JPS6063204A - Production of quaternarized polystyrene - Google Patents
Production of quaternarized polystyreneInfo
- Publication number
- JPS6063204A JPS6063204A JP17081283A JP17081283A JPS6063204A JP S6063204 A JPS6063204 A JP S6063204A JP 17081283 A JP17081283 A JP 17081283A JP 17081283 A JP17081283 A JP 17081283A JP S6063204 A JPS6063204 A JP S6063204A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- reaction
- chloromethylated
- trialkylamine
- aqueous solution
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/35—Polyalkenes, e.g. polystyrene
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は四級化ポリスチレン類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 quaternized polystyrenes.
さらに詳しくは、無色、無臭、透明で夾雑物の少い四級
化ポリスチレン類の製造方法に関するものである。More specifically, the present invention relates to a method for producing quaternized polystyrene that is colorless, odorless, transparent, and has few impurities.
従来から紙および合成紙の加工剤として低分子量の界面
活性剤、ノニオニソクポリマー、アニオニソクポリマー
およびカチオニソクポリマーか紙力増強、帯電防止、導
電性付与を目的として用いられており、特に第四級アン
モニウムポリマーは導電剤として優れていることか知ら
れており、それらについてU、S、Pat、 3011
918、特公昭50−1154単量体を単独、又は共重
合したもので、モノマーの収量が低く、さらに安定性か
悪く、製造コストが高い等の欠点を有する。Traditionally, low molecular weight surfactants, nonionic polymers, anionic polymers, and cationic polymers have been used as processing agents for paper and synthetic paper for the purpose of increasing paper strength, preventing static electricity, and imparting electrical conductivity. In particular, quaternary ammonium polymers are known to be excellent as conductive agents, and are described in U, S, Pat, 3011.
918, Japanese Patent Publication No. 50-1154 monomer, or a copolymer of monomers, and has drawbacks such as low monomer yield, poor stability, and high production cost.
後者は、第4級アンモニウム塩置換メチル基を有するス
チレン単位を少くとも30重量%含む重合体であり、第
4級アンモニウム塩置換メチル基を有する単量体の重合
、又はポリスチレンに第4級アンモニウム塩置換メチル
基を導入することにより目的物を作成しつるとしている
か単量体の重合による製造は前記ノU、S、Pat、3
011918 (!:同し欠点を有し、又スチレン単位
を有する重合体に第4級アンモニウム塩置換メチル基を
導入する製造法は、クロロメチル化ポリスチレンの固形
分にトリメチルアミン等の三級アミンと直接反応させた
後、過剰のアミンを留去するもので、反応か均一に進行
せず、又反応時間も長くそのため目的物か着色する傾向
かあり、さらに夾雑物の混入か多く製品の性状に問題が
ある。その結果、用途上透明性、印刷適性か十分なもの
ではない。The latter is a polymer containing at least 30% by weight of styrene units having quaternary ammonium salt-substituted methyl groups; The desired product is prepared by introducing a salt-substituted methyl group, or the production by polymerization of monomers is performed using the above-mentioned No.U, S, Pat, 3.
011918 (!: A production method that has the same drawback and introduces a quaternary ammonium salt-substituted methyl group into a polymer having styrene units is to directly add a tertiary amine such as trimethylamine to the solid content of chloromethylated polystyrene. After the reaction, the excess amine is distilled off, so the reaction does not proceed uniformly, and the reaction time is long, so the target product tends to be colored, and there are many problems with the product properties due to the contamination of contaminants. As a result, the transparency and printability are not sufficient for the purpose of use.
本発明者らは、そのような問題点に着目し、鋭意検討を
行った結果、透明性に優れ、着色せず、反応原料による
臭いの少い四級化ポリスチレン類の製造方法を見いたし
、本発明を完成した。The present inventors focused on such problems, and as a result of intensive studies, they discovered a method for producing quaternized polystyrene that has excellent transparency, is not colored, and has little odor due to the reaction raw materials, The invention has been completed.
