JPS62207304A - Production of copolymer having surface activity - Google Patents

Production of copolymer having surface activity

Info

Publication number
JPS62207304A
JPS62207304A JP5074286A JP5074286A JPS62207304A JP S62207304 A JPS62207304 A JP S62207304A JP 5074286 A JP5074286 A JP 5074286A JP 5074286 A JP5074286 A JP 5074286A JP S62207304 A JPS62207304 A JP S62207304A
Authority
JP
Japan
Prior art keywords
copolymer
polymerization
group
hydrocarbon group
saponification
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.)
Pending
Application number
JP5074286A
Other languages
Japanese (ja)
Inventor
Tomohiko Nomura
智彦 野村
Osamu Ishiguro
修 石黒
Hiroshi Inoue
弘 井上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Denka Co Ltd
Original Assignee
Denki Kagaku Kogyo KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Denki Kagaku Kogyo KK filed Critical Denki Kagaku Kogyo KK
Priority to JP5074286A priority Critical patent/JPS62207304A/en
Publication of JPS62207304A publication Critical patent/JPS62207304A/en
Pending legal-status Critical Current

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
    • 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
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof
    • 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)
  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

PURPOSE:To obtain the titled copolymer which is excellent in water solubility and can give a water-resistant film and is useful as an emulsion stabilizer, a paper-making chemical, a binder, or the like, by copolymerizing a quat. ammonium salt-containing unsaturated monomer with a vinyl ester and saponifying the obtained copolymer with an alkali in an alcohol. CONSTITUTION:An unsaturated monomer (A) having a quat. ammonium salt group having at least one 8-22C hydrocarbon group, represented by formula I, II or III [wherein R1 is an 8-22C (substituted) hydrocarbon group, R2-3 are each a 1-22C alkyl, R4 is H or a lower alkyl, R7-9 are each R4 or a (substituted) phenyl and X<-> is an anion] is copolymerized with a vinyl ester (B) such as vinyl acetate at 50-70 deg.C in the presence of a radical polymerization initiator (C) to obtain a copolymer having a degree of polymerization of 200-5,000 and a content of component A of 0.01-20mol%. This copolymer is saponified at 10-50 deg.C in the presence of an alkali catalyst (e.g., NaOH) to a degree of saponification of 99.99-70mol% to form a white gel or precipitate, which is, if necessary, ground, washed and dried.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はポリビニルアルコール（以下ＰＶＡと略記）鎖
中に界面活性能を有する基を導入した新規な共重合体の
製法に関する。この新規な共重合体は従来のＰＴＡの用
途に加えて、エマルジョン重合乳化安定剤、高分子凝集
剤、紙力増強・サイズ性向上・歩留向上環の製紙用薬剤
、経糸サイジング用糊剤、繊維染色性改良剤、帯電防止
剤、紙用表面サイズ剤、顔料コーティング用バインダー
、無機繊維等のバインダー、防錆剤、防カビ剤、懸濁重
合用安定剤、セメントモルタル用混和剤、紙・繊維・プ
ラスチック・木材等の接着剤用途が期待される。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing a novel copolymer in which a group having surface-active ability is introduced into the polyvinyl alcohol (hereinafter abbreviated as PVA) chain. In addition to the conventional uses of PTA, this new copolymer can be used as an emulsion polymer emulsion stabilizer, a polymer flocculant, a papermaking agent that strengthens paper strength, improves sizing properties, and improves yield, a sizing agent for warp sizing, Fiber dyeability improver, antistatic agent, surface sizing agent for paper, binder for pigment coating, binder for inorganic fibers, rust preventive, anti-mold agent, stabilizer for suspension polymerization, admixture for cement mortar, paper and It is expected to be used as an adhesive for fibers, plastics, wood, etc.

〔従来の技術〕[Conventional technology]

従来よ、り　ＰＶＡは乳化剤、接着剤、紙用コーティン
グ剤、繊維サイジング用糊剤、フィルムあるいは合成繊
維等広範な用途に利用されてきた。Traditionally, PVA has been used in a wide range of applications such as emulsifiers, adhesives, paper coatings, fiber sizing pastes, films, and synthetic fibers.

ＰＶＡの残存酢酸基は一種の疎水性基と考えることがで
き、未ケン化の酢酸基を残すことにょ）、さらには酢酸
基の分布状態をブロック的に不均一化することにより界
面活性能を高めよつとすることはよく知られている。The residual acetate groups in PVA can be considered as a type of hydrophobic group, leaving unsaponified acetate groups), and furthermore, by making the distribution of acetate groups uneven in a block-like manner, the surfactant ability can be improved. It is well known that it tends to be expensive.

