４　
　（ｍ、　　５　Ｈ，ＣＬ　　　ＣＪＬ　　ＣＪＬｚ　
　　）Ｈ （３）　”　Ｃ−核磁気共鳴スペクトル特性吸収値１！
（溶媒＝ＤｚＯ１単位δ（ｐｐｍ）） ６７、７２ （Ｃ−５） １２３゜ （Ｃ ２， ３） １３６゜ ６ （Ｃ−１） （５）固有粘度〔η〕 （溶媒：水、 ２５°Ｃ） ０．７２ 以上の結果から樹脂Ａは、 なる構造を有するものであることが判る。(1) Infrared absorption spectrum characteristics absorption position (KBr method,
Unit 1-1) 3400.2040.1620.156o, 144o,
134o, 116o, 1100.760.630 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: D20, unit δ (pp+w)) 3, 9 to 4.4
(m, 5 H, CL CJL CJLz
)H (3) ”C-nuclear magnetic resonance spectrum characteristic absorption value 1!
(Solvent = DzO1 unit δ (ppm)) 67, 72 (C-5) 123° (C 2, 3) 136°6 (C-1) (5) Intrinsic viscosity [η] (Solvent: Water, 25°C ) 0.72 From the above results, it can be seen that resin A has the following structure.

（なお、式中、核磁気共鳴スペクトルデータより算出し
たｎの値は３１である。） （製造例２） ２−メチルイミダゾール４１ｇ（０，５モル）を水６０
ｔｔｒｌに溶かし３００Ｉ＋１１．の四つロフラスコに
入れた。次にエピクロルヒドリン４６．３ｇ（０，５モ
ル）を滴下ロートにより、５０°Ｃで２時間かけて加え
た後、１００℃に昇温しこの温度で１４時間反応を行な
った。製造例１と同様な後処理を行ない８３．９　ｇの
白色粉末状樹脂（樹脂Ｂとする）を得た。(In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 31.) (Production Example 2) 41 g (0.5 mol) of 2-methylimidazole was dissolved in 60 g of water.
Dissolve in ttrl 300I+11. I put four of them into a flask. Next, 46.3 g (0.5 mol) of epichlorohydrin was added via a dropping funnel at 50°C over 2 hours, and then the temperature was raised to 100°C and the reaction was carried out at this temperature for 14 hours. The same post-treatment as in Production Example 1 was performed to obtain 83.9 g of a white powdery resin (referred to as Resin B).

得られた上記樹脂を製造例１と同様に分析して以下の結
果を得た。The obtained resin was analyzed in the same manner as in Production Example 1, and the following results were obtained.

（１）赤外線吸収スペクトル特性吸収値Ｗ（ＫＢｒ法、
単位Ｃｍ−’） ３４００．２０５０．１６２０．１５８０．１５２０．
１４２０．１３４０．１２６０．１１８０．１１００．
１０３０．８７０．７６０　、６６０（２）プロトン核
磁気共鳴スペクトル特性吸収位置（溶媒：０２０、単位
δ（ｐｐｍ）　）２．５２ （Ｓ、 ３Ｈ，ＣＩ。(1) Infrared absorption spectrum characteristic absorption value W (KBr method,
Unit Cm-') 3400.2050.1620.1580.1520.
1420.1340.1260.1180.1100.
1030.870.760, 660(2) Proton Nuclear Magnetic Resonance Spectrum Characteristics Absorption position (solvent: 020, unit δ (ppm)) 2.52 (S, 3H, CI.

） ４．０〜４．４ （ｍ、 ５　Ｈ、Ｃｆ１ｚＣＪＬＣｆｌｚ ） １ｈ （３）　”　Ｃ−核磁気共鳴スペクトル特性吸収位置（
溶 媒：Ｄ２０ 単位δ （ｐｐｏ＋）　） （５）固有粘度〔η］　（溶媒：水、２５°Ｃ）１．０
０ 以上の結果から本製造例で得られた樹脂Ｂは、ＣＨ。) 4.0 to 4.4 (m, 5 H, Cf1zCJLCflz) 1h (3) ”C-nuclear magnetic resonance spectral characteristics absorption position (
Solvent: D20 unit δ (ppo+) ) (5) Intrinsic viscosity [η] (Solvent: water, 25°C) 1.0
0 From the above results, the resin B obtained in this production example was CH.

