JP2012177053A - Method for producing n-vinyl carboxylic acid amide polymer - Google Patents
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本発明は、Ｎ−ビニルカルボン酸アミド、または該Ｎ−ビニルカルボン酸アミドと他の共重合可能な単量体の混合物を原料とし、懸濁重合法により安定な懸濁系を維持しながらＮ−ビニルカルボン酸アミド重合体を製造する方法に関するものである。本発明方法により得られる重合体及び該重合体を更に加水分解して得られるＮ−ビニルカルボン酸アミド重合体の変性物は、高分子凝集剤、紙力増強剤、染料固着剤、スケール防止剤、金属イオン封鎖剤等として有効に利用することができる。 The present invention uses N-vinylcarboxylic acid amide or a mixture of the N-vinylcarboxylic acid amide and another copolymerizable monomer as a raw material, and maintains a stable suspension system by suspension polymerization. -It relates to a process for producing vinyl carboxylic acid amide polymers. A polymer obtained by the method of the present invention and a modified product of N-vinylcarboxylic acid amide polymer obtained by further hydrolyzing the polymer are a polymer flocculant, a paper strength enhancer, a dye fixing agent, and a scale inhibitor. It can be effectively used as a sequestering agent.
Ｎ−ビニルカルボン酸アミド重合体の製造方法として、Ｎ−ビニルカルボン酸アミドを水溶液状で重合しこれを変性する方法（特許文献１）や有機溶媒中で逆相懸濁重合しこれを変性する方法（特許文献２〜４）等が多く提案されている。 As a method for producing an N-vinylcarboxylic acid amide polymer, a method of polymerizing N-vinylcarboxylic acid amide in an aqueous solution and modifying it (Patent Document 1), or reverse-phase suspension polymerization in an organic solvent to modify this. Many methods (patent documents 2 to 4) have been proposed.
水溶液状で重合する場合は、容易に重合体を得ることができるが、重合の進行に伴い重合系が粘稠となる問題がある。すなわち、高い単量体濃度や高分子量になるとゲル状の非流動性状態となるため、これを使用することや変性工程での取り扱い性が極めて悪くなる。また、水溶液状態ではその重合体濃度が低いため膨大な量の輸送が必要となり、その費用が高くなる問題がある。 When polymerizing in the form of an aqueous solution, a polymer can be easily obtained, but there is a problem that the polymerization system becomes viscous as the polymerization proceeds. That is, since it becomes a gel-like non-fluid state at a high monomer concentration or high molecular weight, the use of this or the handling property in the modification step becomes extremely poor. Moreover, since the polymer concentration is low in an aqueous solution state, a huge amount of transport is required, which increases the cost.
一方、炭化水素分散媒にＮ−ビニルカルボン酸アミド水溶液を分散させて油中水型で逆相懸濁重合する方法は、重合と加水分解を続けて行うことができる点において簡便であり、乾燥粉末状の水溶性重合体が得られる特徴がある。 On the other hand, the method of carrying out reverse phase suspension polymerization in a water-in-oil type by dispersing an aqueous N-vinylcarboxylic acid amide solution in a hydrocarbon dispersion medium is simple in that polymerization and hydrolysis can be carried out continuously, and drying is performed. There is a feature that a powdery water-soluble polymer can be obtained.
