JPS584730B2 - Method for producing cationic polymer - Google Patents
Method for producing cationic polymerInfo
- Publication number
- JPS584730B2 JPS584730B2 JP50102812A JP10281275A JPS584730B2 JP S584730 B2 JPS584730 B2 JP S584730B2 JP 50102812 A JP50102812 A JP 50102812A JP 10281275 A JP10281275 A JP 10281275A JP S584730 B2 JPS584730 B2 JP S584730B2
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- JP
- Japan
- Prior art keywords
- polymer
- cationic polymer
- reaction
- mol
- epichlorohydrin
- 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
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】
本発明は抄成紙の湿潤強度を高めることなく、製紙用定
着剤として優れた効果を奏し、凝集剤、帯電防止剤、防
錆剤等としての用途をも有する新規な陽イオン性ポリマ
ーの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is a novel product that exhibits excellent effects as a fixing agent for papermaking without increasing the wet strength of paper, and also has uses as a flocculant, an antistatic agent, a rust preventive agent, etc. The present invention relates to a method for producing a cationic polymer.
パルプ抄成紙に種々の性質を附与する目的で、原料パル
プに各種の物質を添加し、これを定着せしめるための定
着剤として各種陽イオン性ポリマーが使用されているが
、これらの陽イオン性ポリマーの多くは同時に抄成紙の
湿潤強度を高めてしまう。In order to impart various properties to pulp paper, various substances are added to the raw pulp, and various cationic polymers are used as fixing agents to fix the substances. Many of these polymers also increase the wet strength of the paper.
したがって、かかる陽イオン性ポリマーを製紙用定着剤
として使用した抄成紙の損紙を回収して再性利用する際
の離解作用が著しく困難となる欠点を伴なうことになり
、抄成紙の湿潤強度を上昇せしめることのない、しかも
優れた製紙用定着剤としての効果を奏する陽イオン性ポ
リマーの出現が当業界で望まれていたのが現状である。Therefore, when the waste paper of paper made using such a cationic polymer is used as a papermaking fixing agent is recovered and reused, the disintegrating action becomes extremely difficult. There has been a desire in the art for a cationic polymer that does not increase the wet strength of paper and that also has an excellent effect as a fixing agent for papermaking.
本発明は、特許請求の範囲に記載した構成とすることに
より、上記のような欠点を伴なうことなく、製紙用定着
剤としての優れた効果を有し、且つ貯蔵安定性が大きく
、しかも凝集剤、帯電防止剤、防錆剤等の用途をも有す
る新規な陽イオン性ポリマーの製造方法を提供するもの
である。The present invention, having the configuration described in the claims, has excellent effects as a papermaking fixing agent without the above-mentioned drawbacks, has high storage stability, and The present invention provides a method for producing a novel cationic polymer that also has uses such as a flocculant, an antistatic agent, and a rust preventive agent.
本発明の陽イオン性ポリマーの製造方法は、モノメチル
アミンとエピクロルヒドリンとを反応させて或る程度以
上の高分子量のポリマーを確実に生成させる第１段階反
応と、前記第１段階反応で得られたポリマーに一定量の
エビクロルヒドリン、即ち、第１段階反応でのポリマー
を得る際に使用したモノメチルアミン１モルに対して０
．３〜１モルのエピクロルヒドリンを添加反応させ、第
４級アンモニウム化合物とする第２段階反応とからなる
ものであり、かくして第４級アンモニウム化合物たる陽
イオン性ポリマーを得るものである。The method for producing a cationic polymer of the present invention includes a first stage reaction in which monomethylamine and epichlorohydrin are reacted to reliably produce a polymer having a high molecular weight above a certain level, and a polymer obtained in the first stage reaction. A certain amount of shrimp chlorohydrin was added to the polymer, i.e. 0 per mole of monomethylamine used in obtaining the polymer in the first stage reaction.