Ｏ３ なる構造を有するものであることが判る。O3 It can be seen that it has the following structure.

（なお、式中、核磁気共鳴スペクトルデータより算出し
たｎの値は３５である。） （製造例３） ２−フェニルイミダゾール６３．５ｇ（０，４４モル）
を水１００＋ｗｆに一部分溶けた状態で分散させ３００
Ｉｌｌの四ツロフラスコに入れた。次にエピクロルヒド
リン４０．８ｇ（０，４４モル）を滴下ロートにより５
０°Ｃで２時間かけて加えた後、１００℃に昇温しこの
温度で１６時間反応を行なった。製造例１と同様な後処
理を行ない９９．７　ｇの白色粉末状樹脂（樹脂Ｃとす
る）を得た。(In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 35.) (Production Example 3) 63.5 g (0.44 mol) of 2-phenylimidazole
Disperse it in a partially dissolved state in water 100+wf and add 300%
Ill put it in a four-piece flask. Next, 40.8 g (0.44 mol) of epichlorohydrin was added to the
After the addition over 2 hours at 0°C, the temperature was raised to 100°C and the reaction was carried out at this temperature for 16 hours. The same post-treatment as in Production Example 1 was performed to obtain 99.7 g of a white powdery resin (referred to as Resin C).

この樹脂を製造例１と同様に分析した。This resin was analyzed in the same manner as in Production Example 1.

（１）赤外吸収スペクトル特性吸収位置（ＫＢｒ法、単
位＝０１） ３４００．３２００．１６２０．１６００．１５８０．
１５００．１４７０．１４３０．１２６０．１１７０．
１１００．１０３０．８７０．７７０、９０ （２）プロトン核磁気共鳴スペクトル特性吸収位置（溶
媒：ＤｚＯ１単位：δ（ｐｐｎ＋））３、６〜３．９　
（ｍ、　５　Ｈ，（、ＨｚＣＪＬＣＪｉｚ）Ｈ （３）　”　Ｃ 核磁気共鳴スペク トル特性吸収位置（溶 ｌυ １２９、６３ （Ｃ ８， １２） ２９、８３ （Ｃ−９， １１） ３２、７７ （Ｃ−１０） １４５、３５ （Ｃ−１） （５）固有粘度〔η〕 （溶媒：水、 ２５°Ｃ） ０．４１ 以上の結果から樹脂Ｃは、 なる構造を有するものであることが判る。(1) Infrared absorption spectrum characteristics Absorption position (KBr method, unit = 01) 3400.3200.1620.1600.1580.
1500.1470.1430.1260.1170.
1100.1030.870.770, 90 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: DzO 1 unit: δ (ppn+)) 3, 6 to 3.9
(m, 5 H, (, HzCJLCJiz)H (3) ” C Nuclear magnetic resonance spectral characteristics Absorption position (Solution lυ 129, 63 (C 8, 12) 29, 83 (C-9, 11) 32, 77 (C -10) 145,35 (C-1) (5) Intrinsic viscosity [η] (Solvent: Water, 25°C) 0.41 From the above results, it can be seen that Resin C has the following structure.

（なお、式中、核磁気共鳴スペクトルにより算出したｎ
の値は２３である。） （製造例４） ２−ウンデシルイミダゾール９７．９ｇ（０，４４モル
）を水１２０ｊ！に一部分溶けた状態で分散させ３００
ｓｆの四ツロフラスコに入れた。次にエピクロルヒドリ
ン４０．８ｇ（０，４４モル）を滴下ロートにより５０
℃で２時間かけて加えた後、１００″Ｃに昇温しこの温
度で１６時間反応を行なった。製造例１と同様な後処理
を行ない１３４．７ｇの白色粉末状樹脂（樹脂りとする
）を得た。(In the formula, n calculated by nuclear magnetic resonance spectrum
The value of is 23. ) (Production Example 4) 97.9 g (0.44 mol) of 2-undecylimidazole was mixed with 120 g of water! 300% by dispersing it in a partially dissolved state.
I put it in an SF Yotsuro flask. Next, 40.8 g (0.44 mol) of epichlorohydrin was added to the
℃ for 2 hours, the temperature was raised to 100''C, and the reaction was carried out at this temperature for 16 hours.The same post-treatment as in Production Example 1 was carried out to obtain 134.7g of white powdery resin (resin resin). ) was obtained.