そして、単量体水溶液をＨＬＢが９〜２０である非イオン系界面活性剤の存在下で逆相懸濁重合を行うことにより、加水分解性の改善とその界面活性剤の回収を可能とする方法（特許文献２）、ポリオキシエチレンアルキルエーテル系またはポリオキシエチレンアルキルアリールエーテル系の界面活性剤、および酸化エチレンの重合体または酸化エチレンと酸化プロピレンの共重合体の存在下で逆相懸濁重合を行うことにより、粒子同士の固着の改善を図る方法（特許文献３）、水の全使用量の２０％以上を予め炭化水素分散媒に懸濁した状態にある敷液中に単量体を供給しつつ重合し、次いで酸性加水分解することにより、ゲル化することなく、効率よく高分子量の水溶性重合体を製造する方法（特許文献４）がある。 The monomer aqueous solution is subjected to reverse phase suspension polymerization in the presence of a nonionic surfactant having an HLB of 9 to 20, thereby improving the hydrolyzability and recovering the surfactant. Method (Patent Document 2), polyoxyethylene alkyl ether type or polyoxyethylene alkyl aryl ether type surfactant, and reverse phase suspension in the presence of ethylene oxide polymer or ethylene oxide and propylene oxide copolymer A method for improving the adhesion between particles by performing polymerization (Patent Document 3), a monomer in a bed solution in which 20% or more of the total amount of water used is suspended in a hydrocarbon dispersion medium in advance. There is a method (Patent Document 4) for efficiently producing a high-molecular-weight water-soluble polymer without gelation by polymerizing while supplying water, and then performing acidic hydrolysis.
しかしながら、上記の何れ方法においても、重合時の懸濁液が乳化状態に変化することで系内が急激に増粘され温度制御が困難となって暴走反応が生じる場合があり、また、水溶性重合体の粒子径が粗大化して後工程において閉塞の原因となる場合もあり、工業的に安定製造を行う条件は未だ見出されてはいない。 However, in any of the above-mentioned methods, the suspension during polymerization changes to an emulsified state, and thus the inside of the system is suddenly thickened, making temperature control difficult and causing a runaway reaction. In some cases, the particle size of the polymer becomes coarse and may cause clogging in a subsequent process, and conditions for stable industrial production have not yet been found.
本発明は、上記実情に鑑みなされたものであり、その目的は、Ｎ−ビニルカルボン酸アミド水溶液の逆相懸濁重合において、乳化状態を発生させず安定な懸濁状態を保ちながら細粒化されたＮ−ビニルカルボン酸アミド重合体を製造する方法を提供することにある。 The present invention has been made in view of the above circumstances, and its purpose is to make fine particles while maintaining a stable suspended state without generating an emulsified state in reverse phase suspension polymerization of an aqueous N-vinylcarboxylic acid amide solution. Another object of the present invention is to provide a method for producing a prepared N-vinylcarboxylic acid amide polymer.
本発明者らは、鋭意検討した結果、Ｎ−ビニルカルボン酸アミドの逆相懸濁重合においては、重合中の炭化水素分散媒、Ｎ−ビニルカルボン酸アミド、水、界面活性剤の割合が、乳化現象と粒子径細粒化に強い因果関係があり、そして、これらを特定条件に設定するならば、安定的に懸濁状態を維持して細粒化が可能であるとの知見を得た。 As a result of intensive studies, the inventors of the present invention, in the reverse phase suspension polymerization of N-vinyl carboxylic acid amide, the ratio of hydrocarbon dispersion medium, N-vinyl carboxylic acid amide, water, surfactant during polymerization, There is a strong causal relationship between the emulsification phenomenon and particle size refinement, and if these are set to specific conditions, we obtained the knowledge that stable suspension can be maintained and refinement is possible. .
本発明は、上記の知見を基に更に検討を重ねた結果完成されたものであり、その要旨は、炭化水素系分散媒、界面活性剤、及び任意成分としての助剤の存在下、一般式ＣＨ２＝ＣＨＮＨＣＯＲ（式中、Ｒは水素原子またはメチル基を表す。）で示されるＮ−ビニルカルボン酸アミド単量体単独、または共重合可能な他の単量体との混合物を、水を予め炭化水素分散媒に懸濁させた後にそのまま添加するか、または、水を加えた水溶液として添加する逆相懸濁重合する方法において、炭化水素分散媒に対する界面活性剤の割合が１〜３重量％であり、予め炭化水素分散媒に懸濁させる水の比率が炭化水素分散媒に対する界面活性剤の重量％で表される式（１）又は式（２）を満たす条件とすることを特徴とするＮ−ビニルカルボン酸アミド重合体の製造方法に存する。 The present invention has been completed as a result of further studies based on the above findings, and the gist thereof is the general formula in the presence of a hydrocarbon-based dispersion medium, a surfactant, and an auxiliary agent as an optional component. N 2 -vinylcarboxylic acid amide monomer represented by CH 2 ═CHNHCOR (wherein R represents a hydrogen atom or a methyl group) alone or a mixture with another copolymerizable monomer is added with water. In the method of reverse phase suspension polymerization, which is added as it is after being suspended in a hydrocarbon dispersion medium in advance or as an aqueous solution to which water is added, the ratio of the surfactant to the hydrocarbon dispersion medium is 1 to 3 weights. Characterized in that the ratio of water previously suspended in the hydrocarbon dispersion medium satisfies the condition (1) or (2) expressed by the weight percent of the surfactant with respect to the hydrocarbon dispersion medium. N-vinylcarboxylic acid amide heavy It resides in the method of manufacturing the body.
