JP3147440B2 - Method for producing water-soluble polymer - Google Patents
Method for producing water-soluble polymerInfo
- Publication number
- JP3147440B2 JP3147440B2 JP28884291A JP28884291A JP3147440B2 JP 3147440 B2 JP3147440 B2 JP 3147440B2 JP 28884291 A JP28884291 A JP 28884291A JP 28884291 A JP28884291 A JP 28884291A JP 3147440 B2 JP3147440 B2 JP 3147440B2
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- Prior art keywords
- water
- monomer
- soluble polymer
- polymerization
- weight
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Description
【０００１】[0001]
【産業上の利用分野】本発明は水溶性ポリマーの製造法
に関する。詳しくは、水溶性のＮ−ビニルカルボン酸ア
ミド（共）重合体の変性物を製造する方法に関するもの
である。The present invention relates to a method for producing a water-soluble polymer. More specifically, the present invention relates to a method for producing a modified product of a water-soluble N-vinylcarboxylic acid amide (co) polymer.
【０００２】[0002]
【従来の技術】Ｎ−ビニルカルボン酸アミド、および場
合により他の水溶性ビニル化合物との混合物を懸濁重合
し、該重合体を更に加水分解することにより、Ｎ−ビニ
ルカルボン酸アミド重合体の水溶性変性物を得る方法は
知られている（特開昭６１−１４１７１２）。該変性物
ポリマーは、有機汚泥の脱水用凝集剤、紙用薬剤等とし
て卓越した効果が期待されている。2. Description of the Related Art N-vinyl carboxylic acid amide and, if necessary, a mixture with another water-soluble vinyl compound are subjected to suspension polymerization, and the resulting polymer is further hydrolyzed to give an N-vinyl carboxylic acid amide polymer. A method for obtaining a water-soluble modified product is known (JP-A-61-141712). The modified polymer is expected to have an excellent effect as a flocculant for dewatering organic sludge, a chemical for paper and the like.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、従来の
方法においては、加水分解工程において変性物のゲル化
（水不溶化）が生じやすく、品質の良い粉末状の水溶性
ポリマーを効率よく製造することが困難であった。However, in the conventional method, gelation (water insolubilization) of the denatured product is apt to occur in the hydrolysis step, and it is necessary to efficiently produce a high-quality powdery water-soluble polymer. It was difficult.
【０００４】[0004]
【課題を解決するための手段】そこで、本発明者等は上
記の問題点につき鋭意検討を行った結果、特定の方法で
重合を進行させた場合に、懸濁重合後、酸性加水分解し
た後の変性物ポリマーのゲル化が防止されて粉末状で高
分子量の水溶性ポリマーが得られることを見い出し本発
明に到達した。The inventors of the present invention have conducted intensive studies on the above-mentioned problems, and as a result, when the polymerization was advanced by a specific method, after the suspension polymerization and after the acidic hydrolysis, It has been found that gelation of the modified polymer is prevented and that a high molecular weight water-soluble polymer can be obtained in the form of powder.
【０００５】即ち、本発明の要旨は、モノマーとして一
般式That is, the gist of the present invention is that a monomer represented by the general formula
【０００６】[0006]
【化２】ＣＨ2 ＝ＣＨＮＨＣＯＲEmbedded image CH 2 ＣＨCHNHCOR
【０００７】（式中、Ｒは水素原子またはメチル基を表
わす。）で示されるＮ−ビニルカルボン酸アミド単独、
または該Ｎ−ビニルカルボン酸アミドと共重合可能な他
の水溶性ビニル化合物との混合物を、炭化水素系分散
媒、水、分散剤および重合開始剤の存在下で懸濁重合
し、次いで酸性加水分解することにより水溶性ポリマー
を製造する方法において、分散剤の存在下、水の全使用
量の２０重量％以上をあらかじめ炭化水素分散媒に懸濁
させた後、前記モノマーを、そのまま、または、残りの
水を加えた水溶液として添加することを特徴とする水溶
性ポリマーの製造法に存する。(Wherein, R represents a hydrogen atom or a methyl group)
Alternatively, a mixture of the N-vinylcarboxylic acid amide and another water-soluble vinyl compound copolymerizable with the N-vinylcarboxylic acid amide is subjected to suspension polymerization in the presence of a hydrocarbon-based dispersion medium, water, a dispersant, and a polymerization initiator, and then subjected to acidic hydrolysis. In a method for producing a water-soluble polymer by decomposing, in the presence of a dispersant, 20% by weight or more of the total amount of water is previously suspended in a hydrocarbon dispersion medium, and then the monomer is used as it is, or The present invention relates to a method for producing a water-soluble polymer, which comprises adding the remaining water as an aqueous solution.