またＰＶＡに酢酸基よシも大きな疎水基を導入すること
によシ、界面活性能を高める方法としては％公昭３６−
２８４３号公報にアルキルビニルエーテルを共重合する
ことによシ導入することがまた特公昭４５−９９４９号
公報にＰＶＡに分岐脂肪酸ビニルエステルを共重合する
ことにより導入することが公知である。In addition, as a method of increasing the surfactant ability by introducing a hydrophobic group larger than an acetate group into PVA,
It is known in Japanese Patent Publication No. 2843 to introduce an alkyl vinyl ether by copolymerizing it, and in Japanese Patent Publication No. 45-9949 to introduce a branched fatty acid vinyl ester into PVA by copolymerizing it.

さらにＰＶＡ　Ｋ疎水基を有するエチレン性単量体とカ
チオン基を有するエチレン性単量体を共重合により導入
するものとして特開昭５７−２０９９０１号公報が開示
されている。Further, JP-A-57-209901 discloses a method in which an ethylenic monomer having a PVA K hydrophobic group and an ethylenic monomer having a cationic group are introduced by copolymerization.

〔本発明が解決しようとする問題点〕[Problems to be solved by the present invention]

ＰＶＡに未ケン化の酢酸基を残すことや、ブロック的に
不均一化して界面活性能を高めたとしても、ＰＶＡの界
面活性能力には限界があり、酢酸）５ニルの乳化重合等
に使用できても、アクリル酸エステル等の乳化重合には
充分な乳化安定性、保護コロイド能に欠けるという欠点
があった。Even if you leave unsaponified acetate groups in PVA or make it heterogeneous in a block manner to increase the surfactant ability, there is a limit to the surfactant ability of PVA, and it is used for emulsion polymerization of 5-nyl acetate, etc. Even if it is possible, it has the disadvantage that it lacks sufficient emulsion stability and protective colloid ability for emulsion polymerization of acrylic esters and the like.

またＰＶＡに酢酸基よりも大きな疎水基を導入すること
により界面活性能を高める方法では、顕著な性能を得る
為に多く含有させようとするとＰＶＡが水不溶性になっ
た夛、水溶液の粘度が極めて高くなったシ、水浴液全加
熱すると白濁または凝集沈澱したりする等実用上難点が
あった。In addition, in the method of increasing surfactant ability by introducing a hydrophobic group larger than an acetate group into PVA, when trying to increase the content in order to obtain remarkable performance, PVA becomes water-insoluble and the viscosity of the aqueous solution becomes extremely high. There were practical difficulties such as the high temperature and the fact that the water bath solution became cloudy or coagulated and precipitated when it was completely heated.

ＰＶＡ疎水基を有するエチレン性単量体とカチオン基を
有するエチレン性単量体を共重合によシ導入する方法で
は、重合体が５元共重合体となるのでモノマー反応性比
によっては単量体の添加方法の制御が繁雑であったり、
組成の不均一なものができた）、カチオン性基のブロッ
ク的に存在するところでは著しく耐水性に欠けたりして
均質な重合体フィルムを得ることが困難であった。In the method of copolymerizing an ethylenic monomer having a PVA hydrophobic group and an ethylenic monomer having a cationic group, the polymer becomes a 5-component copolymer, so the monomer content may vary depending on the monomer reactivity ratio. It is difficult to control the method of adding the body,
However, it was difficult to obtain a homogeneous polymer film due to a marked lack of water resistance where cationic groups existed in the form of blocks.

以上界面活性能の優れたＰＶＡを得ることは極めて困難
な現状である。As described above, it is currently extremely difficult to obtain PVA with excellent surfactant ability.

〔問題点を解決する為の手段〕[Means for solving problems]

本発明は炭素数８〜２２の炭化水素基を少なくとも１個
もつ第４級アンモニウム塩含有不飽和単量体トビニルエ
ステルとをラジカル重合開始剤存在下共重合させた後、
アルコール中アルカリ触媒によりケン化させることを特
徴とする界面活性能を有する共重合体の製造法である。In the present invention, after copolymerizing an unsaturated monomer tovinyl ester containing a quaternary ammonium salt having at least one hydrocarbon group having 8 to 22 carbon atoms in the presence of a radical polymerization initiator,
This is a method for producing a copolymer having surface-active ability, which is characterized by saponification using an alkali catalyst in alcohol.

炭素数８〜２２の炭化水素基を少なくとも１個以上もつ
第４級アンモニウム塩を含有する不飽和単量体としては
ビニルエステルと共重合しつる単量体全てを包含するも
のであるが例えば下記の（１）〜（Ｖ）で示される単量
体があげられる。Examples of unsaturated monomers containing quaternary ammonium salts having at least one hydrocarbon group having 8 to 22 carbon atoms include all monomers that copolymerize with vinyl esters, such as the following: Monomers represented by (1) to (V) are mentioned.