すなIvち、本発明は平均分子量500以上を有する重
合体中の単量体単位として、少くとも10重量%のクロ
ロメチルスチレン又は/および少くとも10重リアルキ
ルアミンを水溶液、又はそれと水を別々に加え反応を行
い、クロロメチル基にトリアルキルアンモニウム基を導
入した後、反応系を水層と溶剤層の2層に分離し、さら
に未反応トリアルキルアミンを含む溶剤層を分別する事
より、1段の反応で未反応原料を含まない四級化ポリス
チレン類を水溶液として製造する方法である。In other words, the present invention provides an aqueous solution of at least 10% by weight of chloromethylstyrene or/and at least a 10-fold alkylamine as a monomer unit in a polymer having an average molecular weight of 500 or more, or a combination thereof with water. After adding them separately and conducting a reaction to introduce a trialkylammonium group into a chloromethyl group, the reaction system is separated into two layers: an aqueous layer and a solvent layer, and the solvent layer containing unreacted trialkylamine is further separated. , is a method for producing quaternized polystyrene as an aqueous solution in a one-stage reaction that does not contain unreacted raw materials.
これにより得られた四級化ポリスチレン類の水溶液は上
記の問題点を解決し極めて優れたものである。The aqueous solution of quaternized polystyrene thus obtained solves the above problems and is extremely excellent.
本願発明の方法に用いる原料並ひに製造方法について述
へると、本願発明のポリスチレン類としてはスチレン単
体の重合体またはα−メチルスチレン単体の重合体また
はスチレンとα−メチルスチレンの共重合体か挙けられ
る。Regarding the raw materials and manufacturing method used in the method of the present invention, the polystyrene of the present invention is a polymer of simple styrene, a polymer of simple α-methylstyrene, or a copolymer of styrene and α-methylstyrene. can be mentioned.
りOr+メチル化ポリスチレン類としては、少くとも1
0重量%のクロロメチル化スチレン及び/又は少(とも
10重量%のクロロメチル化α−メチルスチレンと残部
をスチレン及び/又はα−メチルスチレンから構成され
る平均分子量500以上の重合体で、クロロメチルスチ
レン又は及びクロロメチルα−メチルスチレンを重合す
るか又は前記ポリスチレン類をクロロメチル化して得ら
れるか、後者の方法か安価て一般的である。ポリスチレ
ン類をクロロメチル化する方法としては公知の方法でよ
く一般に使用されているクロロメチル化剤をフリーデル
クラフッ触媒の存在下、例えばクロロメチルエーテルを
三塩化アルミニウム又は塩化亜鉛の存在下に反応させる
ものであり、その際溶剤の存在下に反応させる方法もあ
る。Or + methylated polystyrenes, at least 1
A polymer with an average molecular weight of 500 or more consisting of 0% by weight of chloromethylated styrene and/or a small amount (both 10% by weight of chloromethylated α-methylstyrene and the balance of styrene and/or α-methylstyrene). The latter method is inexpensive and common, either by polymerizing methylstyrene or chloromethyl α-methylstyrene or by chloromethylating the polystyrenes.As a known method for chloromethylating polystyrenes, The process involves reacting a commonly used chloromethylating agent in the presence of a Friedelkraff catalyst, e.g. chloromethyl ether in the presence of aluminum trichloride or zinc chloride, in the presence of a solvent. There is also a way to react.
以上のごとく得られたクロロメチル化ポリスチレン類に
対し、重量比にて1〜10倍量の水溶性情シ
剤を加え、溶解する。それに奏母廿とクロロメチル化ポ
リスチレン類に導入されているクロロメチル基に対しモ
ル比で1〜1.3倍量のトリアルキルアミンを水溶液と
して、又は水と別々に加えて10〜60℃で1〜10時
間反応させトリアルキルアンモニウム基を導入する。I
・リアルキルアミンとしてはトリメチルアミン、トルエ
チルアミン等が挙けられる。To the chloromethylated polystyrene obtained as described above, a water-soluble stimulant in an amount of 1 to 10 times by weight is added and dissolved. Add trialkylamine in an amount of 1 to 1.3 times in molar ratio to the chloromethyl group introduced into the chloride and chloromethylated polystyrene as an aqueous solution or separately with water and heat at 10 to 60°C. The reaction is carried out for 1 to 10 hours to introduce a trialkylammonium group. I
- Examples of realkylamines include trimethylamine and toluethylamine.