．． This process consists of a second step reaction in which 3 to 1 mol of epichlorohydrin is added and reacted to form a quaternary ammonium compound, thus obtaining a cationic polymer which is a quaternary ammonium compound.
本発明で得られる新規化合物たる陽イオン性ポリマーが
前述の通りの製紙用定着剤として優れた効果を奏するた
めには、該ポリマーの分子量が或る程度大きくなってい
ることが必要である。In order for the cationic polymer, which is the new compound obtained in the present invention, to exhibit excellent effects as a fixing agent for paper manufacturing as described above, it is necessary that the molecular weight of the polymer be increased to a certain extent.
したがって、本発明においては、第１段階反応でのポリ
マー生成反応で、分子量が或る程度大きなポリマーを確
実に得ることが必要であり、このため、この第１段階反
応は、モノメチルアミンとエピクロルヒドリンとの等モ
ル反応を、温和な条件下で、即ち、常温〜１００℃のも
とて比較的長時間かけて行うものである。Therefore, in the present invention, it is necessary to reliably obtain a polymer with a relatively large molecular weight in the polymer production reaction in the first stage reaction, and for this reason, this first stage reaction is performed by combining monomethylamine and epichlorohydrin. The equimolar reaction is carried out under mild conditions, that is, at room temperature to 100°C over a relatively long period of time.
この第１段階反応で得られたポリマーに更にエビクロル
ヒドリンを反応させ、第４級アンモニウム化合物たる陽
イオン性ポリマ一を得る本発明の第２段階反応は、前記
第１段階反応におけるポリマー生成反応で使用したモノ
メチルアミン１モル（即ちエビクロルヒドリン１モルで
もある）に対して、エピクロルヒドリン０．３〜１モル
を前記第１段階反応で得られたポリマーに添加して反応
させ、目的生成物たる第４級アンモニウム化合物による
陽イオン性ポリマーを得るものである。The second step reaction of the present invention involves further reacting shrimp chlorohydrin with the polymer obtained in the first step reaction to obtain a cationic polymer which is a quaternary ammonium compound. For 1 mol of monomethylamine (that is, 1 mol of epichlorohydrin) used in the reaction, 0.3 to 1 mol of epichlorohydrin is added to the polymer obtained in the first step reaction and reacted to produce the desired product. A cationic polymer is obtained using a quaternary ammonium compound.
この第２段階における反応は、加温により比較的短時間
で完了するが、この段階で使用するエピクロルヒドリン
の量を、第１段階でのポリマー生成反応で使用したモノ
メチルアミン１モルに対して０．３モル未満にすると、
得られる陽イオン性ポリマーのカチオン性が十分でなく
、該化合物による前述の製紙用定着剤としての効果は十
分ではなくなる。The reaction in this second stage is completed in a relatively short time due to heating, but the amount of epichlorohydrin used in this stage is 0.00% per mole of monomethylamine used in the polymer production reaction in the first stage. If it is less than 3 moles,
The resulting cationic polymer does not have sufficient cationic properties, and the effect of the compound as a fixing agent for paper manufacturing is no longer sufficient.
本発明の陽イオン性ポリマーの製造方法においでは、モ
ノメチルアミンに対してエビクロルヒドリンの添加及び
反応は必らず二段に行なわなければならなく、使用する
エピクロルヒドリンの全量をモノメチルアミンに対して
最初に添加し、一段で反応を行なった場合には製紙用定
着剤としての優れた効果を奏する陽イオン性ポリマーを
得ることはできない。In the method for producing a cationic polymer of the present invention, the addition and reaction of epichlorohydrin to monomethylamine must be carried out in two stages, and the total amount of epichlorohydrin used must be adjusted to the monomethylamine. If it is added first and the reaction is carried out in one step, it is not possible to obtain a cationic polymer that exhibits excellent effects as a fixing agent for paper manufacturing.