【０００８】以下、本発明を詳細に説明する。本発明に
用いられる一般式 ＣＨ2 ＝ＣＨＮＨＣＯＲ （式中、Ｒは、水素原子またはメチル基を表わす。）で
示されるＮ−ビニルカルボン酸アミドとしてはＮ−ビニ
ルホルムアミドおよびＮ−ビニルアセトアミドが挙げら
れるが、Ｎ−ビニルカルボン酸アミド重合体の変性物を
得る目的のためには重合体の加水分解性の良いことから
Ｎ−ビニルホルムアミドが好ましい。Hereinafter, the present invention will be described in detail. Examples of the N-vinylcarboxylic acid amide represented by the general formula CH 2 ＣＨCHNHCOR (wherein R represents a hydrogen atom or a methyl group) used in the present invention include N-vinylformamide and N-vinylacetamide. However, for the purpose of obtaining a modified N-vinylcarboxylic acid amide polymer, N-vinylformamide is preferred because of its good hydrolyzability.
【０００９】本発明の重合には、モノマーとしてＮ−ビ
ニルカルボン酸アミド単独またはＮ−ビニルカルボン酸
アミドと他の水溶性ビニル化合物との混合物が用いられ
る。水溶性ビニル化合物としてはＮ−ビニルカルボン酸
アミドと共重合可能で本発明に用いられる炭化水素系分
散媒に実質的に不溶性である化合物が用いられ、アクリ
ロニトリル、メタアクリロニトリル、アクリルアミド、
メタアクリルアミド、アクリル酸、メタクリル酸、アク
リロイルオキシエチルトリメチルアンモニウムクロライ
ド、メタアクリロイルオキシエチルトリメチルアンモニ
ウムクロライドなどの水溶性ビニル化合物が例示され
る。In the polymerization of the present invention, N-vinylcarboxylic acid amide alone or a mixture of N-vinylcarboxylic acid amide and another water-soluble vinyl compound is used as a monomer. As the water-soluble vinyl compound, a compound which is copolymerizable with N-vinylcarboxylic acid amide and is substantially insoluble in the hydrocarbon dispersion medium used in the present invention is used, and acrylonitrile, methacrylonitrile, acrylamide,
Examples thereof include water-soluble vinyl compounds such as methacrylamide, acrylic acid, methacrylic acid, acryloyloxyethyltrimethylammonium chloride, and methacryloyloxyethyltrimethylammonium chloride.
【００１０】Ｎ−ビニルカルボン酸アミド（Ａ）を上記
の水溶性ビニル化合物（Ｂ）と共重合する場合は、
（Ａ）と（Ｂ）の共重合モル比は、通常２０：８０〜９
５：５、好ましくは３０：７０〜９０：１０、更に好ま
しくは４０：６０〜８０：２０であるが、この範囲に特
に限定されるものではない。本発明の懸濁重合に用いる
炭化水素系分散媒としては、水と共沸する炭化水素が好
ましい。例えばｎ−ヘキサン、ｎ−ヘプタン、ｎ−オク
タン、ノナン、デカン、ウンデカン、ドデカンなどの鎖
状飽和炭化水素、沸点６５〜２５０℃の石油留分好まし
くは沸点８０℃〜１８０℃の石油留分、シクロヘキサ
ン、メチルシクロヘキサンなどの脂環族炭化水素、ベン
ゼン、トルエン、キシレン、エチルベンゼンなどの芳香
族炭化水素が挙げられる。When the N-vinylcarboxylic acid amide (A) is copolymerized with the water-soluble vinyl compound (B),
The copolymerization molar ratio of (A) and (B) is usually from 20:80 to 9
The ratio is 5: 5, preferably 30:70 to 90:10, and more preferably 40:60 to 80:20, but is not particularly limited to this range. As the hydrocarbon dispersion medium used in the suspension polymerization of the present invention, a hydrocarbon azeotropic with water is preferable. For example, chain saturated hydrocarbons such as n-hexane, n-heptane, n-octane, nonane, decane, undecane and dodecane, a petroleum fraction having a boiling point of 65 to 250 ° C, preferably a petroleum fraction having a boiling point of 80 ° C to 180 ° C, Alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene.