ＯＨＲ３ ＣＨ２閣ＣＨ （ここでＲ１は置換基を有してもよい炭素数８〜２２の
炭化水素基を、Ｒ２及びＲ３は炭素数１〜２２のアルキ
ル基を、Ｒ４、Ｒ５、Ｒ６は水素原子又は低級アルキル
基を、Ｒ７、Ｒ８、Ｒ９、Ｒ１０は水素原子、低級アル
キル基、又はフェニル基（置換基を含んでもよい）を、
Ａは窒素原子とアミド基の窒素原子とを連結する基を、
Ｄは窒素原子とエーテル基の酸素原子を連結する基を、
ｘ嘱アーオンを意味する。） このうち（１）の構造で示される単量体はビニルエステ
ルとの重合性、単量体の安定性も良好で性能の優れたＰ
ＶＡが得られるので特に好ましい。第４級アンモニウム
基のうちＲ２、Ｒ３は通常の目的では炭素数１〜４のア
ルキル基から選ばれる。OHR3 CH2 Cabinet CH (Here, R1 is a hydrocarbon group having 8 to 22 carbon atoms that may have a substituent, R2 and R3 are alkyl groups having 1 to 22 carbon atoms, and R4, R5, and R6 are hydrogen atoms. or a lower alkyl group, R7, R8, R9, R10 are hydrogen atoms, lower alkyl groups, or phenyl groups (which may contain substituents),
A is a group that connects the nitrogen atom and the nitrogen atom of the amide group,
D is a group that connects the nitrogen atom and the oxygen atom of the ether group,
x 嘱 aon means. ) Among these, the monomer shown by the structure (1) is P that has excellent polymerizability with vinyl ester, good monomer stability, and excellent performance.
This is particularly preferred since VA can be obtained. Among the quaternary ammonium groups, R2 and R3 are selected from alkyl groups having 1 to 4 carbon atoms for normal purposes.

又　としては、塩素、シュウ索、ヨウ素などのハｅ ロデン原子またはＣＨ３０８０３，ＣＨ２Ｏ，Ｈ，ＳＯ
２が好ましく特に塩素原子が経済上・安全上好ましい。Also, examples include halide atoms such as chlorine, chlorine, iodine, etc., or CH30803, CH2O, H, SO
2 is preferred, and a chlorine atom is particularly preferred from the economic and safety standpoints.

Ａ、Ｄは安定な結合を含む基であれは何でも用いられる
が通常は直鎖状、または分岐した脂肪族の基が用いられ
る。Any group containing a stable bond can be used for A and D, but usually a linear or branched aliphatic group is used.

式（１）で示される単量体の具体例としては３−アリル
オキシ−２−ヒドロキシプロＶルジメチルステアリルア
ンモニウムクロリド、３−メタアリルオキシ−２−ヒド
ロキシプロピルジメチルヘキサデシルアンモニウムトリ
ルサルフェート、３−７１ルオキシ−２−ヒドロキシプ
ロピルゾエチルドデシルアンモニウムブロミド、５−ア
リルオキシ−２−ヒドロキシプロぎルジブチルオクチル
アンモニウムブロミド、３−メタアリルオキシ−２−ヒ
ドロキシプロピルジメチルドデシルアンモニウムプロミ
ド等があげられる。Specific examples of the monomer represented by formula (1) include 3-allyloxy-2-hydroxyprov-dimethylstearylammonium chloride, 3-methallyloxy-2-hydroxypropyldimethylhexadecyl ammonium tolylsulfate, 3-71 Examples include hydroxy-2-hydroxypropylzoethyldodecylammonium bromide, 5-allyloxy-2-hydroxyprogyldibutyloctylammonium bromide, and 3-methallyloxy-2-hydroxypropyldimethyldodecylammonium bromide.

式（［Ｉ）で示される単量体の具体例としては、（２−
アクリルアミげエチル）−ジメチルステアリルアンモニ
ウムクロリド、（２−メタクリルアミドエチル）−ジブ
チルヘキサデシルアンモニウムクロリド、（３−アクリ
ルアミドプロピル）−ジエチルドテシルアンモニウムク
ロリド、（３−アクリルアミドプロピル）−ジエチルオ
クチルアンモニウムサルフェート、（３−アクリルアミ
ド−６，６−シメチルプロビル）−ジメチルオクチルア
ンモニウムクロリＰ１　（３−メタクリルアミドプロざ
ル）−メチルブチルステアリルアンモニウムトリルサル
フェート、（３−クロトンアミＰ−２，２−ジメチルプ
ロ？ル）−メチルエチルドデシルアンモニウムプロミド
、（４−アクリルアミドブチル）−ジメチルステアリル
アンモニウムヨーシト、（４−メタクリルアミ）Ｆ−３
，３−ジメチルブチル）−メチルブチルオクチルアンモ
ニウムトリルサルフェート等があげられる。Specific examples of the monomer represented by formula ([I) include (2-
(acrylamidopropyl)-dimethylstearylammonium chloride, (2-methacrylamidoethyl)-dibutylhexadecyl ammonium chloride, (3-acrylamidopropyl)-diethyldotecylammonium chloride, (3-acrylamidopropyl)-diethyloctylammonium sulfate, (3-acrylamido-6,6-dimethylprobyl)-dimethyloctylammonium chloriP1 (3-methacrylamidoprozal)-methylbutylstearylammonium tolylsulfate, (3-crotonamido-6,6-dimethylpropyl)-dimethyloctylammoniumchloriP1 )-methylethyldodecylammonium bromide, (4-acrylamidobutyl)-dimethylstearylammonium iosito, (4-methacrylami)F-3
, 3-dimethylbutyl)-methylbutyloctylammonium tolylsulfate, and the like.