クロロメチル化ポリスチレン類を溶解する水溶これらを
単独もしくは二種以上混合して使用してもよい。Aqueous solutions that dissolve chloromethylated polystyrenes may be used alone or in combination of two or more.
上記のトリアルキルアンモニウムクロリド基の、初め
導入反応において祢斯工は均一な反応系であるか反応か
進行するに従い、未反応原料はクロロメチル化ポリスチ
レン類を溶解するに使用した溶剤層に、又目的とする四
級化ポリスチレン類は水層に移行し、反応終了後静置す
ると溶剤層き水層の2層に分離する。静置後溶剤眉を分
離除去して、未反応原料を含まない四級化ポリスチレン
類を水溶液として得る。必要に応して水溶液中に含まれ
る微量の溶剤はl・ノピング又は水蒸気蒸留等で除去で
きる。In the initial reaction of introducing the above-mentioned trialkylammonium chloride group, the reaction system is homogeneous, or as the reaction progresses, unreacted raw materials are transferred to the solvent layer used to dissolve the chloromethylated polystyrene. The target quaternized polystyrene migrates to the aqueous layer, and when the reaction is left standing after the reaction is completed, it separates into two layers: a solvent layer and an aqueous layer. After standing, the solvent is separated and removed to obtain a quaternized polystyrene containing no unreacted raw materials as an aqueous solution. If necessary, trace amounts of solvent contained in the aqueous solution can be removed by l.knopping or steam distillation.
この様にして得た四級化ポリスチレン類の水溶液は透明
度か高く、着色も無く、臭いも少く、長期保存安定性に
優れている。The aqueous solution of quaternized polystyrene obtained in this manner is highly transparent, has no coloration, has little odor, and has excellent long-term storage stability.
本願発明の四級化ポリスチレン水溶液を紙又は合成紙の
加工剤として使用する場合、得られた水溶液をそのまま
で、又は水で希釈して直接塗布するか又は浸漬して塗布
でき、塗布時未反応アミン等の臭いか無い為作業環境」
二好ましく、夾雑物か少い為塗りむらか無く印刷適性の
優れた塗布面が得られる。When the aqueous solution of quaternized polystyrene of the present invention is used as a processing agent for paper or synthetic paper, the resulting aqueous solution can be applied as is, or diluted with water and applied directly or by dipping, and no reaction occurs at the time of application. Work environment is good as there is no smell of amine etc.
2. It is preferable that the amount of impurities is small, so that a coated surface with excellent printability without uneven coating can be obtained.
以下、実施例により詐細に説明するか本方法はこれら実
施例に限定されるものではない。Hereinafter, the present method will be described in detail with reference to examples, but the present method is not limited to these examples.
実施例1
ポリビニルヘンシルホモポリマー(平均分子量約200
00.100%クロロメチル化物) 98.59をジメ
チルポルムアミド975gに溶解し+温度30℃にてト
リメチルアミンの10%水溶液383.59を徐々に添
加した。添加終了後同温度にて5時間反応し、室温まで
冷却して撹拌を停止すると、反応混合液は水層と溶剤層
の2層に分離した。溶剤層を分別し無色透明でかつ臭い
の少い284%のポリビニルへノシルトリメヂルアンモ
ニウムクロリドを含む水溶液を得た。Example 1 Polyvinylhensyl homopolymer (average molecular weight approximately 200
00.100% chloromethylated product) 98.59 was dissolved in 975 g of dimethylpolamide, and 383.59 of a 10% aqueous solution of trimethylamine was gradually added at a temperature of 30°C. After the addition was completed, the reaction was carried out at the same temperature for 5 hours, and when the mixture was cooled to room temperature and stirring was stopped, the reaction mixture was separated into two layers: an aqueous layer and a solvent layer. The solvent layer was separated to obtain a colorless and transparent aqueous solution with little odor and containing 284% polyvinylhenosyltrimedyl ammonium chloride.