【００１１】分散剤としては、通常、非乳化性油溶性高
分子、または、一般的な界面活性剤が使用される。非乳
化性油溶性高分子としては、エチルセルロースやヒドロ
キシエチルセルロース等の油溶性セルロース、オレフィ
ン類と無水マレイン酸との付加物が例示される。また、
界面活性剤としては、好ましくはＨ．Ｌ．Ｂ．が９以上
程度のノニオン系界面活性剤、例えば、ポリオキシエチ
レンアルキルエーテル、ポリオキシエチレンアルキルフ
ェニルエーテル等が用いられる。以上の分散剤の使用量
は、分散媒に対して、通常０．０１〜５重量％、好まし
くは０．０５〜１重量％である。As the dispersant, a non-emulsifiable oil-soluble polymer or a general surfactant is usually used. Examples of the non-emulsifying oil-soluble polymer include oil-soluble celluloses such as ethyl cellulose and hydroxyethyl cellulose, and adducts of olefins and maleic anhydride. Also,
As the surfactant, H.I. L. B. And about 9 or more nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether. The amount of the above dispersant to be used is generally 0.01 to 5% by weight, preferably 0.05 to 1% by weight, based on the dispersion medium.
【００１２】次に、重合開始剤としては、一般的なラジ
カル重合開始剤を用いることができるが、アゾ化合物が
好ましい。特に好ましくは水溶性のアゾ化合物であり、
２，２′−アゾビス−２−アミジノプロパンの塩酸塩、
硫酸塩および酢酸塩、アゾビス−Ｎ，Ｎ′−ジメチレン
イソブチルアミジンの塩酸塩、硫酸塩および酢酸塩、
４，４′−アゾビス−４−シアノ吉草酸のアルカリ金属
塩およびアンモニウム塩などが例示される。ラジカル重
合開始剤は、原料モノマーに対して重量基準で通常１０
０〜１００００ｐｐｍ、好ましくは、５００〜５０００
ｐｐｍの範囲で用いられる。Next, a general radical polymerization initiator can be used as the polymerization initiator, but an azo compound is preferred. Particularly preferred is a water-soluble azo compound,
2,2'-azobis-2-amidinopropane hydrochloride,
Sulfates and acetates, hydrochlorides, sulfates and acetates of azobis-N, N'-dimethyleneisobutylamidine,
Examples thereof include alkali metal salts and ammonium salts of 4,4'-azobis-4-cyanovaleric acid. The radical polymerization initiator is usually 10 parts by weight based on the raw material monomer.
0 to 10000 ppm, preferably 500 to 5000 ppm
Used in the ppm range.
【００１３】更に、場合によっては、重合安定剤として
各種の添加物を使用してもよく、例えば、塩化アンモニ
ウム、塩化カルシウム等が、モノマーに対して通常１〜
１０重量％使用される。以上に説明したモノマー、炭化
水素系分散媒、分散剤および重合開始剤に、水を添加し
た反応系で懸濁重合を行う。本発明の重合方法の特徴と
するところは、該重合に際し、モノマーを反応系に添加
する段階にある。Further, depending on the case, various additives may be used as a polymerization stabilizer. For example, ammonium chloride, calcium chloride and the like are usually used in an amount of 1 to 1 with respect to the monomer.
Used at 10% by weight. Suspension polymerization is performed in a reaction system in which water is added to the above-described monomer, hydrocarbon-based dispersion medium, dispersant, and polymerization initiator. The feature of the polymerization method of the present invention resides in the step of adding a monomer to the reaction system during the polymerization.