この樹脂を製造例１と同様に分析した。This resin was analyzed in the same manner as in Production Example 1.

（１）赤外吸収スペクトル特性吸収位置ＣＫＢｒ法、単
位：ｃｌ’） ３４００．３２００．２９００．２８５０．１６２０．
１５８０．１５２０．１４６０．１４４０．１３７０．
１２６０．１１８０．１１００．８７０．７６０．７２
０ （２）プロトン核磁気共鳴スペクトル特性吸収位置（溶
媒：ＤｚＯ２単位δ（ｐｐｍ）　）０．７〜１．４（ｍ
、２３Ｈ，Ｃ，、且２３）３、７〜４．４　（ｍ、　５
　Ｈ，Ｃｆ１ｚＣｔＬＣＪＬｚ　　）ＩＩＨｚｚ （３）　”　Ｃ−核磁気共鳴スペクトル特性吸収位置（
溶Ｃ＋＋ ５０、７９ ６８、２４ １２１、８９ ２　１０、８３ （Ｃ−４，６） （Ｃ−５） （Ｃ−２，３） （Ｃ−１） （５）固有粘度〔η〕　（溶媒：水、２５°Ｃ）０．２
７ 以上の結果から樹脂りは、 Ｃ目Ｈｔｚ　　　　　　　　　　Ｃ＋　＋ｌｂｓなる構
造を有するものであることが判る。(1) Infrared absorption spectrum characteristics Absorption position CKBr method, unit: cl') 3400.3200.2900.2850.1620.
1580.1520.1460.1440.1370.
1260.1180.1100.870.760.72
0 (2) Proton nuclear magnetic resonance spectral characteristics Absorption position (solvent: DzO2 unit δ (ppm)) 0.7 to 1.4 (m
, 23H,C,, and 23) 3, 7 to 4.4 (m, 5
H, Cf1zCtLCJLz )IIHz (3) ” C-Nuclear magnetic resonance spectral characteristic absorption position (
Solvent C++ 50, 79 68, 24 121, 89 2 10, 83 (C-4,6) (C-5) (C-2,3) (C-1) (5) Intrinsic viscosity [η] (Solvent: water, 25°C) 0.2
7 From the above results, it can be seen that the resin resin has a structure of C-order Htz C+ +lbs.

（なお、式中、核磁気共鳴スペクトルデータにより算出
したｎの値は１２である。） （製造例５） ２−エチル−４−メチルイミダゾール４８．６　ｇ（０
，４４モル）を水６０ｒａｌに溶かし３００ｍｆの四ツ
ロフラスコに入れた。次にエピクロルヒドリン４０．８
ｇ（０，４４モル）を滴下ロートにより５０°Ｃで２時
間かけて加えた後、１００°Ｃに昇温しこの温度で１４
時間反応を行なった。製造例１と同様な後処理を行ない
８９．３　ｇの白色粉末状樹脂（樹脂Ｅとする）を得た
。(In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 12.) (Production Example 5) 2-ethyl-4-methylimidazole 48.6 g (0
, 44 mol) was dissolved in 60 ral of water and placed in a 300 mf four-tube flask. Next, epichlorohydrin 40.8
g (0.44 mol) was added via a dropping funnel at 50°C over 2 hours, the temperature was raised to 100°C, and at this temperature 14
A time reaction was performed. The same post-treatment as in Production Example 1 was performed to obtain 89.3 g of a white powdery resin (referred to as Resin E).

この樹脂を製造例１と同様に分析した。This resin was analyzed in the same manner as in Production Example 1.