かかるモノメチルアミンに対して、大過剰量のエピクロ
ルヒドリンを最初に添加して一段で反応を行なった場合
に得られる陽イオン性ポリマーが、本発明の製造方法に
よって得られる陽イオン性ポリマーと区別されるのは、
前者の生成ポリマーは、過剰量のエピクロルヒドリンに
よって一度出来た，主鎖が切断されてしまうために、後
者の生成ポリマーに比較して、その平均分子量が著しく
低減されたものとなる点であると推測される。The cationic polymer obtained when a large excess amount of epichlorohydrin is first added to such monomethylamine and the reaction is carried out in one step is distinguished from the cationic polymer obtained by the production method of the present invention. The thing is,
It is speculated that the average molecular weight of the former polymer is significantly reduced compared to the latter polymer, as the main chain once formed is cleaved by an excessive amount of epichlorohydrin. be done.
したかって、一段の反応で得られた陽イオン性ポリマー
が、製紙用定着剤としての優れた好果を奏しなくても、
二段の反応で得られた陽イオン性ポリマーがその優れた
効果を発揮するものと考えられるが、この点は注目され
るべき点である。Therefore, even if the cationic polymer obtained by one-step reaction does not show excellent results as a fixing agent for papermaking,
It is thought that the cationic polymer obtained through the two-stage reaction exhibits its excellent effects, and this point should be noted.
本発明の製造方法によって得られる陽イオン性ポリマー
は、本発明の製造方法における反応の第一段階で生成す
る（−Ｎ−ＣＨ２ＣＨ（ＯＨ）Ｃ｛２−）の繰り返し単
位を有するポリマーを主成分としたポリマーを、反応の
第二段階で、
の繰り返し単位を有する第４級アンモニウム化合物を主
成分とする陽イオン性ポリマーとすることによって得ら
れる新規化合物であり、凝集剤、帯電防止剤、防錆剤等
としての用途も有するが、特に貯蔵安定性が犬で、抄成
紙の湿潤強度を高めることのない優れた製紙用定着剤と
しての用途を有する点で特徴づけられ、特にその効果は
中性紙抄成において顕著である。The cationic polymer obtained by the production method of the present invention is mainly composed of a polymer having repeating units of (-N-CH2CH(OH)C{2-) produced in the first step of the reaction in the production method of the present invention. This is a new compound obtained by converting the polymer into a cationic polymer whose main component is a quaternary ammonium compound having repeating units in the second step of the reaction. It also has uses as a rusting agent, etc., but it is particularly characterized by its excellent storage stability and its use as an excellent fixative for papermaking without increasing the wet strength of papermaking. This is noticeable in neutral paper making.
以下、本発明の陽イオン性ポリマーの製造方法を各実施
例により説明し、得られた陽イオン性ポリマーの製紙用
定着剤としての効果および凝集剤としての効果を併せて
明瞭にする。Hereinafter, the method for producing the cationic polymer of the present invention will be explained using Examples, and the effects of the obtained cationic polymer as a papermaking fixing agent and as a flocculant will be clarified.
実施例 １
温度計、還流冷却器、滴下ロ一ト、攪拌機を付した四ツ
目丸底フラスコにモノメチルアミン４０％水溶液７７．
５９（ｘモル）を仕込み、温度を３０℃以下に保ちなが
らエピクロルヒドリン９２．５９（１モル）を２時間か
けて滴下した。Example 1 A 40% aqueous solution of monomethylamine was placed in a four-eye round bottom flask equipped with a thermometer, reflux condenser, dropping funnel, and stirrer.
59 (x mol) was charged, and 92.59 (1 mol) of epichlorohydrin was added dropwise over 2 hours while keeping the temperature below 30°C.