水比率≧−１．４×炭化水素分散媒に対する界面活性剤の重量％＋１８・・・（１）
水比率≦−１．４×炭化水素分散媒に対する界面活性剤の重量％＋１２・・・（２）
ここで、水比率は予め炭化水素分散媒に懸濁させる水の炭化水素分散媒との合計質量に対する重量％である。
Water ratio ≧ −1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 18 (1)
Water ratio ≦ −1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 12 (2)
Here, the water ratio is weight% with respect to the total mass of the water and the hydrocarbon dispersion medium suspended in advance in the hydrocarbon dispersion medium.
本発明によれば乳化状態を経ず微細な粒子形状のＮ−ビニルカルボン酸アミド重合体を得ることが可能になる。 According to the present invention, it is possible to obtain an N-vinylcarboxylic acid amide polymer having a fine particle shape without undergoing an emulsified state.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
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。 Examples of the N-vinylcarboxylic amide represented by the general formula CH 2 ═CHNHCOR (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 product of the N-vinylcarboxylic acid amide polymer, N-vinylformamide is preferred because the polymer has good hydrolyzability.
本発明の重合には原料ビニル単量体として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共重合可能な他の単量体との混合物が用いられる。当該単量体としては本発明に用いられる炭化水素系溶媒に実質的に不溶性である化合物が用いられ、例えば、（メタ）アクリロニトリル、（メタ）アクリルアミド、Ｎ−アルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド、Ｎ，Ｎ′−ジアルキルアミノアルキル（メタ）アクリルアミド、（メタ）アクリルアミド−アルキル−トリメチルアンモニウム塩、（メタ）アクリルアミドアルカンスルホン酸のアルカリ金属塩またはアンモニウム塩、（メタ）アクリル酸のアルカリ金属塩またはアンモニウム塩、ヒドロキシアルキル（メタ）アクリレート、ジアルキルアミノアルキル（メタ）アクリレート、（メタ）アクリロイルオキシアルキル−トリメチルアンモニウム塩、（メタ）アクリロイルオキシアルカンスルホン酸のアルカリ金属塩またはアンモニウム塩、Ｎ−ビニルピロリドン、Ｎ−アルキル−Ｎ−ビニルホルムアミド、Ｎ−アルキル−Ｎ−ビニルアセトアミド、ジアリル−ジアルキルアンモニウム塩、ビニルピリジン、ビニルイミダゾール、ビニルペンジルトリアルキルアンモニウム塩、ビニルスルホン酸のアルカリ金属塩またはアンモニウム塩、酢酸ビニル等のビニル化合物等が例示される。これらは２種以上を用いることもできる。 In the polymerization of the present invention, N-vinylcarboxylic acid amide alone or a mixture of other monomers copolymerizable with N-vinylcarboxylic acid amide is used as a starting vinyl monomer. As the monomer, a compound that is substantially insoluble in the hydrocarbon solvent used in the present invention is used. For example, (meth) acrylonitrile, (meth) acrylamide, N-alkyl (meth) acrylamide, N, N -Dialkyl (meth) acrylamide, N, N'-dialkylaminoalkyl (meth) acrylamide, (meth) acrylamide-alkyl-trimethylammonium salt, alkali metal salt or ammonium salt of (meth) acrylamide alkanesulfonic acid, (meth) acrylic Alkali metal salt or ammonium salt of acid, hydroxyalkyl (meth) acrylate, dialkylaminoalkyl (meth) acrylate, (meth) acryloyloxyalkyl-trimethylammonium salt, (meth) acryloyloxyalkanesulfo Alkali metal salt or ammonium salt of acid, N-vinylpyrrolidone, N-alkyl-N-vinylformamide, N-alkyl-N-vinylacetamide, diallyl-dialkylammonium salt, vinylpyridine, vinylimidazole, vinylpentyltrialkylammonium Examples thereof include vinyl compounds such as salts, alkali metal salts or ammonium salts of vinyl sulfonic acid, and vinyl acetate. Two or more of these can be used.
