JP2615681B2 - Method for producing water-soluble copolymer - Google Patents
Method for producing water-soluble copolymerInfo
- Publication number
- JP2615681B2 JP2615681B2 JP62263538A JP26353887A JP2615681B2 JP 2615681 B2 JP2615681 B2 JP 2615681B2 JP 62263538 A JP62263538 A JP 62263538A JP 26353887 A JP26353887 A JP 26353887A JP 2615681 B2 JP2615681 B2 JP 2615681B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylamide
- compound
- mol
- diallylamine
- derivative monomer
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
- C08F226/04—Diallylamine
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は、アクリルアミド系化合物とジアリルアミン
誘導体モノマーを共重合体してなるカチオン性共重合
体、又は、アクリルアミド系化合物、α，β−不飽和カ
ルボン酸化合物及びジアリルアミン誘導体モノマーを共
重合してなる両性共重合体の製造方法に関する。かかる
カチオン性又は両性の共重合体は、製紙用添加剤など、
特に紙質向上剤として有用なものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a cationic copolymer obtained by copolymerizing an acrylamide compound and a diallylamine derivative monomer, or an acrylamide compound, α, β-unsaturated The present invention relates to a method for producing an amphoteric copolymer obtained by copolymerizing a carboxylic acid compound and a diallylamine derivative monomer. Such cationic or amphoteric copolymers, such as papermaking additives,
It is particularly useful as a paper quality improver.
〈従来の技術〉 ジアリルアミンの塩などのジアリルアミン誘導体モノ
マーは、種々の文献等にも記載されているように、環化
反応を起こし、環状構造を有する重合物を与えるもので
あるが、その分子内にアリル基を有するため、いわゆる
アリル型破壊的連鎖移動（allylic degradative chain
−transfer）を起こし、必ずしもその重合活性は高くな
い。<Conventional technology> A diallylamine derivative monomer such as a diallylamine salt causes a cyclization reaction to give a polymer having a cyclic structure, as described in various literatures. Has an allyl group, so-called allylic degradative chain transfer
-Transfer), and its polymerization activity is not always high.
この重合活性の低さは、他の単量体との共重合反応に
おいてより顕著に現れる。例えば、J.Polym.Sci.:Poly
m.Chem.Ed.,24,29−36（1986）には、ジアリルアミン誘
導体モノマーの一種であるジアリルジメチルアンモニウ
ムクロライド（DADMAC）とアクリルアミドとの共重合反
応において、アクリルアミド（M1）とDADMAC（M2）のモ
ノマー反応性比は、 r1＝6.7、r2＝0.58 であり、DADMACの反応性がアクリルアミドのそれに比し
て極端に小さいことが記されている。This low polymerization activity appears more remarkably in the copolymerization reaction with other monomers. For example, J.Polym.Sci.:Poly
Chem. Ed., 24 , 29-36 (1986) states that acrylamide (M 1 ) and DADMAC (M1) are used in a copolymerization reaction of diallyldimethylammonium chloride (DADMAC), which is a kind of diallylamine derivative monomer, with acrylamide. The monomer reactivity ratio of 2 ) is r 1 = 6.7 and r 2 = 0.58, and it is described that the reactivity of DADMAC is extremely lower than that of acrylamide.
〈発明が解決しようとする問題点〉 ジアリルアミン誘導体モノマーの低い重合活性のた
め、アクリルアミド系化合物やα，β−不飽和カルボン
酸化合物等とジアリルアミン誘導体モノマーの共重合反
応を行う場合、アクリルアミド系化合物やα，β−不飽
和カルボン酸化合物等の重合反応が優先的に進行し、ジ
アリルアミン誘導体モノマーが未反応のまま多量に残存
するという結果になる。一方で、ジアリルアミン誘導体
モノマーの残存量を低減すべく、重合開始剤の逐次添加
を行った場合は、低分子量の重合物しか得られず、極端
な場合にはポリマー鎖の***という好ましからざる事態
に到る危険性がある。<Problems to be Solved by the Invention> Due to the low polymerization activity of the diallylamine derivative monomer, when performing a copolymerization reaction of the diallylamine derivative monomer with an acrylamide compound or an α, β-unsaturated carboxylic acid compound or the like, the acrylamide compound or The polymerization reaction of the α, β-unsaturated carboxylic acid compound or the like proceeds preferentially, resulting in a large amount of the diallylamine derivative monomer remaining unreacted. On the other hand, when the polymerization initiator is added sequentially to reduce the residual amount of the diallylamine derivative monomer, only a low molecular weight polymer is obtained, and in extreme cases, the undesired situation of polymer chain splitting may occur. There is danger.
〈問題点を解決するための手段〉 本発明者らは、このような問題点を解決すべく鋭意検
討した結果、本発明を完成した。<Means for Solving the Problems> The present inventors have made intensive studies to solve such problems, and as a result, completed the present invention.