式（１）で示される単量体の具体例としそは６−ピニル
ー１−ステアリルイミダゾリウムクロリｒ１６−ピニル
ー２−メチル−１−ステアリルイミダシリクムクロリド
、３−ビニル−１−ヘキサデシルイミダゾリウムクロリ
ド、６−ピニルー１−ドデシルイミダゾリウムクロリド
、６−ピニルー１−オクチルイミダゾリウムプロミド、
３−ビニル−２−エチル−１−ステアリルイミダシリク
ムクロリド、３−ビニル−２，４，５−トリメチル−１
−ヘキサデシルイミダゾリウムトリルサルツーエート等
があげられる。Specific examples of the monomer represented by formula (1) include 6-piny-1-stearylimidazolium chloride, 16-piny-2-methyl-1-stearylimidasilicum chloride, and 3-vinyl-1-hexadecyl imidazo. Lium chloride, 6-pinyru-1-dodecylimidazolium chloride, 6-pinyru-1-octylimidazolium bromide,
3-vinyl-2-ethyl-1-stearylimidasilicum chloride, 3-vinyl-2,4,5-trimethyl-1
-Hexadecyl imidazolium tolylsultuate and the like.

式（ＩＶ）で示される単量体の具体例としてけ２−ビニ
ロキシエチルジメチルステアリルアンモニウムクロリド
、（２−ビニロキシエチル）−メチルブチルヘキサデシ
ルアンモニウムトリルサルフェー）（２−ビニロキシエ
チル）−メチルエチルオクチルアンモニウムプロミド、
ｓ−ビニロキシプロチルジブチルヘキサデシルアンモニ
ウムサルフェト等があげられる。Specific examples of the monomer represented by formula (IV) include 2-vinyloxyethyldimethylstearylammonium chloride, (2-vinyloxyethyl)-methylbutylhexadecylammonium tolylsulfate)(2-vinyloxyethyl)-methylethyloctylammonium promid,
Examples include s-vinyloxyprotyldibutylhexadecyl ammonium sulfate.

式（Ｖ）で示される単量体の具体例としてはジアリルメ
チルステアリルアンモニウムクロリド、ジアリルブチル
ヘキサデシルアンモニウムプロミド、ジアリルエチルオ
クチルアンモニウムヨーシト等があげられる。Specific examples of the monomer represented by formula (V) include diallylmethylstearylammonium chloride, diallylbutylhexadecyl ammonium bromide, diallylethyloctylammonium iosite, and the like.

ビニルエステルとしては、酢酸ビニル、プロピオン酸ビ
ニル、ギ酸ビニル等があげられるが経済面で酢酸ビニル
が好ましい。Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl formate, etc., but vinyl acetate is preferred from an economic standpoint.

共重合法については溶液重合、塊状重合、乳化重合等ど
のような重合法も実施可能であるが、アルコールの存在
下での溶液重合が好ましい。アルコールとしては通常メ
タノール、エタノール等の低級アルコールが好ましい。Regarding the copolymerization method, any polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc. can be carried out, but solution polymerization in the presence of alcohol is preferred. As the alcohol, lower alcohols such as methanol and ethanol are usually preferred.

またアルコールに、重合に悪影響を与えない程度に水を
添加して重合させてもよい。Further, water may be added to the alcohol to an extent that does not adversely affect the polymerization.

