JPH0535162B2

JPH0535162B2 -

Info

Publication number: JPH0535162B2
Application number: JP59171560A
Authority: JP
Inventors: Koji Itagaki; Takeshi Ito; Kyoto Ando; Junya Watanabe; Shigeru Sawayama
Original assignee: Mitsubishi Chemical Industries Ltd
Current assignee: Mitsubishi Chemical Corp
Priority date: 1984-08-20
Filing date: 1984-08-20
Publication date: 1993-05-25
Also published as: JPS6151007A

Description

[Detailed description of the invention]

（産業上の利用分野）本発明は、ポリビニルアミン架橋物の新規な製
造方法に関するものである。ポリビニルアミンは、炭素−炭素結合よりなる
主鎖に隣接して結合した構造を持つカチオン性官
能基の高密度な水溶性高分子である。すなわち、
ポリビニルアミンの示す性能としては、炭素−炭
素結合よりなる主鎖に隣接して高密度に結合した
アミノ基のミクロ的或いは主鎖のマクロ的な相互
作用により、その水溶液は強塩基性を示すこと、
又アミノ基の立体的な配置が種種の金属イオン、
とくに銅イオン、鉄イオン等の遷移金属イオンと
のキレート生成に適した位置を占めており、強固
なキレート生成能力を有することなどが知られて
いる。かかる性能を示すポリビニルアミンの構造を充
分に生かしながら架橋化して水に不溶化したポリ
ビニルアミン架橋物を容易に得ることができるな
らば、優れた陰イオン交換樹脂、キレート樹脂が
得られる他、その他の用途として、例えば帯電防
止剤、塗料、化粧品、製紙分野、医療用高分子材
料用等への応用範囲の拡大も可能となる。（従来の技術）ところで従来、ポリビニルアミン架橋物を製造
するには、アクリルアミドモノマーとジビニルベ
ンゼン類との共重合により、水に不溶性の架橋物
を得た後、ホフマン反応によりポリビニルアミン
架橋物を得る方法が用いられている。（発明が解決しようとする問題点）しかしながら、かかる従来公知の製造法は、架
橋後の水不溶の高分子を用いホフマン反応を行う
ことに加えて一般的にホフマン反応の転化率が低
いこと或いはホフマン反応時に副生するカルボン
酸のために、アミノ基含有率の高いポリビニルア
ミン架橋物が得られないばかりか、アミノ基だけ
からなるポリビニルアミン架橋物は得ることがで
きない、という大きな欠点を有するものである。（問題点を解決するための手段）本発明者らは、上記の従来法の欠点を解消し、
アミノ基含有率の高いポリビニルアミン架橋物が
容易に得られる製造方法を提供すべく鋭意研究を
進めた結果、Ｎ−ビニルホルムアミドモノマー
と、該モノマーと共重合可能な架橋性単量体とを
共重合し、さらに得られた共重合物の分子中に存
在するホルムアミド基の加水分解を行うことによ
り、上記の目的とするアミノ基含有率の高いポリ
ビニルアミン架橋物が容易に得られることを初め
て見い出し、本発明を完成するに至つたものであ
る。以下、本発明を詳しく説明するに、本発明のポ
リビニルアミン架橋物の製造方法は、下記式(A) で表わされるＮ−ビニルホルムアミドモノマー
（以下、「単量体(A)」という。）と、該単量体(A)と
共重合可能な下記一般式の(B)、(C)、(D)及び(E) （式中、R¹は水素原子、メチル基、エチル基
若しくはフエニル基又はこれらの複数の組合せと
して選ばれ、かつＸは水素原子、塩素原子、臭素
原子若しくはヨウ素原子又はこれらの複数の組合
せとして選ばれる）、（式中、R²は水素原子若しくはメチル基又は
これらの複数の組合せとして選ばれ、かつｎは１
〜６の整数を示す）、（式中、R³は水素原子若しくはメチル基又は
これらの複数の組合せとして選ばれ、かつｍは１
〜６の整数を示す）及び（式中、R⁴は水素原子若しくはメチル基又は
これらの複数の組合せとして選ばれる）でそれぞ
れ表わされる架橋性単量体から選ばれる単量体と
の共重合により、水不溶性のポリ（単量体(A)）架
橋物を得る第１工程と、さらに得られた架橋物の
分子中に存在するホルムアミド基を加水分解して
アミノ基に変換する第２工程の、通常二つの工程
よりなる。（作用）上記で主原料として用いられる単量体(A)は、架
橋性単量体或いはその他の種々な単量体と容易に
ラジカル共重合を起こす。また、上記の共重合に