すなわち本発明は、一般式（Ｉ） （式中、R1及びR2はそれぞれ水素又はメチル基を表し、
R3及びR4はそれぞれ単独に、水素又は炭素数１〜６のア
ルキル基を表し、X-は有機酸又は無機酸の陰イオンを表
す） で表されるジアリルアミン誘導体モノマー（Ａ）と、一
般式（II） CH2＝Ｃ（R5）−CONH2 （II） （式中、R5は水素又はメチル基を表す） で表されるアクリルアミド系化合物（Ｂ）とを共重合し
てカチオン性共重合体を製造する方法において、ジアリ
ルアミン誘導体モノマー（Ａ）を含有する水溶液に、ア
クリルアミド系化合物（Ｂ）を連続的に添加しながら重
合反応を行うことを特徴とするカチオン性共重合体の製
造方法を提供するものである。That is, the present invention provides a compound represented by the general formula (I): (Wherein, R 1 and R 2 each represent hydrogen or a methyl group,
R 3 and R 4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X − represents an anion of an organic acid or an inorganic acid), and a diallylamine derivative monomer (A) represented by the general formula: Formula (II) CH 2 ＣC (R 5 ) —CONH 2 (II) (wherein, R 5 represents hydrogen or a methyl group) and copolymerizes with an acrylamide-based compound (B) to form a cationic compound In a method for producing a copolymer, a polymerization reaction is carried out while continuously adding an acrylamide compound (B) to an aqueous solution containing a diallylamine derivative monomer (A). It provides a method.
さらに本発明は、上記ジアリルアミン誘導体モノマー
（Ａ）及びアクリルアミド系化合物（Ｂ）に加えて、
α，β−不飽和モノカルボン酸、α，β−不飽和ジカル
ボン酸及びこれらの塩類からなる群より選ばれた１又は
２以上の不飽和カルボン酸化合物（Ｃ）を用い、これら
を共重合して両性共重合体を製造する方法において、ジ
アリルアミン誘導体モノマー（Ａ）を含有する水溶液
に、アクリルアミド系化合物（Ｂ）及び不飽和カルボン
酸化合物（Ｃ）を連続的に添加しながら重合反応を行う
ことを特徴とする両性共重合体の製造方法をも提供する
ものである。The present invention further provides, in addition to the diallylamine derivative monomer (A) and the acrylamide compound (B),
One or two or more unsaturated carboxylic acid compounds (C) selected from the group consisting of α, β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids and salts thereof are copolymerized. In the method for producing an amphoteric copolymer by heating, a polymerization reaction is carried out while continuously adding an acrylamide compound (B) and an unsaturated carboxylic acid compound (C) to an aqueous solution containing a diallylamine derivative monomer (A). The present invention also provides a method for producing an amphoteric copolymer characterized by the following.
本発明で用いる一般式（１）で表されるジアリルアミ
ン誘導体モノマー（Ａ）としては、ジアリルアミンやジ
メタアリルアミンで代表される２級アミンの無機又は有
機酸塩、ジアリルメチルアミン、ジアリルエチルアミ
ン、ジアリルブチルアミン等で代表される３級アミンの
無機又は有機酸塩、ジアリルジメチルアンモニウムクロ
ライド、ジアリルジメチルアンモニウムブロマイド、ジ
アリルジエチルアンモニウムクロライド、ジアリルジブ
チルアンモニウムクロライド、ジアリルメチルエチルア
ンモニウムクロライド等で代表される４級アンモニウム
塩が、具体例としてあげられる。The diallylamine derivative monomer (A) represented by the general formula (1) used in the present invention includes inorganic or organic acid salts of secondary amines represented by diallylamine and dialmethallylamine, diallylmethylamine, diallylethylamine, diallylbutylamine Quaternary ammonium salts such as inorganic or organic acid salts of tertiary amines, diallyldimethylammonium chloride, diallyldimethylammonium bromide, diallyldiethylammonium chloride, diallyldibutylammonium chloride, diallylmethylethylammonium chloride, etc. , As a specific example.
また、一般式（II）で表されるアクリルアミド系化合
物（Ｂ）は、アクリルアミド又はメタクリルアミドであ
る。The acrylamide compound (B) represented by the general formula (II) is acrylamide or methacrylamide.
任意に用いられる不飽和カルボン酸化合物（Ｃ）のう
ち、α，β−不飽和モノカルボン酸としては、アクリル
酸、メタクリル酸等が、α，β−不飽和ジカルボン酸と
しては、マレイン酸、フマル酸、イタコン酸等が、また
塩類としては、これら不飽和モノ又はジカルボン酸のナ
トリウム塩やカリウム塩の如きアルカリ金属塩類又はア
ンモニウム塩類等が例示される。Among the optionally used unsaturated carboxylic acid compounds (C), acrylic acid, methacrylic acid and the like are used as α, β-unsaturated monocarboxylic acids, and maleic acid and fumaric acid are used as α, β-unsaturated dicarboxylic acids. Acids, itaconic acids and the like, and salts thereof include alkali metal salts and ammonium salts such as sodium and potassium salts of these unsaturated mono- or dicarboxylic acids.