重合開始剤としては２．２′−アゾビスイソブチロニト
リル、過酸化ベンゾイル、過酸化ラウロイル、過酸化ア
セチル等の公知のラジカル重合開始剤が使用できる。そ
の際の重合温度は５０℃〜７０℃から選ばれる。重合度
及び炭素数８〜２２の炭化水素基をもつ第４級アンモニ
ウム塩含有不飽和単量体は、用途に応じて適宜選択され
るが、重合度は２００〜５０００（数平均分子量として
５０００〜２００，０００　”）、含有量は０．０１〜
２０モルチの範囲から選ぶのが好ましい。未反応のビニ
ルエステル単量体は蒸留等によって除去することが可能
であるが、炭素数８〜２２の炭化水素基をもつ第４級ア
ンモ゛ニウム塩含Ｍ不飽和単量体はケン化工程において
残留していても差支えな（１゜ 得られた共重合体のケン化工程は、現在ＰＶＡの工業的
製造で利用されている方法をそのまま用いるのが好適で
ある。すなわちアルコール溶液中、アルカリ触媒を用（
・るケン化方法である。アルカリ触媒の例としては、ナ
トリウム又はカリウムの水酸化物及びアルコラード等で
あるが、経済的にはメタノール溶液中、水酸化ナトリウ
ム触媒を用いる方法が望ましい。酸触媒によシケン化す
ることも可能であるがケン化反応速度が遅いという難点
がある。またアルコールに酢酸メチル、酢酸エチル等の
有機溶剤や水を任意に混合させてケン化することもでき
る。ケン化温度は通常１０〜５０℃の範囲から選ばれる
。ケン化度は目的に応じて種々変えてもよいが、工業的
に有利に製造できる範囲として９９．９９〜７０モルチ
よシ好ましく選ばれる。ケン化反応の進行にともない、
通常のＰＶＡの場合と同様に白色のゲル又は沈澱物を生
成させる方法を行うことが製造上望ましいが、必要に応
じ℃これを粉砕、洗浄、乾燥することによシ該共重合体
の粉末を得ることができる。As the polymerization initiator, known radical polymerization initiators such as 2,2'-azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, and acetyl peroxide can be used. The polymerization temperature at that time is selected from 50°C to 70°C. The degree of polymerization and the quaternary ammonium salt-containing unsaturated monomer having a hydrocarbon group having 8 to 22 carbon atoms are appropriately selected depending on the application, but the degree of polymerization is 200 to 5000 (number average molecular weight is 5000 to 5000). 200,000”), content is 0.01~
It is preferable to select from a range of 20 molti. Unreacted vinyl ester monomers can be removed by distillation, etc., but quaternary ammonium salt-containing M unsaturated monomers having a hydrocarbon group having 8 to 22 carbon atoms can be removed by a saponification process. (1°) It is preferable to use the saponification process of the obtained copolymer by the method currently used in the industrial production of PVA. Using a catalyst (
・This is a saponification method. Examples of alkali catalysts include sodium or potassium hydroxide and alcolade, but from an economic standpoint, it is desirable to use a sodium hydroxide catalyst in a methanol solution. It is also possible to carry out saponification using an acid catalyst, but the problem is that the saponification reaction rate is slow. Alternatively, alcohol can be optionally mixed with an organic solvent such as methyl acetate or ethyl acetate or water for saponification. The saponification temperature is usually selected from the range of 10 to 50°C. Although the degree of saponification may be varied depending on the purpose, it is preferably selected from 99.99 to 70 molty as it can be industrially advantageously produced. As the saponification reaction progresses,
It is desirable for production to produce a white gel or precipitate in the same way as in the case of ordinary PVA, but if necessary, the copolymer powder can be obtained by crushing, washing and drying the copolymer at °C. Obtainable.

また共重合にあっては炭素数８〜２２の炭化水素基をも
つ第４級アンモニウム基金石不飽和単量体とビニルエス
テル以外にこれらの単量体と共重合可能な他の不飽和単
量体、例えば、エチレン、プロぎレンのようなα−オレ
フィン：アクリルアミド、メタクリルアミド、Ｎ−メチ
ロールアクリルアミド等の不飽和アミド；アクリル酸、
メタクリル酸、クロトン酸、無水マレイン酸、フマル酸
、イタコン酸あるいはこれらの場やアルキルエステルあ
るいは不飽和酸のアルカリ塩；２−アクリル７ミ）’−
２−メチルプロパンスルホン酸またはその塩；アルキル
ビニルエーテル、その他力チオン性不飽和単量体のうち
１種又は２種以上共存させて共重合させることもできる
。その場合の上記単量体の含弔意は用途によって適宜選
択できる。In addition, in copolymerization, other unsaturated monomers that can be copolymerized with these monomers, in addition to the quaternary ammonium foundation stone unsaturated monomer having a hydrocarbon group having 8 to 22 carbon atoms and vinyl ester, are used. α-olefins such as ethylene, progylene; unsaturated amides such as acrylamide, methacrylamide, N-methylolacrylamide; acrylic acid,
Methacrylic acid, crotonic acid, maleic anhydride, fumaric acid, itaconic acid, or alkyl esters or alkali salts of unsaturated acids; 2-acrylic 7)'-
It is also possible to copolymerize one or more of 2-methylpropanesulfonic acid or a salt thereof, alkyl vinyl ether, and other thionic unsaturated monomers. In that case, the meaning of the monomers mentioned above can be appropriately selected depending on the intended use.

〔実施例〕〔Example〕

以下本発明を実施例により具体的に説明するが、本発明
はこれら実施例に限定されるものではない。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

「部」は重量部を、チは特にことわらない限９重Ｉｋ％
を意味する。"Part" means part by weight, unless otherwise specified, 9-weight Ik%
means.