全単量体中のＮ−ビニルカルボン酸アミドの含有割合は、特に限定されるものではないが、通常５モル％以上、好ましくは１０モル％以上、更に好ましくは５０モル％以上である。また、重合後に変性する場合は、好ましくは８０モル％以上、更に好ましくは９０〜１００モル％である。 The content ratio of N-vinylcarboxylic acid amide in all monomers is not particularly limited, but is usually 5 mol% or more, preferably 10 mol% or more, and more preferably 50 mol% or more. Moreover, when it modifies after superposition | polymerization, Preferably it is 80 mol% or more, More preferably, it is 90-100 mol%.
懸濁重合に必要とする水の量は、全単量体に対して、通常０．１〜３重量倍、好ましくは０．４〜２重量倍、更に好ましくは０．６〜１重量倍である。水の量が上記の範囲より多い場合は分子量が低下傾向となり、また、上記の範囲より少ない場合は水滴の分散が不充分となる。 The amount of water required for the suspension polymerization is usually 0.1 to 3 times by weight, preferably 0.4 to 2 times by weight, more preferably 0.6 to 1 times by weight based on the total monomers. is there. When the amount of water is greater than the above range, the molecular weight tends to decrease, and when it is less than the above range, the dispersion of water droplets is insufficient.
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、ドデカン等の鎖状飽和炭化水素、沸点６５〜２５０℃（好ましくは８０℃〜１８０℃）の石油留分の石油留分、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素が挙げられる。分散媒は、単量体の水溶液に対し、通常０．５〜１０重量倍、好ましくは１〜５重量倍の範囲で用いられる。 The hydrocarbon-based dispersion medium is preferably a hydrocarbon azeotropic with water. For example, petroleum fractions of chain saturated hydrocarbons such as n-hexane, n-heptane, n-octane, nonane, decane, undecane, dodecane, etc. And alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. The dispersion medium is generally used in an amount of 0.5 to 10 times by weight, preferably 1 to 5 times by weight, with respect to the aqueous monomer solution.
水の全使用量の２０重量％以上、好ましくは５０重量％以上、更に好ましくは７５重量％以上であり、予め分散媒中に水を添加し、攪拌により懸濁相を形成させ、そこに、単量体を、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が好ましい。懸濁相への水の添加量が２０重量％未満の場合は、得られた重合体を酸性加水分解したＮ−ビニルカルボン酸アミドの変性物がゲル化する。 20% by weight or more of the total amount of water used, preferably 50% by weight or more, more preferably 75% by weight or more, water is added to the dispersion medium in advance, and a suspension phase is formed by stirring, It is preferable to add the monomer as it is or as an aqueous solution to which the remaining water is added. When the amount of water added to the suspension phase is less than 20% by weight, a modified product of N-vinylcarboxylic acid amide obtained by acidic hydrolysis of the obtained polymer is gelled.