本発明の共重合体の製造方法を実施するにあたって、
全使用モノマー中のジアリルアミン誘導体モノマー
（Ａ）の割合は、好ましくは１〜70モル％、より好まし
くは２〜50モル％であり、アクリルアミド系化合物
（Ｂ）の割合は、好ましくは30〜99モル％、より好まし
くは50〜98モル％であり、また不飽和カルボン酸化合物
（Ｃ）を用いる場合、その割合は好ましくは０〜20モル
％である。In carrying out the method for producing a copolymer of the present invention,
The proportion of the diallylamine derivative monomer (A) in all the monomers used is preferably 1 to 70 mol%, more preferably 2 to 50 mol%, and the proportion of the acrylamide compound (B) is preferably 30 to 99 mol%. %, More preferably 50 to 98 mol%, and when the unsaturated carboxylic acid compound (C) is used, the proportion is preferably 0 to 20 mol%.
さらに、本発明の製造方法を実施するにあたっては、
上記の化合物と共重合可能な他のモノマーを導入するこ
ともできる。このようなモノマーとしては、（メタ）ア
クリロニトリル、（メタ）アクリル酸メチル、ヒドロキ
シエチル（メタ）アクリレート、スチレン、酢酸ビニル
の如きノニオン性モノマー、ジメチルアミノエチル（メ
タ）アクリレート、ジメチルアミノプロピル（メタ）ア
クリルアミド等、又はそれらの４級化物の如きカチオン
性モノマー、エチレングリコールジ（メタ）アクリレー
ト、メチレンビス（メタ）アクリルアミドの如き二官能
性モノマーなどが例示される。Further, in carrying out the production method of the present invention,
Other monomers copolymerizable with the above compounds can also be introduced. Examples of such a monomer include nonionic monomers such as (meth) acrylonitrile, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, styrene and vinyl acetate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) Examples thereof include cationic monomers such as acrylamide and the like, and quaternized products thereof, and bifunctional monomers such as ethylene glycol di (meth) acrylate and methylenebis (meth) acrylamide.
重合開始剤は、通常用いられる開始剤が使用できる。
例えば、過硫酸アンモニウム、過硫酸カリウムの如き過
硫酸塩、2,2′−ジアミジノ−2,2′−アゾジプロパンジ
塩酸塩、アゾビスイロブチロニトリルの如きアゾ化合
物、ジ−ｔ−ブチルポーオキサイド、クメンハイドロパ
ーオキサイド、過酸化水素の如き過酸化物などが例示で
きる。また、公知のレドックス系開始剤、例えば、過硫
酸カリウムと亜硫酸水素ナトリウム又は３級アミンとの
組合せも使用できる。As the polymerization initiator, a commonly used initiator can be used.
For example, persulfates such as ammonium persulfate and potassium persulfate, 2,2'-diamidino-2,2'-azodipropane dihydrochloride, azo compounds such as azobisirobutyronitrile, di-t-butyl peroxide, cumene Examples thereof include peroxides such as hydroperoxide and hydrogen peroxide. Known redox initiators, for example, a combination of potassium persulfate and sodium bisulfite or a tertiary amine can also be used.
重合は、通常10〜100℃、好ましくは40〜90℃で１〜1
2時間行われる。この重合反応は、酸素存在下でも可能
であるが、窒素ガスなどの不活性ガスの雰囲気中で行う
のが好ましい。The polymerization is usually carried out at 10 to 100 ° C, preferably at 40 to 90 ° C for 1 to 1
Performed for 2 hours. This polymerization reaction can be carried out in the presence of oxygen, but is preferably carried out in an atmosphere of an inert gas such as nitrogen gas.
重合反応は、ジアリルアミン誘導体モノマー（Ａ）を
含む水溶液に、アクリルアミド系化合物（Ｂ）を、ある
いはアクリルアミド系化合物（Ｂ）及び不飽和カルボン
酸化合物（Ｃ）を連続的に添加することによって実施さ
れる。この際の添加速度は、等速でも非等速でもよい。
また添加時間は、通常10分〜10時間である。両性共重合
体の製造にあたり、アクリルアミド系化合物（Ｂ）及び
不飽和カルボン酸化合物（Ｃ）は、両者を別個に連続添
加してもよいし、両者を混合した状態で連続添加しても
よい。アクリルアミド系化合物（Ｂ）及び任意に用いら
れる不飽和カルボン酸化合物（Ｃ）の添加が終わった後
は、さらに反応を進行させるために、引き続き上記反応
時間の範囲内で保持を続けることもできる。The polymerization reaction is carried out by continuously adding the acrylamide compound (B) or the acrylamide compound (B) and the unsaturated carboxylic acid compound (C) to an aqueous solution containing the diallylamine derivative monomer (A). . The addition speed at this time may be constant or non-constant.
The addition time is usually 10 minutes to 10 hours. In the production of the amphoteric copolymer, the acrylamide compound (B) and the unsaturated carboxylic acid compound (C) may be added separately and continuously, or may be added continuously in a state where both are mixed. After the addition of the acrylamide-based compound (B) and the optionally used unsaturated carboxylic acid compound (C), the reaction can be continued within the above-mentioned reaction time in order to further promote the reaction.