（１）赤外吸収スペクトル特性吸収位置ＣＫＢｒ法、単
位：ａｉ−’） ３４００．３０００．２０５０．１６３０．１５２０．
１４５０．１３９０．１２４０．１１８０．１１００．
１０６０．８８０．７８０（２）プロトン核磁気共鳴ス
ペクトル特性吸収位置（溶媒＝Ｄ２０、単位：δ（ｐｐ
ｍ）　）１．０９　　（Ｓ、　　３　Ｈ，ＣＨｚＣ１３
）２．１４（ｓ、３Ｈ１−岨、　） ２．９２　　（ｂｒｄ　、　　２Ｈ，ＣＪ１ｚＣＨ３）
４．１〜４．６ （ｍ　５ ５Ｈ１ −ＣＨ□ＣｌＣｆ１ｙ ） ２Ｈ５ （３）　”　Ｃ−核磁気共鳴スペク トル特性吸収位置（熔 媒＝Ｄ２０ 単位δ （ｐｐｍ）　） ８．６７ （Ｃ−８）、 〆 １３０、７８ （Ｃ−２） １４９、１３ （Ｃ−１） （４）元素分析 （５）固有粘度〔ｆｆ　　（ｆ４媒：水、２５°Ｃ）０
．２０ 以上の結果から樹脂Ｅは、 なる構造を有することが判る。(1) Infrared absorption spectrum characteristics Absorption position CKBr method, unit: ai-') 3400.3000.2050.1630.1520.
1450.1390.1240.1180.1100.
1060.880.780 (2) Proton nuclear magnetic resonance spectral characteristics absorption position (solvent = D20, unit: δ (pp
m) )1.09 (S, 3H, CHzC13
) 2.14 (s, 3H1-岨, ) 2.92 (brd, 2H, CJ1zCH3)
4.1 to 4.6 (m 5 5H1 -CH□ClCf1y) 2H5 (3) ” C-Nuclear magnetic resonance spectral characteristics absorption position (melting medium = D20 unit δ (ppm)) 8.67 (C-8), 〆130, 78 (C-2) 149, 13 (C-1) (4) Elemental analysis (5) Intrinsic viscosity [ff (F4 medium: water, 25°C) 0
．． 20 From the above results, it can be seen that resin E has the following structure.

（なお、式中、核磁気共鳴スペクトルデータより算出し
たｎの値は１５である。） （耐熱性試験例） 本発明樹脂の方法により製造される高分子四級塩の耐熱
性を調べるため前記製造例１及び２で得られた樹脂Ａ及
びＢと市販高分子四級塩（アルドリッチ社製ポリジアリ
ルジメチルアンモニウムクロライド）について示差熱天
秤装置（理学電機型、恒温型示差熱天秤８００２Ｈ型）
を用いて熱減量を次の条件で測定した。(In the formula, the value of n calculated from nuclear magnetic resonance spectrum data is 15.) (Example of heat resistance test) In order to investigate the heat resistance of the polymer quaternary salt produced by the method of the resin of the present invention, Resins A and B obtained in Production Examples 1 and 2 and a commercially available polymer quaternary salt (polydiallyldimethylammonium chloride manufactured by Aldrich) were measured using a differential thermal balance device (Rigaku Denki model, constant temperature differential thermal balance 8002H model).
Thermal loss was measured using the following conditions.

雰囲気：空気中 昇温速度：１０°Ｃ／分 結果を第１図に示す。Atmosphere: in the air Heating rate: 10°C/min The results are shown in Figure 1.

図から明らかなように、本発明の方法により製造される
高分子四級塩は３００°Ｃ迄はとんど重量減が認められ
なかった。As is clear from the figure, almost no weight loss was observed in the polymer quaternary salt produced by the method of the present invention up to 300°C.

一方、市販高分子四級塩は、１００　”Ｃ位から重量減
少が認められ、３００°Ｃで約１７％の熱減量があるこ
とがわかる。On the other hand, in the commercially available polymeric quaternary salt, a weight loss is observed from the 100''C position, and it can be seen that there is a heat loss of about 17% at 300°C.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は、本発明の方法により製造される高分子四級塩
と従来品との耐熱性を示す熱天秤チャートである。FIG. 1 is a thermobalance chart showing the heat resistance of the polymer quaternary salt produced by the method of the present invention and a conventional product.