マー(平均分子ffl 10000 )の50%クロロ
メチル化物944yをジオキサン472gに溶解し、さ
らに水247.69を加え温度35℃にてトリエチルア
ミン38.9 ’jを徐々に添加する。添加終了後2時
間で50℃まて昇温し、同温度で4時間反応を続け、そ
の後常温まで冷却すると、2層に分離した。溶剤層を分
別し無色透明で臭いの無い四級化ポリマーの水溶液を得
た。固形分濃度は344%であった。50% chloromethylated product 944y of mer (average molecule ffl 10000) was dissolved in 472 g of dioxane, 247.69 g of water was further added, and 38.9'j of triethylamine was gradually added at a temperature of 35°C. The temperature was raised to 50° C. 2 hours after the addition was completed, the reaction was continued at the same temperature for 4 hours, and then the mixture was cooled to room temperature and separated into two layers. The solvent layer was separated to obtain a colorless, transparent, and odorless aqueous solution of the quaternized polymer. The solid content concentration was 344%.
実施例3
クロロメチル化率10%のポリスチレン(平均分子量約
1000 )108.79を109gのアセトノに溶解
し、さらに水108.7 !を加え温度40℃で30%
トリメチルアミン水溶液256gを徐々に添加し、同温
度で3時間反応を行い、ついて常温まで冷却し撹拌を停
止すると2層に分離した。溶剤層を分別してはとんと無
色で臭いが無くやや濁った四級化ポリマーの水溶液を得
た。固形分濃度は475%であった。Example 3 Polystyrene with a chloromethylation rate of 10% (average molecular weight approximately 1000) 108.79 g was dissolved in 109 g of acetonate, and water was further added 108.7 g! and 30% at a temperature of 40℃.
256 g of a trimethylamine aqueous solution was gradually added, and the reaction was carried out at the same temperature for 3 hours. When the mixture was cooled to room temperature and stirring was stopped, the mixture was separated into two layers. The solvent layer was separated to obtain a colorless, odorless, slightly cloudy aqueous solution of the quaternized polymer. The solid content concentration was 475%.
実施例4
クロロメチル化率30%のポリスチレン(平均分子量約
2500) 118.39を354.89のテトラヒド
ロフランに溶解し、温度45℃にて8看7%トリエチル
アミン水溶液203.9 f/を徐々に添加し、添加終
了後同温度て3時間反応を続け、その後常温まで冷却す
ると2層に分離した。溶剤層を分別しはとんと無色透明
て臭いの少い四級化ポリマー水溶液(固形分濃度40%
)を得た。Example 4 Polystyrene 118.39 (average molecular weight approximately 2500) with a chloromethylation rate of 30% was dissolved in 354.89 tetrahydrofuran, and 203.9 f/8% 7% triethylamine aqueous solution was gradually added at a temperature of 45°C. After the addition was completed, the reaction was continued at the same temperature for 3 hours, and then cooled to room temperature and separated into two layers. The solvent layer is separated and a clear, colorless and odorless quaternized polymer aqueous solution (solid content concentration 40%) is obtained.
) was obtained.
比較例1
クロロメチル化率30%のポリスチレン(平均分子量約
2500 ) 118.39を354.89のテトラヒ
ドロフランに溶解し、さらに88′7%トリエヂルアミ
ン水溶液203.99を添加して実施例4と同様に反応
を行った。反応終了後エバポレーターで溶剤を除去し、
さらに539の純水を加えて固形分濃度を40%に調整
して、濁った黄色て異臭のある四級化ポリマー水溶液を
得た。Comparative Example 1 Polystyrene with a chloromethylation rate of 30% (average molecular weight about 2500) 118.39 was dissolved in 354.89 of tetrahydrofuran, and 203.99 of an 88'7% triedylamine aqueous solution was added and the same procedure as in Example 4 was carried out. The reaction was carried out. After the reaction is complete, remove the solvent with an evaporator,
Furthermore, 539 pure water was added to adjust the solid content concentration to 40% to obtain a turbid yellow quaternized polymer aqueous solution with a strange odor.