実施例１ 攪拌機、温度計、還流冷却管、滴下漏斗を備えた５１セ
パラブルフラスコに酢酸ビニル１８００部、メタノール
７２４部、２，２′−ア・戸ビスイソブチロニトリル１
．２部、３−アリルオキシ−２−ヒドロキシプロピルジ
メチルステアリルアンモニウムクロリド１０８部を仕込
み、窒素ガスをバブリングして脱酸素後、６０℃で１０
時間共重合させた。共重合体の重合率は６２．５　％で
あった。Example 1 In a 51 separable flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel, 1800 parts of vinyl acetate, 724 parts of methanol, and 1 part of 2,2'-a-bisisobutyronitrile were added.
．． 2 parts, 108 parts of 3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride were charged, and after deoxidizing by bubbling nitrogen gas, the mixture was heated at 60°C for 10 minutes.
Copolymerized over time. The polymerization rate of the copolymer was 62.5%.

重合反応液中にメタノール蒸気を吹き込んで未反応モノ
マーを除去した後、共重合体の３０℃、３５％のメタノ
ール溶液を調製した。このメタノール溶ｆｆ３１８０部
に、２．２Ｎの水酸化ナトリウムのメタノール溶液４８
部を添加して混合すると２８分後に系は粘稠となシ粒子
が析出した。メタノールで洗浄後、乾燥して白色の共重
合体を得た、同、６−アリルオキシ−２−ヒドロキシゾ
ロビルジメチルステアリルアンモニウムクロリＰの含有
率は窒素分析値によシ１．１モＡ／％であった。酢酸ビ
ニル成分のケン化度は８７．４モルチであった。After removing unreacted monomers by blowing methanol vapor into the polymerization reaction solution, a 35% methanol solution of the copolymer was prepared at 30°C. To 3180 parts of this methanol solution, add 48 parts of a 2.2N methanol solution of sodium hydroxide.
After 28 minutes, the system became viscous and particles were precipitated. After washing with methanol and drying, a white copolymer was obtained.The content of 6-allyloxy-2-hydroxyzorobyldimethylstearylammonium chloride P was 1.1 moA/% according to the nitrogen analysis value. Met. The degree of saponification of the vinyl acetate component was 87.4 mol.

デルパーミェーションクロマトグラフィーで求めた数平
均分子量は約５０，０００であった（東洋曹達工業製ｃ
ｃｐ　−８０［１０、カラムＦＩｗｘＬ＋Ｇ３０００Ｐ
ＷＸＬ　＋　Ｇ　５０００　ＦＷＸＬで測定しり）。得
られ九共重合体の水溶性は良好で白濁やゲル化も見られ
ず安定であった。The number average molecular weight determined by del permeation chromatography was approximately 50,000 (Toyo Soda Kogyo c.
cp -80[10, column FIwxL+G3000P
Measured with WXL + G 5000 FWXL). The resulting nine copolymer had good water solubility and was stable with no clouding or gelation.

＊１ 該共重合体の０．５％水溶液の表面張力　は４９ダイン
／ｃＩｒＬであシ高い界面活性能を示した。また＊２ パルプへの定着率　を求めたところ９３チであシはとん
ど該共重合体がパルプへ吸着されておシ、高い吸着能を
もつことがわかった。*1 The surface tension of a 0.5% aqueous solution of the copolymer was 49 dynes/cIrL, indicating high surface activity. *2 When the adhesion rate to pulp was determined, it was found that most of the copolymer of 93 Chiadashi was adsorbed to the pulp and had a high adsorption capacity.

実施例２〜８ 実施例１の３−アリルオキシ−２−ヒドロキシプロピル
ジメチルステアリルアンモニウムクロリドに替えて表に
示す単量体を所定量使用する以外は実施例１に準じた方
法によシ共重合、ケン化して後処理した。Examples 2 to 8 Copolymerization in the same manner as in Example 1, except that a prescribed amount of the monomer shown in the table was used in place of 3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride in Example 1, Post-processed by saponification.

比較例１ ３−アリルオキシ−２−ヒドロキシプロぎルジメチルス
テアリルアンモニウムクロリドを用いることな〈実施例
１と同様にして３−アリルオキシ−２−ヒドロキシプロ
ピルトリメチルアンモニウムクロリドヲ１．８モルチ、
数平均分子量約４５，０００ケン化度９８．４モルチの
カチオン化ＰＶＡを得た。Comparative Example 1 3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride was not used (1.8 mol of 3-allyloxy-2-hydroxypropyltrimethylammonium chloride was prepared in the same manner as in Example 1,
Cationized PVA having a number average molecular weight of about 45,000 and a degree of saponification of 98.4 molti was obtained.

この共重合体の０．５％水溶液の表面張力は５５ダイン
／ａｎであシ、先の実施例に比較すると界面活性能が大
巾に低いことがわかる。The surface tension of a 0.5% aqueous solution of this copolymer was 55 dynes/an, which indicates that the surface active ability is significantly lower than in the previous example.

比較例２ ３−アリルオキシ−２−ヒドロキシプロピルジメチルス
テアリルアンモニウムクロリドを用いることな〈実施例
１と同様にしてラウリルビニルエーテルを３〜４モルチ
含有するように共重合させケン化したが、該共重合体は
冷水、熱水ともに不溶性とな９界面活性能は測定できな
かった。Comparative Example 2 Without using 3-allyloxy-2-hydroxypropyldimethylstearylammonium chloride (copolymerization and saponification of lauryl vinyl ether to contain 3 to 4 moles was carried out in the same manner as in Example 1, but the copolymer It was insoluble in both cold water and hot water, and the surfactant ability could not be measured.