本発明で用いられる界面活性剤は、逆相懸濁系にて、所望の粒性形状、粒子径を形成し得るものであればよい。例えば、ＨＬＢ（Ｈｙｄｒｏｐｈｉｌｉｃ Ｌｉｐｏｐｈｉｌｉｃ Ｂａｌａｎｃｅ）が通常９〜２０、好ましくは１２〜１９のノニオン系界面活性剤が使用される。斯かるノニオン系界面活性剤としては、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、ポリオキシエチレンアルキルエーテル、モリグリセリド、ソルビトールアルキルエステル、スクロースアルキルエステル等であり、好ましくは、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である。具体的には、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレントリデシルエーテル、ポリオキシエチレンセチルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンフェニルエーテル、ポリオキシエチレンラウレート、ポリオキシエチレンオレエート、ポリオキシエチレンステアレート、ポリオキシエチレンソルビタンラウレート、ポリオキシエチレンソルビタンオレエート、ポリオキシエチレンソルビタンステアレート等の化合物が例示される。 The surfactant used in the present invention may be any surfactant that can form a desired granular shape and particle size in a reversed phase suspension system. For example, a nonionic surfactant having an HLB (Hydrophilic Lipophilic Balance) of usually 9 to 20, preferably 12 to 19 is used. Such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, molyglyceride, sorbitol alkyl ester, sucrose alkyl ester, etc., preferably polyoxyethylene alkyl Ether, polyoxyethylene alkylphenyl ether. Specifically, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene phenyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan oleate, and polyoxyethylene sorbitan stearate. The
界面活性剤の使用量は、微細な粒子を得るため、炭化水素系分散媒に対し、１〜３重量％、好ましくは１．５〜２．５重量％である。界面活性剤の使用量が上記の範囲より多い場合は乳化が生じ易くなり、また、上記の範囲より少ない場合は粒子径の肥大化を招く。 The amount of the surfactant used is 1 to 3% by weight, preferably 1.5 to 2.5% by weight with respect to the hydrocarbon-based dispersion medium in order to obtain fine particles. When the amount of the surfactant used is larger than the above range, emulsification is likely to occur, and when it is smaller than the above range, the particle diameter is enlarged.
重合開始剤に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の使用量は、原料ビニル単量体に対する重量基準として、通常１００〜１００００ｐｐｍ、好ましくは５００〜７０００ｐｐｍの範囲である。ラジカル重合開始剤の添加方法は、特に限定されないが、原料ビニル単量体を含有する水溶液にラジカル重合開始剤を溶解した後、これを炭化水素系分散媒中に添加して分散する方法が好ましい。 A general radical polymerization initiator can be used as the polymerization initiator, but an azo compound is preferred. Particularly preferred are water-soluble azo compounds such as 2,2′-azobis-2-amidinopropane hydrochloride, sulfate and acetate, azobis-N, N′-dimethyleneisobutylamidine hydrochloride, sulfate and Examples thereof include acetates, alkali metal salts and ammonium salts of 4,4′-azobis-4-cyanovaleric acid. The usage-amount of a radical polymerization initiator is 100-10000 ppm normally as a weight reference | standard with respect to a raw material vinyl monomer, Preferably it is the range of 500-7000 ppm. The method for adding the radical polymerization initiator is not particularly limited, but it is preferable to dissolve the radical polymerization initiator in an aqueous solution containing the raw vinyl monomer, and then add and disperse it in a hydrocarbon-based dispersion medium. .
更に、場合によっては、重合安定剤として、塩化アンモニウム、塩化カルシウム等の添加物が使用される。添加物の使用量は、全単量体に対し、通常０．１〜２０重量％、好ましくは１〜１５重量％である。 In some cases, additives such as ammonium chloride and calcium chloride are used as a polymerization stabilizer. The usage-amount of an additive is 0.1-20 weight% normally with respect to all the monomers, Preferably it is 1-15 weight%.
予め炭化水素分散媒に懸濁させる水の比率は、後述の実施例および比較例に示すように、炭化水素分散媒に対する界面活性剤の重量％で表される式（１）又は式（２）を満たす条件にする必要がある。 The ratio of water previously suspended in the hydrocarbon dispersion medium is expressed by the formula (1) or (2) represented by the weight percent of the surfactant with respect to the hydrocarbon dispersion medium, as shown in Examples and Comparative Examples described later. It is necessary to satisfy the conditions.