【００１４】従来の懸濁重合法においては、予めモノマ
ーと重合開始剤の両者を含む水溶液を調整しておき、該
水溶液を攪拌下分散媒中に添加し、該水溶液を分散媒中
に水滴状に分散させて重合する方法が一般的である。そ
して、該従来法でも、重合、変性し、ゲル化することな
く水溶性ポリマーを得ることは可能である。しかしなが
ら、従来法を採用することにより得られる水溶性ポリマ
ーは、比較的低分子量の場合に限られる。通常、高分子
量の重合体を得る場合は、反応系の重合開始剤の量を少
なくしたり、モノマー水溶液の濃度を高める等の手段が
選択されるが、従来法では、特にモノマー水溶液の濃度
の影響が強く、モノマー水溶液の濃度が例えば、２０重
量％以上、特に３０重量％以上とした場合にゲル化が顕
著となる傾向がある。In the conventional suspension polymerization method, an aqueous solution containing both a monomer and a polymerization initiator is prepared in advance, and the aqueous solution is added to a dispersion medium with stirring, and the aqueous solution is added dropwise to the dispersion medium. In general, a method of dispersing and polymerizing the mixture is used. And even with the conventional method, it is possible to obtain a water-soluble polymer without polymerizing, modifying and gelling. However, the water-soluble polymer obtained by employing the conventional method is limited to a case of a relatively low molecular weight. Usually, when a polymer having a high molecular weight is obtained, means such as reducing the amount of the polymerization initiator in the reaction system or increasing the concentration of the aqueous monomer solution is selected. The influence is strong, and when the concentration of the monomer aqueous solution is, for example, 20% by weight or more, particularly 30% by weight or more, gelation tends to be remarkable.
【００１５】以下、本発明の重合方法について更に詳細
に述べる。懸濁重合に必要とする水の使用量は、モノマ
ーに対して、通常０．１〜３重量倍、好ましくは０．４
〜２重量倍である。該範囲より多くすると分子量が低下
傾向となり、また、該範囲より少ないと水滴の分散が不
充分となる。また、分散媒の量は、前記のモノマーと水
の全量の通常０．５〜１０容量倍、好ましくは１〜５容
量倍である。Hereinafter, the polymerization method of the present invention will be described in more detail. The amount of water required for suspension polymerization is usually 0.1 to 3 times by weight, preferably 0.4
~ 2 times the weight. If it exceeds this range, the molecular weight tends to decrease, and if it is less than this range, the dispersion of water droplets becomes insufficient. The amount of the dispersion medium is usually 0.5 to 10 times by volume, preferably 1 to 5 times by volume of the total amount of the monomer and water.
【００１６】水の全使用量の２０重量％以上、好ましく
は５０重量％以上、特に好ましくは９０重量％以上を予
め分散媒中に添加し攪拌により懸濁相を形成させてお
き、そこに、モノマーを、そのまま、または、残りの水
を加えた水溶液として添加する。懸濁相への水の添加量
が２０重量％以下では、従来法と比較した場合のゲル化
防止の効果の差が明確でなくなる。At least 20% by weight, preferably at least 50% by weight, particularly preferably at least 90% by weight, of the total amount of water used is added in advance to a dispersion medium, and a suspension phase is formed by stirring. The monomer is added neat or as an aqueous solution with the remaining water. When the amount of water added to the suspension phase is 20% by weight or less, the difference in the effect of preventing gelation as compared with the conventional method is not clear.
【００１７】モノマーまたはモノマー水溶液の添加方法
は、通常、モノマーを少量づつゆっくり滴下していくも
のである。回分式反応器を用いて重合を行う場合は、全
量を添加するために通常０．５〜８時間、好ましくは１
〜５時間を要する。この間、ある程度間欠的に添加して
も特に支障はないが、該範囲以上に時間をかけても操作
上効率的でなく、また、重合体の分子量が低下する傾向
も認められる。一方、該範囲よりも早く添加する場合
は、重合系の条件が従来法と実質的に差がなくなるので
好ましくない。また、重合に用いる水の量を少なくする
ほど、一般にモノマー添加時間を長くする方が好まし
い。The method of adding the monomer or the aqueous monomer solution is usually a method in which the monomer is slowly dropped in small amounts. When the polymerization is carried out using a batch reactor, usually 0.5 to 8 hours, preferably 1 to 8 hours, in order to add the whole amount.
It takes ~ 5 hours. During this time, there is no particular problem even if it is added intermittently to some extent, but operation is not efficient even if the time is longer than this range, and the molecular weight of the polymer tends to decrease. On the other hand, if it is added earlier than this range, the polymerization system conditions are not substantially different from those of the conventional method, which is not preferable. In general, the smaller the amount of water used for the polymerization, the longer the monomer addition time is preferably.