実施例９ 攪拌機、還流冷却管、温度計、滴下ロートを付設したセ
ペラブルフラスコ中に、実施例１で得念該共重合体２４
．５部、蒸留水３８５ｇを攪拌しながら入れ、内温を６
５°Ｃに昇温した。完溶後アクリル酸メチル／アクリル
酸ブチル−済、４２ｇ、２．２’−アゾビス（２−アミ
ジノプロパン）二塩酸塩１部と蒸留水１０部からなる開
始剤溶液を添加し、アクリル酸メチル／アクリル酸ブチ
ル−何２５３ｇを３時間にわたって滴下し、更に１時間
熟成を行い、該重合体エマルジョンを得た。こうして得
られた重＊６ 合体エマルジョンの重合安定性　は全般にわたつ＊４ ℃良好な重合性を示し、また耐水性　は白化に要□する
時間１１ｔ１日以上であシ良好な耐水性を示した。Example 9 The copolymer 24 obtained in Example 1 was placed in a separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a dropping funnel.
．． Add 5 parts and 385 g of distilled water while stirring, and bring the internal temperature to 6.
The temperature was raised to 5°C. After complete dissolution, an initiator solution consisting of 42 g of methyl acrylate/butyl acrylate, 1 part of 2.2'-azobis(2-amidinopropane) dihydrochloride and 10 parts of distilled water was added, and methyl acrylate/butyl acrylate was dissolved. 253 g of butyl acrylate was added dropwise over 3 hours, and the mixture was further aged for 1 hour to obtain the polymer emulsion. The polymerization stability of the thus obtained heavy*6 combined emulsion showed good polymerization across all *4 degrees Celsius, and the water resistance showed good water resistance at a time of 11t or more than 1 day for whitening. Ta.

比較例６ 実施例９で用いた該共重合体に替えて、比較例１で得た
カチオン化ＰＶＡ　’ｉ用いた以外は実施例９に準じた
方法で重合体エマルジョンを得た。こうして得られた重
合体エマルジョンの重合安定性は粒子に粗粒が見られ、
耐水性では１時間以内に白化して耐水性は不良であった
。Comparative Example 6 A polymer emulsion was obtained in the same manner as in Example 9, except that the cationized PVA'i obtained in Comparative Example 1 was used instead of the copolymer used in Example 9. The polymerization stability of the polymer emulsion thus obtained showed that coarse particles were observed;
The water resistance was poor as it turned white within 1 hour.

測定法 ＊１　表面張力 、ｙｘｓｘ　−３３６２に準じて滴数法により測定温度
２０℃で測定した。Measurement method *1 Surface tension was measured at a measurement temperature of 20°C by the drop count method according to YXSX-3362.

＊２　パルプへの定着率 ２．５％ＮＢＫＦパルプスラリーに対パルプ０．４チの
該共重合体を添加し２分間攪拌後１００メツシュ金網、
続いてＡ６濾紙にて濾過する。濾液１〇−に４％ホウ酸
水溶液１５ｍ１、ｌ２−ＫＩ　（１２，７９−２５９／
ｌ＞溶液３ｍｌを加え、全体ｔ−５Ｑｍｊに稀釈する。*2 The copolymer was added to the NBKF pulp slurry with a fixation rate of 2.5% to the pulp, and after stirring for 2 minutes, a 100 mesh wire mesh was added.
Subsequently, it is filtered using A6 filter paper. Add 15ml of 4% boric acid aqueous solution to filtrate 1〇-, l2-KI (12,79-259/
Add 3 ml of solution and dilute to total t-5Qmj.

６４０〜６８０ＨのＵＶの極大吸収波長にて吸光度を測
定し、定着率を算出した。The absorbance was measured at a UV maximum absorption wavelength of 640 to 680H, and the fixing rate was calculated.

＊３　　Ｍ合安定性 重合体エマルジョンｆ：１００メツシュの金網で濾過し
、濾過残渣を水で洗浄後１０５±２℃で１２時間乾燥し
、凝塊物を得る。この乾燥重量を使用モノマーに対する
重量％で表わしその大小によって重合安定性を比較した
。*3 M polymerization stable polymer emulsion f: Filter through a 100-mesh wire mesh, wash the filtration residue with water, and then dry at 105±2°C for 12 hours to obtain a coagulum. This dry weight was expressed as a weight % based on the monomer used, and the polymerization stability was compared based on its size.

＊４　耐水性 約０．２順の膜を調製して水浸漬法による白化に要する
時間を測定して耐水性能とした。*4 Films with a water resistance of about 0.2 were prepared, and the time required for whitening by water immersion was measured to determine water resistance.