ジアリルアミン誘導体モノマー（Ａ）及びアクリルア
ミド系化合物（Ｂ）に加えて、あるいはさらに不飽和カ
ルボン酸化合物（Ｃ）に加えて、それらと共重合可能な
他のモノマーを用いる場合、こうした他のモノマーは、
アクリルアミド系化合物（Ｂ）と、あるいはアクリルア
ミド系化合物（Ｂ）及び不飽和カルボン酸化合物（Ｃ）
と混合して連続添加しても、またこれらとは別個に連続
添加してもよいし、重合反応当初から一部を系中に添加
しておいてもよい。When other monomers copolymerizable with the diallylamine derivative monomer (A) and the acrylamide compound (B), or in addition to the unsaturated carboxylic acid compound (C), are used, such other monomers are
Acrylamide compound (B), or acrylamide compound (B) and unsaturated carboxylic acid compound (C)
And may be added continuously, or separately and continuously added thereto, or a part thereof may be added to the system from the beginning of the polymerization reaction.
重合開始剤は、ジアリルアミン誘導体モノマー（Ａ）
を含む水溶液に予め添加しておいてもよいし、あるいは
アクリルアミド系化合物（Ｂ）と同時に、又はアクリル
アミド系化合物（Ｂ）及び不飽和カルボン酸化合物
（Ｃ）と同時に、連続的に添加しても差し支えない。The polymerization initiator is a diallylamine derivative monomer (A)
May be added in advance to an aqueous solution containing, or may be continuously added simultaneously with, or simultaneously with, the acrylamide compound (B) or the acrylamide compound (B) and the unsaturated carboxylic acid compound (C). No problem.
〈実施例〉 以下、実施例により本発明をさらに詳細に説明する
が、本発明はこれらの実施例に限定されるものではな
い。例中にある％は、特に断りのない限り重量％を表
す。なお、実施例及び比較例中の未反応モノマーの定量
は、ガスクロマトグラフィーによる分析、ヨード法によ
る二重結合の定量及びコロイド当量の測定により行っ
た。<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The percentages in the examples represent% by weight unless otherwise specified. In addition, the quantification of the unreacted monomer in the examples and comparative examples was performed by analysis by gas chromatography, quantification of double bonds by iodine method, and measurement of colloid equivalent.
実施例１ 98％ジアリルメチルアミン塩酸塩3.8g（0.025モル）
及びイオン交換水97.6gを撹拌機付反応器に仕込み、pH
＝7.0に調整した。次いで、窒素ガスで充分装置内の空
気を置換して酸素不含とした後、70℃の過硫酸アンモニ
ウム0.1gを添加した。続いて、内温を70℃に保ちなが
ら、50％アクリルアミド水溶液32.0g（0.225モル）を２
時間かけて反応系内に滴下した。その後、70℃で２時間
保温して反応を完結させた。未反応モノマーの定量によ
り、ジアリルメチルアミン塩酸塩及びアクリルアミドの
反応率は、それぞれ99％以上であった。Example 1 98 g of 98% diallylmethylamine hydrochloride (0.025 mol)
And 97.6 g of ion-exchanged water in a reactor equipped with a stirrer,
= 7.0 was adjusted. Next, the air in the apparatus was sufficiently replaced with nitrogen gas to make it oxygen-free, and then 0.1 g of ammonium persulfate at 70 ° C was added. Subsequently, while maintaining the internal temperature at 70 ° C., 32.0 g (0.225 mol) of a 50% acrylamide aqueous solution was added to 2
It was dropped into the reaction system over time. Thereafter, the temperature was kept at 70 ° C. for 2 hours to complete the reaction. According to the quantification of the unreacted monomer, the reaction rates of diallylmethylamine hydrochloride and acrylamide were each 99% or more.
生成物はポリマー成分15％で、pH＝3.9、25℃におけ
るブルックフィールド粘度が55Ps（ポアズ）であった。The product had a polymer component of 15%, a Brookfield viscosity of 55 Ps (Poise) at pH = 3.9 and 25 ° C.
実施例２ 50％ジアリルアミン塩酸塩水溶液10.7g（0.04モル）
及びイオン交換水144.1gを撹拌機付反応器に仕込み、微
量の28％苛性ソーダ水溶液にてpH＝6.0に調整した。次
いで、窒素ガスで充分装置内の空気を置換して酸素不含
とした後、70℃で過硫酸アンモニウム0.28gを添加し
た。続いて内温を70℃に保ちながら、50％アクリルアミ
ド水溶液51.2g（0.36モル）を３時間かけて反応系内に
滴下した。その後、70℃で２時間保温して反応を完結さ
せた。未反応モノマーの定量により、ジアリルアミン塩
酸塩及びアクリルアミドの反応率は、それぞれ99％以上
であった。Example 2 10.7 g (0.04 mol) of a 50% aqueous solution of diallylamine hydrochloride
And 144.1 g of ion-exchanged water were charged into a reactor equipped with a stirrer, and adjusted to pH = 6.0 with a trace amount of a 28% aqueous sodium hydroxide solution. Next, the air in the apparatus was sufficiently replaced with nitrogen gas to make it oxygen-free, and then 0.28 g of ammonium persulfate was added at 70 ° C. Subsequently, while maintaining the internal temperature at 70 ° C., 51.2 g (0.36 mol) of a 50% acrylamide aqueous solution was dropped into the reaction system over 3 hours. Thereafter, the temperature was kept at 70 ° C. for 2 hours to complete the reaction. According to the quantification of the unreacted monomer, the conversion of diallylamine hydrochloride and acrylamide was 99% or more, respectively.