水比率≧１．４×炭化水素分散媒に対する界面活性剤の重量％＋１８・・・（１）
水比率≦１．４×炭化水素分散媒に対する界面活性剤の重量％＋１２・・・（２）
ここで、水比率は水と炭化水素分散媒の合計質量に対する水の質量の重量％である。
Water ratio ≧ 1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 18 (1)
Water ratio ≦ 1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 12 (2)
Here, the water ratio is weight% of the mass of water with respect to the total mass of water and the hydrocarbon dispersion medium.
重合温度は、通常３０〜１００℃、好ましくは５０〜８０℃である。また、重合時間は、通常０．５〜１０時間、好ましくは１〜５時間である。なお、重合に際しては、重合熱が発生するため、通常、重合系を冷却することにより、重合温度が上記範囲内に保持されるように調節される。重合を実施するには、界面活性剤を含有する分散媒を重合温度に保持し、窒素ガス気流中、重合開始剤を含む単量体水溶液を、攪拌下へ分散媒中に添加することによる方法が例示されるが、特に、単量体、溶媒、助剤の混合順次に限定されるものではない。 The polymerization temperature is usually from 30 to 100 ° C, preferably from 50 to 80 ° C. The polymerization time is usually 0.5 to 10 hours, preferably 1 to 5 hours. In the polymerization, since heat of polymerization is generated, the polymerization temperature is usually adjusted to be maintained within the above range by cooling the polymerization system. To carry out the polymerization, the dispersion medium containing the surfactant is kept at the polymerization temperature, and an aqueous monomer solution containing a polymerization initiator is added to the dispersion medium under stirring in a nitrogen gas stream. However, it is not particularly limited to the mixing order of the monomer, the solvent and the auxiliary agent.
得られる重合体の分子量の調節は、重合条件によっても行えるが、必要に応じて、イソプロピルアルコール、アリルアルコール等のアルコール類、チオグリコール酸、チオグリセロール等のメルカプタン類、次亜燐酸ソーダ等の亜燐酸塩類等の連鎖移動剤を使用することができる。 The molecular weight of the resulting polymer can be adjusted depending on the polymerization conditions, but if necessary, alcohols such as isopropyl alcohol and allyl alcohol, mercaptans such as thioglycolic acid and thioglycerol, and sub-substances such as sodium hypophosphite. Chain transfer agents such as phosphates can be used.
かくして得られた含水Ｎ−ビニルカルボン酸アミド重合体は、通常、粒径０．０５〜３ｍｍ、特に０．５〜２ｍｍ程度のビーズ状の形状を示す。 The water-containing N-vinylcarboxylic acid amide polymer thus obtained usually has a bead shape with a particle size of 0.05 to 3 mm, particularly about 0.5 to 2 mm.
以上の方法で得られた重合体は、前記の特許文献４等で例示される方法により当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供することができる。 The polymer obtained by the above method can be subjected to acidic hydrolysis in the form of a solution or dispersion containing the polymer by the method exemplified in Patent Document 4 and the like.
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
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３４５．０ｇ、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）３．５ｇ、イオン交換水８２．６ｇ、塩化アンモニウム６．２ｇを入れ、攪拌下５５℃に昇温した。
Example 1:
To a 1 L four-necked flask equipped with a stirrer, a condenser, a dropping funnel and a nitrogen gas inlet tube, 345.0 g of cyclohexane, polyoxyethylene oleyl ether (trade name “Neugen ET140E”, Daiichi Kogyo Seiyaku Co., Ltd., H.C. (LB = 14.0) 3.5 g, ion-exchanged water 82.6 g, and ammonium chloride 6.2 g were added, and the temperature was raised to 55 ° C. with stirring.