滴下終了後そのまま室温に２４時間放置し、次いで８０
℃に加温して１２時間反応させしかる後水３５０ｇを加
え、さらにエピクロルヒドリン４６．３ｇ（０．５モル
）を加えて、８０℃以上で３時間反応させ、繰り返し単
位
を有する陽イオン性ポリマーを主成分とするポリマー（
イ）の濃度２４．８％の反応生成物溶液６１２ｇを得た
。After dropping, leave it at room temperature for 24 hours, then leave it at room temperature for 80 hours.
℃ and reacted for 12 hours, then added 350 g of water, further added 46.3 g (0.5 mol) of epichlorohydrin, and reacted at 80℃ or higher for 3 hours to form a cationic polymer having repeating units. The main component is polymer (
612 g of a reaction product solution having a concentration of 24.8% was obtained.
得られた陽イオン性ポリマーの溶液は、半透明で貯蔵安
定性の良好なものであった。The resulting cationic polymer solution was translucent and had good storage stability.
実施例 ２
温度計、還流冷却器、滴下ロート、攪拌機を付した四ツ
ロ丸底フラスコにモノメチルアミン４０％水溶液７７．
５ｇ（１モル）を仕込み、温度を３０℃以下に保ちなが
らエピクロルヒドリン９２．５ｇ（１モル）を２時間か
けて滴下した。Example 2 A 40% aqueous solution of monomethylamine was placed in a four-sided round bottom flask equipped with a thermometer, reflux condenser, dropping funnel, and stirrer.
5 g (1 mol) of epichlorohydrin was charged, and 92.5 g (1 mol) of epichlorohydrin was added dropwise over 2 hours while keeping the temperature below 30°C.
滴下終了後そのまま室温に２４時間放置し、次いで８０
℃に加温して１２時間反応させ、しかる後水４５７ｇを
加え、さらにエピクロルヒドリン９２．５ｇ（１モル）
を加えて、８０℃以上で３時間反応させ、ポリマー（Ａ
）の主成分と同様の繰り返し単位を有する陽イオン性ポ
リマーを主成分とするポリマー（Ｂ）の濃度２５．９％
の反応生成物溶液７２０ｇを得た。After dropping, leave it at room temperature for 24 hours, then leave it at room temperature for 80 hours.
℃ and reacted for 12 hours, then 457 g of water was added, and further 92.5 g (1 mol) of epichlorohydrin was added.
was added and reacted at 80°C or higher for 3 hours to form a polymer (A
) Concentration of polymer (B) whose main component is a cationic polymer having the same repeating unit as the main component of 25.9%
720 g of reaction product solution was obtained.
得られた陽イオン性ポリマーの溶液は、実施例１で得ら
れたものと同様に、半透明で、貯蔵安定性の良好なもの
であった。The resulting cationic polymer solution, similar to that obtained in Example 1, was translucent and had good storage stability.
上記実施例１および実施例２によって得られた第４級ア
ンモニウム化合物である陽イオン性ポリマー（Ａ）およ
び（Ｂ）の製紙用定着剤としての効果および凝集剤とし
ての効果を、繰り返し単位
マーを主成分としたポリマーと比較して検討するために
次の様な方法によって二種のポリマー（Ｃｌ（Ｄｉを得
た。The effect of the cationic polymers (A) and (B), which are the quaternary ammonium compounds obtained in Example 1 and Example 2 above, as a fixing agent for papermaking and as a flocculant was evaluated using the repeating unit mer. Two types of polymers (Cl(Di) were obtained by the following method for comparison and study with the polymer as the main component.
ポリマー（Ｃ）の製造
温度計、還流冷却器、滴下ロート、攪拌機を付した四ツ
目丸底フラスコにモノメチルアミン４０％水溶液７７．
５ｇ（１モル）を仕込み温度３０℃以下に保ちながらエ
ピクロルヒドリン９２．５ｇ（１モル）を２時間かけて
滴下した。Preparation of Polymer (C) A 40% aqueous monomethylamine solution (77.
92.5 g (1 mol) of epichlorohydrin was added dropwise over 2 hours while maintaining the charging temperature at 30° C. or lower.