生成物はポリマー成分15％で、pH＝3,5、25℃におけ
るブルックフィールド粘度が38Psであった。The product had a polymer component of 15% and a Brookfield viscosity of 38 Ps at 25 ° C., pH = 3.5.
実施例３ 50％ジアリルアミン塩酸塩水溶液10.7g（0.04モル）
及びイオン交換水116.1gを撹拌機付反応器に仕込み、微
量の28％苛性ソーダ水溶液にてpH＝5.5に調整した。次
いで、窒素ガスで充分装置内の空気を置換して酸素不含
とした。次に内温を70℃に保ちながら、１％過硫酸アン
モニア水溶液28.0g及び50％アクリルアミド水溶液51.2g
（0.36モル）を、それぞれ同時に２時間かけて反応系内
に滴下した。その後、70℃で５時間保温して反応を完結
させた。未反応モノマーの定量により、ジアリルアミン
塩酸塩及びアクリルアミドの反応率は、それぞれ95％及
び99％であった。Example 3 10.7 g (0.04 mol) of a 50% diallylamine hydrochloride aqueous solution
Then, 116.1 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and the pH was adjusted to 5.5 with a trace amount of a 28% aqueous sodium hydroxide solution. Next, the air in the apparatus was sufficiently replaced with nitrogen gas to make it oxygen-free. Next, while maintaining the internal temperature at 70 ° C., 28.0 g of a 1% aqueous solution of ammonium persulfate and 51.2 g of a 50% aqueous solution of acrylamide
(0.36 mol) were simultaneously dropped into the reaction system over 2 hours. Thereafter, the temperature was maintained at 70 ° C. for 5 hours to complete the reaction. The conversion of diallylamine hydrochloride and acrylamide was 95% and 99%, respectively, by quantification of unreacted monomer.
生成物はポリマー成分15％で、pH＝3.9、25℃におけ
るブルックフィールド粘度が18Psであった。The product had a polymer component of 15%, a pH = 3.9 and a Brookfield viscosity at 25 ° C. of 18 Ps.
実施例４ 71.4％ジアリルジメチルアンモニウムクロライド水溶
液23.8g（0.106モル）及びイオン交換水71.0gを撹拌機
付反応器に仕込み、窒素ガスで充分装置内の空気を置換
して酸素不含とした。次に内温70℃で過硫酸カリウム1.
88gを添加した後、内温を70℃に保ちながら、50％アク
リルアミド水溶液60g（0.423モル）を２時間30分かけて
反応系内に滴下した。その後、70℃で３時間保温して反
応を完結させた。未反応モノマーの定量により、ジアリ
ルジメチルアンモニウムクロライド及びアクリルアミド
の反応率は、それぞれ99％以上であった。Example 4 A reactor equipped with a stirrer was charged with 23.8 g (0.106 mol) of a 71.4% diallyldimethylammonium chloride aqueous solution and 71.0 g of ion-exchanged water, and the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen. Next, potassium persulfate 1.
After adding 88 g, 60 g (0.423 mol) of a 50% aqueous acrylamide solution was dropped into the reaction system over 2 hours and 30 minutes while maintaining the internal temperature at 70 ° C. Thereafter, the temperature was kept at 70 ° C. for 3 hours to complete the reaction. According to the quantification of the unreacted monomer, the reaction rates of diallyldimethylammonium chloride and acrylamide were each 99% or more.
生成物はポリマー成分30％で、pH＝2.3、25℃におけ
るブルックフィールド粘度が39Psであった。The product was 30% polymer component, pH = 2.3, Brookfield viscosity at 25 ° C. was 39 Ps.
実施例５ 50％ジアリルアミン塩酸塩水溶液9.6g（0.036モル）
及びイオン交換水146.5gを撹拌機付反応器に仕込み、次
いで窒素ガスで充分装置内の空気を置換して酸素不含と
した。次に内温70℃で過硫酸カリウム0.39gを添加した
後、内温を70℃に保ちながら、50％アクリルアミド水溶
液47.2g（0.332モル）と80％アクリル酸水溶液2.9g（0.
032モル）の混合液を、２時間かけて反応系内に滴下し
た。その後、70℃で５時間保温して反応を完結させた。
未反応モノマーの定量により、ジアリルアミン塩酸塩、
アクリルアミド及びアクリル酸の反応率は、それぞれ99
％以上であった。Example 5 9.6 g (0.036 mol) of a 50% diallylamine hydrochloride aqueous solution
Then, 146.5 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and then the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen. Next, after adding 0.39 g of potassium persulfate at an internal temperature of 70 ° C., while maintaining the internal temperature at 70 ° C., 47.2 g (0.332 mol) of a 50% aqueous acrylamide solution and 2.9 g of an 80% aqueous acrylic acid solution (0.
032 mol) was dropped into the reaction system over 2 hours. Thereafter, the temperature was maintained at 70 ° C. for 5 hours to complete the reaction.
By quantification of unreacted monomer, diallylamine hydrochloride,
The reaction rates of acrylamide and acrylic acid were 99
% Or more.
生成物はポリマー成分15％で、pH＝29、25℃における
ブルックフィールド粘度が100Psであった。The product had a polymer component of 15%, a Brookfield viscosity of 100 Ps at pH = 29 and 25 ° C.