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（以下ＡＢＡＰと記載）１２重量％水溶液４．２ｇを添加した分散液に、Ｎ−ビニルホルムアミド（純度＝９９．２％）１２６ｇ、次亜リン酸ナトリウム０．０４ｇ、イオン交換水９．６ｇの滴下液を１３５分かけて滴下し乳化状態の有無を観察した。その後、更に反応を１３５分続けた。単量体量を１としたときの水の全使用量は０．７７であった。以上の反応液をろ過して含水重合体を得て、その粒径をスケール付顕微鏡にて測定した。 Next, N-vinylformamide (purity = 99) was added to a dispersion obtained by adding 4.2 g of a 12% by weight aqueous solution of 2,2′-azobis-2-amidinopropane dihydrochloride (hereinafter referred to as ABAP) in a nitrogen gas stream. .2%) 126 g, sodium hypophosphite 0.04 g, and ion-exchanged water 9.6 g in drops were dropped over 135 minutes to observe the presence or absence of an emulsified state. Thereafter, the reaction was continued for 135 minutes. When the monomer amount was 1, the total amount of water used was 0.77. The above reaction solution was filtered to obtain a water-containing polymer, and the particle size was measured with a scaled microscope.
表１に重合中の乳化状態と得られた含水重合体の粒子径の結果を示す。乳化は発生せず微細な粒子が得られた。なお、表１中の水の添加割合の重量％は、分散液中の水と滴下液中の水の合計重量（分散液及び滴下液のイオン交換水とＡＢＡＰ１２重量％水溶液中の水）に対するそれぞれの水の重量％である。水比率の重量％は、分散液中のシクロヘキサンとイオン交換水とＡＢＡＰ１２重量％水溶液の合計に対するイオン交換水とＡＢＡＰ１２重量％水溶液中の水の合計の重量％である。界面活性剤の重量％は、シクロヘキサンに対するポリオキシエチレンオレイルエーテルの重量％である。 Table 1 shows the results of the emulsified state during polymerization and the particle size of the obtained hydropolymer. Emulsification did not occur and fine particles were obtained. In addition, the weight% of the addition ratio of water in Table 1 is relative to the total weight of the water in the dispersion and the water in the dropping liquid (the water in the dispersion and the ion-exchange water and the ABAP 12 wt% aqueous solution in the dropping liquid). % By weight of water. The weight% of the water ratio is the total weight% of water in the ion-exchanged water and the 12% by weight ABAP aqueous solution with respect to the total of cyclohexane, ion-exchanged water and the 12% ABAP aqueous solution in the dispersion. The weight percent of the surfactant is the weight percent of polyoxyethylene oleyl ether relative to cyclohexane.
実施例２〜７：
イオン交換水の全使用量を実施例１と同じとして、水比率と界面活性剤を表１に従い変更した以外は実施例１と同様に行った。炭化水素分散媒に対する界面活性剤の割合が１〜３重量％であり、予め炭化水素分散媒に懸濁させる水の比率が炭化水素分散媒に対する界面活性剤の重量％で表される式（１）又は式（２）を満たす条件とすることにより、乳化は発生せず微細な粒子が得られた。
Examples 2-7:
The same procedure as in Example 1 was performed except that the total amount of ion-exchanged water used was the same as in Example 1 and the water ratio and surfactant were changed according to Table 1. The ratio of the surfactant with respect to the hydrocarbon dispersion medium is 1 to 3% by weight, and the ratio of water previously suspended in the hydrocarbon dispersion medium is expressed by the weight percentage of the surfactant with respect to the hydrocarbon dispersion medium (1 ) Or by satisfying the formula (2), emulsification did not occur and fine particles were obtained.
比較例１〜３：
イオン交換水の全使用量を同じとして、水比率と界面活性剤を表１に従い変更した以外は実施例１と同様に行った。炭化水素分散媒に対する界面活性剤の割合が１〜３重量％の範囲を外れる場合は、予め炭化水素分散媒に懸濁させる水の比率が炭化水素分散媒に対する界面活性剤の重量％で表される式（１）又は式（２）を満たしていても粒子が肥大し塊が生じたり、乳化が発生し温度上昇が生じ重合を中止せざるを得なかった。
Comparative Examples 1-3:
The same procedure as in Example 1 was carried out except that the total amount of ion-exchanged water used was the same and the water ratio and surfactant were changed according to Table 1. When the ratio of the surfactant to the hydrocarbon dispersion medium is outside the range of 1 to 3% by weight, the ratio of water suspended in the hydrocarbon dispersion medium in advance is represented by the weight% of the surfactant to the hydrocarbon dispersion medium. Even if the above formula (1) or formula (2) is satisfied, the particles are enlarged and a lump is formed, or emulsification occurs and the temperature rises and the polymerization must be stopped.