滴下終了後そのまま室温に２４時間放置し、次いで８０
℃に加温し、１２時間反応させて繰り返し単位マーを主
成分とするポリマー（ｃ）の濃度８１．２％反応生成分
物溶液１７０ｇを得た。After dropping, leave it at room temperature for 24 hours, then leave it at room temperature for 80 hours.
C. and reacted for 12 hours to obtain 170 g of a reaction product fraction solution with a concentration of 81.2% polymer (c) whose main component is a repeating unit mer.
得られたポリマ一の溶液は粘稠かつ透明なものであった
。The resulting polymer solution was viscous and transparent.
ポリマー（Ｄ）の製造
温度計、還流冷却器、滴下ロート、攪拌機を付した四ツ
目丸底フラスコにモノメチルアミン４０％水溶液７７．
５ｇ（１モル）を仕込み、温度を３０℃以下に保ちなが
らエピクロルヒドリン１３８．８ｇ（１．５モル）を２
時間かけて滴下した。Preparation of Polymer (D) A 40% aqueous solution of monomethylamine (77.
5g (1 mol) of epichlorohydrin, and while keeping the temperature below 30°C, 138.8g (1.5 mol) of epichlorohydrin was added to 2.
It dripped over time.
滴下終了後そのまま室温に２４時間放置し、次いで８０
℃に加温し、１２時間反応させ、しかる後水３５０ｇ加
え、８０℃以上で３時間反応させて、ポリマー（Ａ）の
主成分と同様の繰り返し単位を有するポリマーを主成分
とするポリマー（ｄ）の濃度２５％の透明な反応生成物
溶液６１２ｇを得た。After dropping, leave it at room temperature for 24 hours, then leave it at room temperature for 80 hours.
℃, reacted for 12 hours, then added 350 g of water, and reacted at 80℃ or higher for 3 hours to obtain a polymer (d 612 g of a clear reaction product solution with a concentration of 25% were obtained.
試験１
上記実施例１，２で得られた陽イオン性ポリマー（Ａ）
，（Ｂ）の製紙用定着剤としての効果。Test 1 Cationic polymer (A) obtained in Examples 1 and 2 above
, (B) as a fixing agent for paper manufacturing.
カナディアンスクンダードフリーネス３５０ＣＣのＬ−
ＢＫＰ２．４％スラリーに、石油樹脂サイズ剤〔商品名
コロパ−ルｐ−ｉｏｏ（星光化学工業株式会社製）〕を
対気乾パルプ固形分換算１％相当量を添加し、前記ポリ
マー類からなる定着剤を対気乾パルプ固形分換算０．１
％相当量を添加し、攪拌後手抄機〔商品名ＴＡＰＰＩス
タンダードシ一トマシン（東洋精機製）〕を用いて抄紙
し、坪量６０ｇの手抄紙を得た。Canadian Scundado Freeness 350CC L-
A petroleum resin sizing agent [trade name Colopal p-ioo (manufactured by Seiko Kagaku Kogyo Co., Ltd.)] was added to the BKP 2.4% slurry in an amount equivalent to 1% in terms of air-dried pulp solid content, and the resulting slurry was made from the above-mentioned polymers. The fixing agent is converted to an air-dried pulp solid content of 0.1
After stirring, paper was made using a hand paper machine [trade name: TAPPI Standard Sheet Machine (manufactured by Toyo Seiki)] to obtain hand paper with a basis weight of 60 g.
得られた手抄紙のステキヒトサイズ度の測定結果は下表
のごとくであり、何れの手抄紙も離解機により容易に離
解でき、かかる手抄紙を損紙として回収する場合の困難
性は皆無である。The results of measuring the Steckigt sizing degree of the obtained handmade paper are as shown in the table below, and all of the handmade papers can be easily disintegrated using a disintegrator, and there is no difficulty in recovering such handmade paper as waste paper. be.