【００１８】以上の重合反応は、一般に、不活性ガス気
流下、３０〜１００℃、好ましくは４０〜８０℃で、上
記のモノマー添加時間も含めた全反応時間を０．５〜１
０時間、好ましくは１〜８時間とした条件で実施され
る。なお、本発明の重合においては、重合開始剤及び重
合安定剤は懸濁状態下にある敷液中又は供給するモノマ
ー側のいずれに添加してもよいが、通常、敷液中に添加
しておくのが望ましい。The above polymerization reaction is generally carried out under an inert gas stream at 30 to 100 ° C., preferably 40 to 80 ° C., for a total reaction time of 0.5 to 1 including the monomer addition time.
It is carried out under the condition of 0 hour, preferably 1 to 8 hours. In the polymerization of the present invention, the polymerization initiator and the polymerization stabilizer may be added to either the suspension under suspension or the monomer side to be supplied, but usually, the suspension is added to the suspension. It is desirable to keep.
【００１９】以上の方法で得られた重合体は、通常、該
重合体を含む溶液または分散液のままで酸性加水分解に
提供される。酸としては、例えば、塩化水素、臭化水
素、フッ化水素、硫酸、硝酸、スルファミン酸、アルカ
ンスルホン酸等が挙げられるが、好ましくは塩化水素で
あり、反応系の導入形態はガス状でも、塩酸水溶液状で
もよい。The polymer obtained by the above method is usually supplied to the acidic hydrolysis in the form of a solution or dispersion containing the polymer. Examples of the acid include hydrogen chloride, hydrogen bromide, hydrogen fluoride, sulfuric acid, nitric acid, sulfamic acid, alkanesulfonic acid and the like, preferably hydrogen chloride, and the reaction system may be introduced in gaseous form. Hydrochloric acid aqueous solution may be used.
【００２０】酸の使用量は、目的とする加水分解率に応
じ適宜決定されるが、通常目的とする加水分解率のアミ
ド基の当量に対し１〜２倍である。加水分解の温度は、
Ｎ−ビニルホルムアミド重合体の場合、２０〜１３０
℃、好ましくは６０〜１２０℃であり、Ｎ−ビニルアセ
トアミド重合体の場合、５０〜１５０℃、好ましくは９
０〜１３０℃である。必要に応じ加圧反応系で実施され
る。The amount of the acid used is appropriately determined according to the desired hydrolysis rate, but is usually 1 to 2 times the equivalent of the amide group having the desired hydrolysis rate. The hydrolysis temperature is
In the case of N-vinylformamide polymer, 20 to 130
C., preferably 60 to 120 ° C., and in the case of an N-vinylacetamide polymer, 50 to 150 ° C., preferably 9
0-130 ° C. It is carried out in a pressurized reaction system as needed.
【００２１】加水分解された変性物は、そのまま、また
は中和処理し、溶媒脱水または分散媒〜水の共沸蒸留等
により分離され、粉末状水溶性ポリマーとして回収され
る。The hydrolyzed denatured product is used as it is or after neutralization, separated by solvent dehydration or azeotropic distillation of water with a dispersion medium, and recovered as a powdery water-soluble polymer.
【００２２】[0022]
【実施例】以下本発明を実施例によりさらに詳しく説明
するが本発明はその要旨を越えない限り以下の実施例に
制約されない。 実施例１ 攪拌機、冷却管、滴下ロートおよび窒素ガス導入管を備
えた１Ｌの４ツ口フラスコに、シクロヘキサン４００
ｇ、ポリオキシエチレンオレイルエーテル（第一工業製
薬（株）商品名「ノイゲンＥＴ１４０Ｅ」、Ｈ．Ｌ．
Ｂ．＝１４．０）２ｇ、水８３ｇ、塩化アンモニウム７
ｇを入れ、攪拌下５５℃に昇温した。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention. Example 1 Cyclohexane 400 was placed in a 1-L four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel, and a nitrogen gas inlet tube.
g, polyoxyethylene oleyl ether (Daiichi Kogyo Seiyaku Co., Ltd. product name “Neugen ET140E”, HL.
B. = 14.0) 2 g, water 83 g, ammonium chloride 7
g was added and the temperature was raised to 55 ° C. with stirring.