実施例６ 50％ジアリルアミン塩酸塩水溶液の量を2.14g（0.008
モル）、50％アクリルアミド水溶液の量を55.7g（0.392
モル）とし、イオン交換水の量を適宜変更した以外は、
実施例２と同様にしてカチオン性重合体を製造した。未
反応モノマーの定量より、ジアリルアミン塩酸塩及びア
クリルアミドの反応率は、それぞれ99％以上であった。Example 6 The amount of a 50% aqueous diallylamine hydrochloride solution was 2.14 g (0.008 g).
Mol), 55.7 g (0.392
Mol) and the amount of ion-exchanged water was changed as appropriate.
A cationic polymer was produced in the same manner as in Example 2. From the quantification of the unreacted monomer, the reaction rates of diallylamine hydrochloride and acrylamide were each 99% or more.
生成物はポリマー成分30％で、pH＝2.70、25℃におけ
るブルックフィールド粘度が10Psであった。The product had a polymer component of 30%, a pH of 2.70 and a Brookfield viscosity at 25 ° C. of 10 Ps.
実施例７ 50％ジアリルアミン塩酸塩水溶液の量を64.2g（0.24
モル）、50％アクリルアミド水溶液の量を22.8g（0.16
モル）とし、イオン交換水の量を適宜変更した以外は、
実施例２と同様にしてカチオン性重合体を製造した。未
反応モノマーの定量より、ジアリルアミン塩酸塩及びア
クリルアミドの反応率は、それぞれ99％以上であった。Example 7 The amount of a 50% aqueous diallylamine hydrochloride solution was adjusted to 64.2 g (0.24 g).
Mole), 22.8 g (0.16
Mol) and the amount of ion-exchanged water was changed as appropriate.
A cationic polymer was produced in the same manner as in Example 2. From the quantification of the unreacted monomer, the reaction rates of diallylamine hydrochloride and acrylamide were each 99% or more.
生成物ポリマー成分30％で、pH＝2.67、25℃における
ブルックフィールド粘度が1Psであった。The Brookfield viscosity at 25 ° C. was 1 Ps at 30% product polymer component.
実施例８ 50％ジアリルアミン塩酸塩水溶液の量を5.35g（0.02
モル）、50％アクリルアミド水溶液の量を42.6g（0.30
モル）、80％アクリル酸水溶液の量を7.2g（0.08モル）
とし、イオン交換水の量を適宜変更した以外は、実施例
５と同様にして両性重合体を製造した。未反応モノマー
の定量より、ジアリルアミン塩酸塩、アクリルアミド及
びアクリル酸の反応率は、それぞれ99％以上であった。Example 8 The amount of an aqueous 50% diallylamine hydrochloride solution was 5.35 g (0.02 g).
Mol), 42.6 g (0.30
Mol), the amount of 80% acrylic acid aqueous solution is 7.2 g (0.08 mol)
An amphoteric polymer was produced in the same manner as in Example 5, except that the amount of ion-exchanged water was appropriately changed. From the quantification of the unreacted monomer, the reaction rates of diallylamine hydrochloride, acrylamide and acrylic acid were each at least 99%.
生成物はポリマー成分15％で、pH＝2.8、25℃におけ
るブルックフィールド粘度が41Psであった。The product had a polymer component of 15%, a pH = 2.8, and a Brookfield viscosity at 25 ° C. of 41 Ps.
実施例９ 98％ジアリルメチルアミン塩酸塩の量を18.2g（0.120
モル）、50％アクリルアミド水溶液の量を39.8g（0.280
モル）とし、イオン交換水の量を適宜変更した以外は、
実施例１と同様にしてカチオン性重合体を製造した。未
反応モノマーの定量より、ジアリルメチルアミン塩酸塩
及びアクリルアミドの反応率は、それぞれ99％以上であ
った。Example 9 The amount of 98% diallylmethylamine hydrochloride was 18.2 g (0.120 g).
Mol), 39.8 g (0.280 g) of 50% acrylamide aqueous solution
Mol) and the amount of ion-exchanged water was changed as appropriate.
A cationic polymer was produced in the same manner as in Example 1. From the quantification of the unreacted monomer, the reaction rates of diallylmethylamine hydrochloride and acrylamide were each 99% or more.
生成物はポリマー成分15％で、pH＝3.5、25℃におけ
るブルックフィールド粘度が28Psであった。The product had a polymer component of 15%, a pH = 3.5 and a Brookfield viscosity at 25 ° C. of 28 Ps.
実施例10 71.4％ジアリルジメチルアンモニウムクロライド水溶
液35.9g（0.16モル）及びイオン交換水213.3gを撹拌機
付反応器に仕込み、次いで、窒素ガスで充分装置内の空
気を置換して酸素不含とした。次に内温70℃で過硫酸カ
リウム0.39gを添加した後、内温を70℃に保ちながら、5
0％アクリルアミド水溶液31.2g（0.22モル）とアクリロ
ニトリル1.06g（0.02モル）の混合液を、２時間かてて
反応系内に滴下した。その後、70℃で５時間保温して反
応を完結させた。未反応モノマーの定量より、ジアリル
ジメチルアンモニウムクロライド、アクリルアミド及び
アクリロニトリルの反応率は、それぞれ99％以上であっ
た。Example 10 A reactor equipped with a stirrer was charged with 35.9 g (0.16 mol) of a 71.4% diallyl dimethyl ammonium chloride aqueous solution and 213.3 g of ion-exchanged water, and then the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen. . Next, after adding 0.39 g of potassium persulfate at an internal temperature of 70 ° C, while maintaining the internal temperature at 70 ° C, 5
A mixture of 31.2 g (0.22 mol) of a 0% acrylamide aqueous solution and 1.06 g (0.02 mol) of acrylonitrile was dropped into the reaction system over 2 hours. Thereafter, the temperature was maintained at 70 ° C. for 5 hours to complete the reaction. From the quantification of the unreacted monomer, the reaction rates of diallyldimethylammonium chloride, acrylamide and acrylonitrile were each 99% or more.