」二質紙に実施例、比較例で製造した四級化ボリスチノ
ン類を塗布量2g/m2となるようにロールにて塗布処
理し、表面抵抗値を測定した。その結果を表−1に示す
。表面抵抗値は25℃、30%相対湿度の条件下てタケ
ダ理研(栢→製エレクトロメーターを用いて測定した。The quaternized boristinones produced in the Examples and Comparative Examples were coated on bi-quality paper using a roll at a coating amount of 2 g/m2, and the surface resistance values were measured. The results are shown in Table-1. The surface resistance value was measured at 25° C. and 30% relative humidity using an electrometer manufactured by Takeda Riken (Haki →).
表−1Table-1
Claims (1)
して、少くとも10重量%のクロロメチル化◇ スチレン又は/および少くとも10重ff1%クロロメ
チル化α−メチルスチレンを含むクロロメチル化ポリス
チレン重合体を水溶性溶剤に溶解し、トリアルキルアミ
ンを水溶液、又はそれと水を別々に加え反応を行い、ク
ロルメチル基にトリアルキルアンモニウム基を導入した
後、反応系を水層と溶剤層の2層に分離し、反応生成物
を水溶液として得ることを特徴とする四級化ポリスチレ
ン類の製造方法。[Scope of Claims] At least 10% by weight of chloromethylated styrene or/and at least 10% by weight of chloromethylated α-methylstyrene as a monomer unit in a polymer having an average molecular weight of 500 or more A chloromethylated polystyrene polymer containing chloromethyl is dissolved in a water-soluble solvent, a trialkylamine is added in an aqueous solution, or it and water separately to perform a reaction. After introducing a trialkylammonium group into a chloromethyl group, the reaction system is separated into an aqueous layer. A method for producing quaternized polystyrene, which comprises separating into two layers, a solvent layer and a solvent layer, and obtaining a reaction product as an aqueous solution.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17081283A JPS6063204A (en) | 1983-09-16 | 1983-09-16 | Production of quaternarized polystyrene |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17081283A JPS6063204A (en) | 1983-09-16 | 1983-09-16 | Production of quaternarized polystyrene |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6063204A true JPS6063204A (en) | 1985-04-11 |
JPH0521124B2 JPH0521124B2 (en) | 1993-03-23 |
Family
ID=15911788
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17081283A Granted JPS6063204A (en) | 1983-09-16 | 1983-09-16 | Production of quaternarized polystyrene |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6063204A (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4952290A (en) * | 1972-09-16 | 1974-05-21 | ||
JPS516730A (en) * | 1974-07-09 | 1976-01-20 | Konishiroku Photo Ind | DENSHISHASHIN FUKUSHAHONIOKERU GENZOHOHO |
JPS5755902A (en) * | 1981-07-24 | 1982-04-03 | Tokyo Organ Chem Ind Ltd | Production of functional crosslinked copolymer |
-
1983
- 1983-09-16 JP JP17081283A patent/JPS6063204A/en active Granted
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4952290A (en) * | 1972-09-16 | 1974-05-21 | ||
JPS516730A (en) * | 1974-07-09 | 1976-01-20 | Konishiroku Photo Ind | DENSHISHASHIN FUKUSHAHONIOKERU GENZOHOHO |
JPS5755902A (en) * | 1981-07-24 | 1982-04-03 | Tokyo Organ Chem Ind Ltd | Production of functional crosslinked copolymer |
Also Published As
Publication number | Publication date |
---|---|
JPH0521124B2 (en) | 1993-03-23 |
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