Claims (1)

【特許請求の範囲】 １、下記式（ I ） ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は水素原子、Ｃ＿１〜＿１＿７のアルキ
ル基またはＣ＿６〜＿８のアリール基を、Ｒ＿２および
Ｒ＿３は同一または異なる置換基で水素原子またはＣ＿
１〜＿３のアルキル基を、Ｒ＿４は水素原子またはメチ
ル基を、Ｘはハロゲン原子を、ｎは２〜５０００の整数
をそれぞれ表わす） で示される新規な高分子四級塩を製造するにあたり、下
記式（II） ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は水素原子、Ｃ＿１〜＿１＿７のアルキ
ル基またはＣ＿６〜＿８のアリール基を、Ｒ＿２および
Ｒ＿３は同一または異なる置換基で水素原子またはＣ＿
１〜＿３のアルキル基をそれぞれ表わす） で示されるイミダゾール類を下記式（III） ▲数式、化学式、表等があります▼ （式中、Ｒ＿４は水素原子またはメチル基を、Ｘはハロ
ゲン原子をそれぞれ表わす） で示されるハロメチルオキシラン化合物と水性溶媒中で
反応させることを特徴とする前記式（ I ）で示される
新規な高分子四級塩の製造方法。[Claims] 1. The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a hydrogen atom, C_1 to_1_7 are alkyl groups or C_6 to_8 are aryl groups, R_2 and R_3 are the same or different substituents and are hydrogen atoms or C_
1 to _3 alkyl group, R_4 is a hydrogen atom or a methyl group, X is a halogen atom, and n is an integer of 2 to 5000, respectively). Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a hydrogen atom, C_1 to_1_7 are alkyl groups or C_6 to_8 are aryl groups, and R_2 and R_3 are the same or different substituents and are hydrogen atoms. or C__
The imidazoles represented by the following formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4 represents a hydrogen atom or a methyl group, and X represents a halogen atom, respectively. 1. A method for producing a novel quaternary polymeric salt represented by the formula (I), which comprises reacting the halomethyloxirane compound represented by the formula (I) in an aqueous solvent.
JP2229917A 1990-08-31 1990-08-31 A method for producing a new polymeric quaternary salt Granted JPH03277631A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
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Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2229917A JPH03277631A (en) 1990-08-31 1990-08-31 A method for producing a new polymeric quaternary salt

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP1190283A Division JPS59138228A (en) 1983-01-27 1983-01-27 Novel polymeric quaternary salt

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JPH0424364B2 JPH0424364B2 (en) 1992-04-24

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007114793A1 (en) * 2006-04-05 2007-10-11 Agency For Science, Technology And Research Polyimidazolium salts and poly-nhc-metal complexes
WO2008110007A1 (en) * 2007-03-12 2008-09-18 The Royal Institution For The Advancement Of Learning/Mcgill University Imidazolium-type ionic oligomers
EP2366692A3 (en) * 2010-03-15 2011-11-02 Rohm and Haas Electronic Materials LLC Copper electropating bath and method
US8262895B2 (en) 2010-03-15 2012-09-11 Rohm And Haas Electronic Materials Llc Plating bath and method
US8268157B2 (en) 2010-03-15 2012-09-18 Rohm And Haas Electronic Materials Llc Plating bath and method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5332344A (en) * 1976-09-08 1978-03-27 Tokyo Shibaura Electric Co Zinc alkali storage battery

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5332344A (en) * 1976-09-08 1978-03-27 Tokyo Shibaura Electric Co Zinc alkali storage battery

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007114793A1 (en) * 2006-04-05 2007-10-11 Agency For Science, Technology And Research Polyimidazolium salts and poly-nhc-metal complexes
JP2009532555A (en) * 2006-04-05 2009-09-10 エイジェンシー・フォー・サイエンス，テクノロジー・アンド・リサーチ Polyimidazolium salts and poly-NHC-metal complexes
US8163851B2 (en) 2006-04-05 2012-04-24 Institute Of Bioengineering And Nanotechnology Polymeric salts and poly-NHC-metal complexes
JP2012177138A (en) * 2006-04-05 2012-09-13 Agency For Science Technology & Research Polyimidazolium salt, and poly-nhc-metal complex
WO2008110007A1 (en) * 2007-03-12 2008-09-18 The Royal Institution For The Advancement Of Learning/Mcgill University Imidazolium-type ionic oligomers
EP2366692A3 (en) * 2010-03-15 2011-11-02 Rohm and Haas Electronic Materials LLC Copper electropating bath and method
US8262895B2 (en) 2010-03-15 2012-09-11 Rohm And Haas Electronic Materials Llc Plating bath and method
US8268157B2 (en) 2010-03-15 2012-09-18 Rohm And Haas Electronic Materials Llc Plating bath and method
US8268158B2 (en) 2010-03-15 2012-09-18 Rohm And Haas Electronic Materials Llc Plating bath and method

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