比較例４〜７：
イオン交換水の全使用量を同じとして、水比率と界面活性剤を表１に従い変更した以外は実施例１と同様に行った。炭化水素分散媒に対する界面活性剤の割合が１〜３重量％の場合でも、予め炭化水素分散媒に懸濁させる水の比率が炭化水素分散媒に対する界面活性剤の重量％で表される式（１）又は式（２）を満たさない条件では乳化が発生し、温度上昇が生じ重合を中止せざるを得なかった。
Comparative Examples 4-7:
The same procedure as in Example 1 was carried out except that the total amount of ion-exchanged water used was the same and the water ratio and surfactant were changed according to Table 1. Even when the ratio of the surfactant to the hydrocarbon dispersion medium is 1 to 3% by weight, the ratio of the water suspended in the hydrocarbon dispersion medium in advance is expressed by the weight percentage of the surfactant to the hydrocarbon dispersion medium ( Under conditions that did not satisfy 1) or formula (2), emulsification occurred, the temperature increased, and the polymerization had to be stopped.
Claims (1)
水比率≧−１．４×炭化水素分散媒に対する界面活性剤の重量％＋１８・・・（１）
水比率≦−１．４×炭化水素分散媒に対する界面活性剤の重量％＋１２・・・（２）
ここで、水比率は予め炭化水素分散媒に懸濁させる水と炭化水素分散媒の合計質量に対する予め炭化水素分散媒に懸濁させる水の質量の重量％である。 N-vinylcarboxylic acid represented by the general formula CH 2 = CHNHCOR (wherein R represents a hydrogen atom or a methyl group) in the presence of a hydrocarbon-based dispersion medium, a surfactant, and an auxiliary agent as an optional component. Add the amide monomer alone or a mixture with other copolymerizable monomers directly after suspending water in a hydrocarbon dispersion medium, or add it as an aqueous solution with water added. In the method of phase suspension polymerization, the ratio of the surfactant to the hydrocarbon dispersion medium is 1 to 3% by weight, and the ratio of the water suspended in the hydrocarbon dispersion medium in advance is the weight of the surfactant to the hydrocarbon dispersion medium. % N-vinylcarboxylic acid amide polymer production method, characterized by satisfying the formula (1) or the formula (2) expressed in%.
Water ratio ≧ −1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 18 (1)
Water ratio ≦ −1.4 × weight% of surfactant with respect to hydrocarbon dispersion medium + 12 (2)
Here, the water ratio is the weight% of the mass of water previously suspended in the hydrocarbon dispersion medium with respect to the total mass of water and hydrocarbon dispersion medium previously suspended in the hydrocarbon dispersion medium.
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| JPH0597931A (en) * | 1991-10-08 | 1993-04-20 | Mitsubishi Kasei Corp | Production of n-vinylcarboxylic acid amide polymer |
| JPH05125117A (en) * | 1991-11-05 | 1993-05-21 | Mitsubishi Kasei Corp | Production of water-soluble polymer |
| JPH06329718A (en) * | 1993-05-20 | 1994-11-29 | Mitsubishi Kasei Corp | Production of water-soluble cationic polymer |
| JP2010159387A (en) * | 2008-07-10 | 2010-07-22 | Hymo Corp | Powdery ionic water-soluble polymer, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH0597931A (en) * | 1991-10-08 | 1993-04-20 | Mitsubishi Kasei Corp | Production of n-vinylcarboxylic acid amide polymer |
| JPH05125117A (en) * | 1991-11-05 | 1993-05-21 | Mitsubishi Kasei Corp | Production of water-soluble polymer |
| JPH06329718A (en) * | 1993-05-20 | 1994-11-29 | Mitsubishi Kasei Corp | Production of water-soluble cationic polymer |
| JP2010159387A (en) * | 2008-07-10 | 2010-07-22 | Hymo Corp | Powdery ionic water-soluble polymer, and use thereof |
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