生成物はポリマー成分15％で、pH＝3.2、25℃におけ
るブルックフィールド粘度が30Psであった。The product had a polymer component of 15%, a pH = 3.2 and a Brookfield viscosity at 25 ° C. of 30 Ps.
実施例11 50％ジアリルアミン塩酸塩水溶液21.4g（0.08モル）
及びイオン交換水43.3gを撹拌機付反応器に仕込み、窒
素ガスで充分装置内の空気を置換して酸素不含とした。
次に、内温70℃で過硫酸カリウム0.39gを添加した後、
内温を70℃に保ちながら、50％アクリルアミド水溶液3
9.8g（0.28モル）、80％アクリル酸水溶液1.8g（0.02モ
ル）及びスチレン2.1g（0.02モル）の混合液を、４時間
かけて反応系内に滴下した。その後70℃で５時間保温し
て反応を完結させた。未反応モノマーの定量より、ジア
リルアミン塩酸塩、アクリルアミド、アクリル酸及びス
チレンの反応率は、それぞれ99％以上であった。Example 11 21.4 g (0.08 mol) of a 50% diallylamine hydrochloride aqueous solution
Then, 43.3 g of ion-exchanged water was charged into a reactor equipped with a stirrer, and the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen.
Next, after adding 0.39 g of potassium persulfate at an internal temperature of 70 ° C,
While maintaining the internal temperature at 70 ° C, a 50% acrylamide aqueous solution 3
A mixture of 9.8 g (0.28 mol), 1.8 g (0.02 mol) of an 80% aqueous solution of acrylic acid and 2.1 g (0.02 mol) of styrene was dropped into the reaction system over 4 hours. Thereafter, the temperature was maintained at 70 ° C. for 5 hours to complete the reaction. From the quantification of the unreacted monomer, the reaction rates of diallylamine hydrochloride, acrylamide, acrylic acid, and styrene were each 99% or more.
生成物はポリマー成分30％で、pH＝3.0、25℃におけ
るブルックフィールド粘度が3Psであった。The product had a polymer component of 30%, a pH = 3.0, and a Brookfield viscosity at 25 ° C. of 3 Ps.
比較例 50％ジアリルアミン塩酸塩水溶液10.7g（0.04モル）
及びイオン交換水144.1gを撹拌機付反応器に仕込み、微
量の28％苛性ソーダ水溶液にてpH＝6.0に調整した。こ
れに50％アクリルアミド水溶液51.2g（0.36モル）を仕
込んだ後、窒素ガスで充分装置内の空気を置換して酸素
不含とした。次いで内温を70℃とし、過硫酸アンモニウ
ム0.28gを添加した後、70℃で６時間保温した。未反応
モノマーの定量より、ジアリルアミン塩酸塩及びアクリ
ルアミドの反応率は、それぞれ63.0％及び95.1％であっ
た。Comparative Example 10.7 g (0.04 mol) of 50% diallylamine hydrochloride aqueous solution
And 144.1 g of ion-exchanged water were charged into a reactor equipped with a stirrer, and adjusted to pH = 6.0 with a trace amount of a 28% aqueous sodium hydroxide solution. After 51.2 g (0.36 mol) of a 50% aqueous acrylamide solution was charged therein, the air in the apparatus was sufficiently replaced with nitrogen gas to eliminate oxygen. Next, the internal temperature was set to 70 ° C., 0.28 g of ammonium persulfate was added, and the mixture was kept at 70 ° C. for 6 hours. From the quantification of the unreacted monomer, the reaction rates of diallylamine hydrochloride and acrylamide were 63.0% and 95.1%, respectively.
生成物の25℃におけるブルックフィールド粘度は23P
s、pH＝3.3であった。The Brookfield viscosity of the product at 25 ° C is 23P
s, pH = 3.3.
〈発明の効果〉 以上の実施例及び比較例の対比からもわかるように、従
来の製造方法では反応しにくかったジアリルアミン誘導
体モノマーが、本発明の製造方法によればほとんど反応
するようになり、したがって得られる共重合体水溶液
は、製紙用添加剤などとして有効に作用するポリマーを
多く含み、紙の製造などに有利に使用することができ
る。<Effect of the Invention> As can be seen from the comparison between the above Examples and Comparative Examples, the diallylamine derivative monomer, which was difficult to react in the conventional production method, almost reacted according to the production method of the present invention, The resulting aqueous copolymer solution contains a large amount of a polymer that effectively acts as an additive for papermaking and the like, and can be advantageously used for paper production and the like.