【００２３】次に、窒素ガス気流下、２，２′−アゾビ
ス−２−アミジノプロパン２塩酸塩１０重量％水溶液
２．７ｇを添加後、Ｎ−ビニルホルムアミド（純度＝９
０．０％）７９ｇ、アクリロニトリル（純度＝９９．５
％）６５ｇの混液を３時間かけて滴下した。その後、更
に反応を３時間続けた。以上の反応液１００ｇを５００
ｍｌフラスコに移し、濃塩酸を１９．４ｇ（Ｎ−ビニル
ホルムアミドに対し１．３倍モル量）を加え、攪拌下９
５℃で５時間加水分解した。室温まで冷却後、濃塩酸−
メタノール混液（容量比１：９）２００ｍｌを加えて攪
拌洗浄し、ろ過して、減圧乾燥し、ポリマーを回収し
た。Next, 2.7 g of a 10% by weight aqueous solution of 2,2'-azobis-2-amidinopropane dihydrochloride was added under a stream of nitrogen gas, followed by N-vinylformamide (purity = 9).
0.0%) 79 g, acrylonitrile (purity = 99.5)
%) Of the mixed solution was added dropwise over 3 hours. Thereafter, the reaction was further continued for 3 hours. 100 g of the above reaction solution was added to 500
Then, 19.4 g of concentrated hydrochloric acid (1.3 times the molar amount of N-vinylformamide) was added, and the mixture was stirred.
Hydrolyzed at 5 ° C for 5 hours. After cooling to room temperature, concentrated hydrochloric acid
200 ml of a methanol mixture (1: 9 by volume) was added, washed with stirring, filtered, and dried under reduced pressure to recover a polymer.
【００２４】表−１に得られたポリマーの還元粘度（η
ｓｐ／ｃ）と水に対する溶解性の結果を示す。 ・還元粘度（ηｓｐ／ｃ）の測定法 ポリマー試料０．１ｇを１００ｇの１規定食塩水にて室
温で４時間浸漬後、溶解させた後、オストワルド粘度計
に２５℃で還元粘度を測定した。 ・水に対する溶解性の評価 ポリマー試料０．１ｇを１００ｇの水にて室温で４時間
攪拌処理し溶解させた場合の不溶解物量を肉眼で観察
し、下記基準により判定した。 ○不溶解物が全く存在しない。 △極く微量の小さな不溶解物が存在する。 ×多量の不溶解物が存在する。The reduced viscosity (η) of the obtained polymer is shown in Table 1.
(sp / c) and solubility in water. Measurement method of reduced viscosity (ηsp / c) 0.1 g of a polymer sample was immersed in 100 g of 1N saline at room temperature for 4 hours, dissolved, and then reduced viscosity was measured at 25 ° C. in an Ostwald viscometer. -Evaluation of solubility in water 0.1 g of a polymer sample was stirred with 100 g of water at room temperature for 4 hours to dissolve, and the amount of insoluble matter was visually observed, and judged based on the following criteria. ○ There are no insolubles. Δ: A trace amount of small insoluble matter is present. X A large amount of insoluble matter is present.
【００２５】実施例２〜４ 重合系への水の添加量を１３６ｇ、２０４ｇと変えた以
外は実施例１と同様に実験を行った結果を表−１に示
す。なお、実施例４は、塩化アンモニウムを使用しなか
った以外は実施例３と同様の条件で実験を行ったもので
ある。Examples 2 to 4 Table 1 shows the results of an experiment conducted in the same manner as in Example 1 except that the amount of water added to the polymerization system was changed to 136 g and 204 g. In Example 4, an experiment was performed under the same conditions as in Example 3 except that ammonium chloride was not used.
【００２６】実施例５〜９ 重合に使用する水を表−１に示す割合に分けて反応系に
添加した以外は、実施例１と同様に実験を行った結果を
表−１に示す。Examples 5 to 9 Table 1 shows the results of an experiment conducted in the same manner as in Example 1 except that the water used for the polymerization was added to the reaction system in the proportions shown in Table 1.
【００２７】比較例１〜３ 実施例１〜３と同量の分散媒と分散剤を敷液とし、これ
に実施例１〜３で使用したと同量のモノマー、水、重合
開始剤および塩化アンモニウムを添加して実験を行った
結果を表−１に示す。Comparative Examples 1 to 3 The same amounts of the dispersing medium and dispersing agent as in Examples 1 to 3 were used as coating liquids, and the same amounts of monomer, water, polymerization initiator and chloride as used in Examples 1 to 3 were used. Table 1 shows the results of experiments conducted with the addition of ammonium.