表より明らかなように、本発明の製造方法により得られ
た陽イオン性ポリマーを製紙用定着剤として使用した場
合には、同時に添加したサイズ剤の定着度が向上し、サ
イズ度の大幅な向上がみられる。As is clear from the table, when the cationic polymer obtained by the production method of the present invention is used as a fixing agent for paper manufacturing, the fixing degree of the sizing agent added at the same time is improved, and the sizing degree is significantly improved. can be seen.
試験２
実施例１，２で得られた陽イオン性ポリマー（Ａ），（
Ｂ）の凝集剤としての効果。Test 2 Cationic polymer (A) obtained in Examples 1 and 2 (
B) Effect as a flocculant.
クレイ１％懸濁水を作り、２００ＣＣ沈降測定用メスフ
ラスコを用いて前記陽イオン性ポリマー（５），（Ｂ）
ポリマー（ｃ），（Ｄ）のそれぞれ０．１％水溶液を１
ｃｃ宛別々のメスフラスコに加えて振盪後静置し、フロ
ック形成能および沈降速度を比較したが、ポリマー（Ｃ
）Ａポリマー（Ｄ）の水溶液を加えたものに比較して、
陽イオン性ポリマー（Ａ），（Ｂｌを加えたものの凝集
効果が優れていた。Make a 1% clay suspension water and add the cationic polymers (5) and (B) using a 200CC volumetric flask for sedimentation measurement.
1% aqueous solution of each of polymers (c) and (D)
The polymer (C
)A compared to the one containing an aqueous solution of polymer (D),
The aggregation effect of the cationic polymer (A) and (Bl) added was excellent.
Claims (1)
ン１モル、温和な条件下で、即ち常温〜１００℃のもと
て比較的長時間かけて反応させることによりポリマーを
生成させる第１段階反応と、前記第１段階反応で得られ
たポリマーに、該第１段階反応で使用したモノメチルア
ミン１モルに対して０．３〜１モルのエピクロルヒドリ
ンを添加反応させ第４級アンモニウム化合物を得る第２
段階反応とからなることを特徴とする陽イオン性ポリマ
ーの製造方法。1. A first step reaction in which a polymer is produced by reacting 1 mol of epichlorohydrin with 1 mol of monomethylamine under mild conditions, that is, at room temperature to 100° C. over a relatively long period of time; A second step in which 0.3 to 1 mol of epichlorohydrin is added to the polymer obtained in the step reaction to obtain a quaternary ammonium compound per 1 mol of monomethylamine used in the first step reaction.
A method for producing a cationic polymer, comprising a stepwise reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50102812A JPS584730B2 (en) | 1975-08-25 | 1975-08-25 | Method for producing cationic polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP50102812A JPS584730B2 (en) | 1975-08-25 | 1975-08-25 | Method for producing cationic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5226600A JPS5226600A (en) | 1977-02-28 |
| JPS584730B2 true JPS584730B2 (en) | 1983-01-27 |
Family
ID=14337442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50102812A Expired JPS584730B2 (en) | 1975-08-25 | 1975-08-25 | Method for producing cationic polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS584730B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5317397A (en) * | 1976-07-30 | 1978-02-17 | Japanese National Railways<Jnr> | Input card for simple type commutation ticket issuing apparatus |
| JPS6163799A (en) * | 1984-08-31 | 1986-04-01 | 三井サイテック株式会社 | Conductive base paper |
| US4944812A (en) * | 1988-11-16 | 1990-07-31 | Henkel Corporation | Tannin mannich adducts for improving corrosion resistance of metals |
| KR102101529B1 (en) * | 2012-09-21 | 2020-04-17 | 다우 글로벌 테크놀로지스 엘엘씨 | Dye fixative agents and methods |
-
1975
- 1975-08-25 JP JP50102812A patent/JPS584730B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5226600A (en) | 1977-02-28 |
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