Claims (2)
R3及びR4はそれぞれ単独に、水素又は炭素数１〜６のア
ルキル基を表し、X-は有機酸又は無機酸の陰イオンを表
す） で表されるジアリルアミン誘導体モノマー（Ａ）と、一
般式（II） CH2＝Ｃ（R5）−CONH2 （II） （式中、R5は水素又はメチル基を表す） で表されるアクリルアミド系化合物（Ｂ）とを共重合し
てカチオン性共重合体を製造する方法において、ジアリ
ルアミン誘導体モノマー（Ａ）を含有する水溶液に、ア
クリルアミド系化合物（Ｂ）を連続的に添加しながら重
合反応を行うことを特徴とするカチオン性共重合体の製
造方法。1. The compound of the general formula (I) (Wherein, R 1 and R 2 each represent hydrogen or a methyl group,
R 3 and R 4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X − represents an anion of an organic acid or an inorganic acid), and a diallylamine derivative monomer (A) represented by the general formula: Formula (II) CH 2 ＣC (R 5 ) —CONH 2 (II) (wherein, R 5 represents hydrogen or a methyl group) and copolymerizes with an acrylamide-based compound (B) to form a cationic compound In a method for producing a copolymer, a polymerization reaction is carried out while continuously adding an acrylamide compound (B) to an aqueous solution containing a diallylamine derivative monomer (A). Method.
R3及びR4はそれぞれ単独に、水素又は炭素数１〜６のア
ルキル基を表し、X-は有機酸又は無機酸の陰イオンを表
す） で表されるジアリルアミン誘導体モノマー（Ａ）、一般
式（II） CH2＝Ｃ（R5）−CONH2 （II） （式中、R5は水素又はメチル基を表す） で表されるアクリルアミド系化合物（Ｂ）並びに、α，
β−不飽和モノカルボン酸、α，β−不飽和ジカルボン
酸及びこれらの塩類からなる群より選ばれた１又は２以
上の不飽和カルボン酸化合物（Ｃ）を共重合して両性共
重合体を製造する方法において、ジアリルアミン誘導体
モノマー（Ａ）を含有する水溶液に、アクリルアミド系
化合物（Ｂ）及び不飽和カルボン酸化合物（Ｃ）を連続
的に添加しながら重合反応を行うことを特徴とする両性
共重合体の製造方法。2. Formula (I) (Wherein, R 1 and R 2 each represent hydrogen or a methyl group,
R 3 and R 4 each independently represent hydrogen or an alkyl group having 1 to 6 carbon atoms, and X − represents an anion of an organic acid or an inorganic acid) a diallylamine derivative monomer (A) represented by the general formula: (II) an acrylamide compound (B) represented by CH 2 ＣC (R 5 ) —CONH 2 (II) (wherein R 5 represents hydrogen or a methyl group);
An amphoteric copolymer is obtained by copolymerizing one or more unsaturated carboxylic acid compounds (C) selected from the group consisting of β-unsaturated monocarboxylic acids, α, β-unsaturated dicarboxylic acids and salts thereof. In the method for producing, the polymerization reaction is carried out while continuously adding the acrylamide compound (B) and the unsaturated carboxylic acid compound (C) to an aqueous solution containing the diallylamine derivative monomer (A). A method for producing a polymer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26098886 | 1986-10-31 | ||
| JP61-260988 | 1986-10-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63225608A JPS63225608A (en) | 1988-09-20 |
| JP2615681B2 true JP2615681B2 (en) | 1997-06-04 |
Family
ID=17355506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62263538A Expired - Lifetime JP2615681B2 (en) | 1986-10-31 | 1987-10-19 | Method for producing water-soluble copolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2615681B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2642263B2 (en) * | 1991-10-21 | 1997-08-20 | 積水化学工業株式会社 | Method for producing solvent-based acrylic pressure-sensitive adhesive |
| JPH083229A (en) | 1994-06-20 | 1996-01-09 | Sumitomo Chem Co Ltd | Production of aqueous copolymer solution |
| US6811839B2 (en) | 2000-11-09 | 2004-11-02 | Canon Kabushiki Kaisha | Recording medium and image forming process using the same |
| CN105568722B (en) * | 2015-12-31 | 2019-01-22 | 浙江大川新材料股份有限公司 | The preparation method of cationic fixing agent lotion |
| CN105908543A (en) * | 2016-06-07 | 2016-08-31 | 苏州联胜化学有限公司 | Environment-friendly chlorine-resistant fastness improving agent for cotton and preparation method of fastness improving agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234076A (en) | 1963-01-08 | 1966-02-08 | Nalco Chemical Co | Method of improving retention of fillers in paper making with acrylamidediallylamine copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0615757B2 (en) * | 1985-04-30 | 1994-03-02 | 住友化学工業株式会社 | Paper manufacturing method |
-
1987
- 1987-10-19 JP JP62263538A patent/JP2615681B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3234076A (en) | 1963-01-08 | 1966-02-08 | Nalco Chemical Co | Method of improving retention of fillers in paper making with acrylamidediallylamine copolymer |
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| Publication number | Publication date |
|---|---|
| JPS63225608A (en) | 1988-09-20 |
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