【００２８】[0028]
【表１】 [Table 1]
【００２９】[0029]
【発明の効果】本発明により、Ｎ−ビニルカルボン酸ア
ミドを原料とした高分子量の水溶性ポリマーを、ゲル化
することなく効率よく製造することができる。該水溶性
ポリマーは凝集剤、紙用薬剤等として多くの産業分野で
広く利用が期待される。According to the present invention, a high molecular weight water-soluble polymer made from N-vinylcarboxylic acid amide can be efficiently produced without gelation. The water-soluble polymer is expected to be widely used in many industrial fields as a flocculant, a paper agent and the like.
Claims (2)
されるＮ−ビニルカルボン酸アミド単独、または該Ｎ−
ビニルカルボン酸アミドと共重合可能な他の水溶性ビニ
ル化合物との混合物を、炭化水素系分散媒、水、分散剤
および重合開始剤の存在下で懸濁重合し、次いで、酸性
加水分解することにより水溶性ポリマーを製造する方法
において、分散剤の存在下、水の全使用量の２０重量％
以上をあらかじめ炭化水素分散媒に懸濁させた後、前記
モノマーを、そのまま、または、残りの水を加えた水溶
液として添加することを特徴とする水溶性ポリマーの製
造法。An N-vinylcarboxylic acid amide represented by the general formula: CH 2 ＣＨCHNHCOR (wherein R represents a hydrogen atom or a methyl group) alone or as a monomer.
Suspension polymerization of a mixture of vinylcarboxylic acid amide and another water-soluble vinyl compound copolymerizable in the presence of a hydrocarbon-based dispersion medium, water, a dispersant and a polymerization initiator, and then acidic hydrolysis. A water-soluble polymer by the method described in the above, in the presence of a dispersant, 20% by weight of the total amount of water used
A method for producing a water-soluble polymer, comprising suspending the above in a hydrocarbon dispersion medium in advance and then adding the monomer as it is or as an aqueous solution to which the remaining water has been added.
量倍である請求項１の方法。2. The process according to claim 1, wherein the total amount of water used is 0.1 to 3 times the weight of the monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28884291A JP3147440B2 (en) | 1991-11-05 | 1991-11-05 | Method for producing water-soluble polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28884291A JP3147440B2 (en) | 1991-11-05 | 1991-11-05 | Method for producing water-soluble polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125117A JPH05125117A (en) | 1993-05-21 |
| JP3147440B2 true JP3147440B2 (en) | 2001-03-19 |
Family
ID=17735455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28884291A Expired - Lifetime JP3147440B2 (en) | 1991-11-05 | 1991-11-05 | Method for producing water-soluble polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3147440B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6178532B1 (en) * | 2017-02-21 | 2017-08-09 | 株式会社モコム | E-type retaining ring insertion tool |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5668463B2 (en) * | 2010-12-22 | 2015-02-12 | 三菱レイヨン株式会社 | Method for producing water-soluble polymer |
| JP5594186B2 (en) * | 2011-02-28 | 2014-09-24 | 三菱レイヨン株式会社 | Process for producing N-vinylcarboxylic acid amide polymer |
| US10385147B2 (en) | 2014-09-18 | 2019-08-20 | Hymo Corporation | Method for producing polyvinylamine crosslinked polymer particles |
| WO2017126355A1 (en) * | 2016-01-20 | 2017-07-27 | ハイモ株式会社 | Iminodiacetic acid type chelate resin and method for producing same |
| JP2018172478A (en) * | 2017-03-31 | 2018-11-08 | ハイモ株式会社 | Amphoteric crosslinked polymer particle and method for producing same |
| US20220153897A1 (en) * | 2019-03-22 | 2022-05-19 | Showa Denko K.K. | Method for producing aqueous solution of n-vinyl carboxylic acid amide copolymer |
-
1991
- 1991-11-05 JP JP28884291A patent/JP3147440B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6178532B1 (en) * | 2017-02-21 | 2017-08-09 | 株式会社モコム | E-type retaining ring insertion tool |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05125117A (en) | 1993-05-21 |
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