〔発明の効果〕〔Effect of the invention〕

本発明の方法による共重合体は炭素数８〜２２の疎水性
の炭化水素基と親水性のカチオン基を同一構造単位中に
有する点に特徴をもち、それによｐ従来にない優れた効
果が発揮される。The copolymer produced by the method of the present invention is characterized by having a hydrophobic hydrocarbon group having 8 to 22 carbon atoms and a hydrophilic cationic group in the same structural unit, which results in excellent effects not seen before. Demonstrated.

（１）　　疎水性基をもつにもかかわらず水溶性に優れ
、水溶液は白濁やゲル化も見られず安定であシ、その水
溶液から得られた膜は耐水性に優れる。(1) Despite having a hydrophobic group, it has excellent water solubility, and the aqueous solution is stable without clouding or gelation, and the membrane obtained from the aqueous solution has excellent water resistance.

（２）　　界面活性能に優れている為に乳化安定剤とし
て用いた場合優れた乳化、保護コロイド能をもつ。また
本発明法による共重合体を用いて製造したエマルション
の皮膜は、従来のカチオン化ＰＶＡを乳化剤とした場合
よりも耐水性に優れる。(2) Due to its excellent surfactant ability, when used as an emulsion stabilizer, it has excellent emulsifying and protective colloid abilities. Furthermore, the emulsion film produced using the copolymer according to the method of the present invention has better water resistance than the case where conventional cationized PVA is used as an emulsifier.

（３）　　水溶液中でパルプ、ガラス、セルロース繊維
、ポリエステル繊維等の負に帯電する物質表面への吸着
能に優れる。(3) Excellent adsorption ability to the surface of negatively charged substances such as pulp, glass, cellulose fibers, and polyester fibers in aqueous solutions.

（４）　　内添の紙加工薬品、繊維処理剤として定着性
が高く耐水性に優れる。特に中性抄紙用サイズ剤の乳化
定着剤として優れた性能が期待される。(4) As an internally added paper processing chemical or fiber treatment agent, it has high fixing properties and excellent water resistance. In particular, it is expected to have excellent performance as an emulsifying fixing agent for neutral paper sizing agents.

Claims (1)

【特許請求の範囲】[Claims] 炭素数８〜２２の炭化水素基を少なくとも１個もつ第４
級アンモニウム塩含有不飽和単量体と、ビニルエステル
とをラジカル重合開始剤存在下共重合させた後、アルコ
ール中アルカリ触媒によりケン化させることを特徴とす
る界面活性能を有する共重合体の製造法。A fourth having at least one hydrocarbon group having 8 to 22 carbon atoms
Production of a copolymer having surface-active ability, which is characterized by copolymerizing an unsaturated monomer containing a grade ammonium salt and a vinyl ester in the presence of a radical polymerization initiator, and then saponifying the product using an alkali catalyst in alcohol. Law.
JP5074286A 1986-03-08 1986-03-08 Production of copolymer having surface activity Pending JPS62207304A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP5074286A JPS62207304A (en) 1986-03-08 1986-03-08 Production of copolymer having surface activity

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP5074286A JPS62207304A (en) 1986-03-08 1986-03-08 Production of copolymer having surface activity

Publications (1)

Publication Number Publication Date
JPS62207304A true JPS62207304A (en) 1987-09-11

Family

ID=12867292

Family Applications (1)

Application Number Title Priority Date Filing Date
JP5074286A Pending JPS62207304A (en) 1986-03-08 1986-03-08 Production of copolymer having surface activity

Country Status (1)

Country Link
JP (1) JPS62207304A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996039447A1 (en) * 1995-06-05 1996-12-12 Kuraray Co., Ltd. Vinyl alcohol polymer
CN1054860C (en) * 1995-06-05 2000-07-26 可乐丽股份有限公司 Vinyl alcohol polymer
JP2001139612A (en) * 1999-11-18 2001-05-22 Nippon Synthetic Chem Ind Co Ltd:The Dispersant for emulsion polymerization and its use
JP2011111583A (en) * 2009-11-30 2011-06-09 Nippon Shokubai Co Ltd Amino group-containing copolymer and manufacturing method thereof
JP2011116811A (en) * 2009-12-01 2011-06-16 Nippon Shokubai Co Ltd Cationic group-containing copolymer and manufacturing method therefor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996039447A1 (en) * 1995-06-05 1996-12-12 Kuraray Co., Ltd. Vinyl alcohol polymer
CN1054860C (en) * 1995-06-05 2000-07-26 可乐丽股份有限公司 Vinyl alcohol polymer
JP2001139612A (en) * 1999-11-18 2001-05-22 Nippon Synthetic Chem Ind Co Ltd:The Dispersant for emulsion polymerization and its use
JP2011111583A (en) * 2009-11-30 2011-06-09 Nippon Shokubai Co Ltd Amino group-containing copolymer and manufacturing method thereof
JP2011116811A (en) * 2009-12-01 2011-06-16 Nippon Shokubai Co Ltd Cationic group-containing copolymer and manufacturing method therefor

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