より得られた水不溶性の架橋物の分子中に存在す
るホルムアミド基は、容易に加水分解してアミノ
基に変換され得るものである。本発明の方法で単量体(A)との共重合に用いる架
橋性単量体としては、単量体(A)と共重合可能であ
りかつホルムアミド基の加水分解の際に不活性な
ものであれば用いることができる。かかる架橋性
単量体の具体例としては、ジビニルベンゼン、ジ
ビニルトルエン、ジビニルキシレン等の芳香族ポ
リビニル化合物（「単量体」という。）、Ｎ，N′−
メチレン−ビス−アクリルアミド又は−メタクリ
ルアミド等のＮ，N′−メチレン（若しくはポリ
メチレン）−ビス−アクリルアミド又は−メタク
リルアミド類（「単量体(D)」という。）、エチレン
グリコール−ジ−アクリレート又はメタクリレー
ト或いはジエチレングリコール−ジ−アクリレー
ト又は−メタクリレート等のポリエチレングリコ
ール−ジ−アクリレート又は−メタクリレート類
（「単量体(C)」という。）、トリメチロールエタン−
トリ−アクリレート又は−メタクリレート、トリ
メチロールプロパン−トリ−アクリレート又は−
メタクリレート等のトリ−アクリレート又は−メ
タクリレート類（「単量体(E)」という。）などが挙
げられる。また、上記の如き架橋性単量体のほかに、単量
体(A)及び当該架橋性単量体と共重合可能なその他
の単量体も、本発明で主原料として用いられる単
量体(A)との共重合に用いることができるが、この
単量体の使用量は、その用途に応じて最適化され
る。架橋性単量体以外のかかる単量体の具体例と
しては、エチレン、プロピレン、ブチレン、アク
リル酸エステル、メタクリル酸エステル等の脂肪
族ビニル化合物、スチレン、ビニルトルエン等の
芳香族ビニル化合物などが挙げられる。本発明方法の共重合反応における単量体の使用
量化は、用いる単量体の性質或いは得られるポリ
ビニルアミン架橋物の使用目的に応じて最適化さ
れるものであるが、一般的には主原料の単量体(A)
の全単量体に対する使用量比は10モル％〜99.5モ
ル％、架橋性単量体の全単量体に対する使用量比
は90モル％〜0.5モル％とする。また、上記の共重合反応は、用いる単量体の性
質或いは得られるポリビニルアミン架橋物の使用
目的に応じて、ラジカル開始剤の存在下、バルク
重合、溶液重合、懸濁重合、乳化重合等の方法に
より行う。例えば単量体(A)とジビニルベンゼン
〔架橋性単量体(B)〕との共重合を行う場合には、
上記のモル比率の条件で、ラジカル開始剤の存在
下、バルク重合法或いは溶液重合法が行われる。
この場合、溶液重合の溶媒としては、好ましくは
ジメチルスルホキシド、ジメチルホルムアミド、
或いはプロピオニトリル等の溶媒が用いられる。さらにまた、例えば、単量体(A)とＮ，N′−メ
チレン−ビス−アクリルアミド〔架橋性単量体の
(D)〕との共重合を懸濁重合法により行う場合に
は、使用単量体類及びラジカル重合開始剤を溶解
した水溶液を重合反応に不活性でかつ水不溶性の
有機溶媒に懸濁させ、重合反応を行うことによ
り、球状のポリ（単量体(A)）架橋物即ちポリ（Ｎ
−ホルムアミド）架橋物を製造することができ
る。本発明のポリビニルアミン架橋物の製造方法に
おけるポリ（単量体(A)）架橋物即ちポリ（Ｎ−ホ
ルムアミド）架橋物の加水分解は、酸性条件下或
いはアルカリ性条件下で容易に行うことができ
る。すなわち、酸性条件下で加水分解を行う場合に
は、ポリ（Ｎ−ビニルホルムアミド）架橋物の分
子中に含有されるホルムアミド基に対し等モルか
ら数倍モルの鉱酸を含む水溶液或いはアルコール
溶液を用いて、反応温度は50℃〜100℃、反応時
間は１時間から30時間で実施する。又、アルカリ性条件下で加水分解を行う場合に
は、ポリ（Ｎ−ビニルホルムアミド）架橋物の分
子中に含まれるホルムアミド基に対し１当量から
数当量の塩基性の電解質を含む水溶液或いはアル
コール溶液を用いて、反応温度は60℃〜120℃、
反応時間は１時間から30時間で実施する。この場
合塩基性の電解質としては、例えば水酸化リチウ
ム、水酸化ナトリウム、水酸化カリウム等が用い
られる。以上のようにして製造されたポリビニルアミン
架橋物は、酸性水溶液、アルカリ性水溶液及び脱
塩水を用いて洗浄する。（実施例）次に本発明を実施例により更に具体的に説明す
るが、本発明はその要旨を超えない限りかかる実
施例により限定されるものではない。なお、「％」
は特に断わらない限り重量によるものである。実施例１単量体(A)（Ｎ−ビニルホルムアミドモノマー）
10.0ｇ及び工業規格のジビニルベンゼン〔架橋性
単量体の(B)〕（純分56.7％、不純物は主としてエ
チルビニルベンゼン）2.3ｇをジメチルホルムア
ミド12mlに溶解させ、さらにラジカル重合開始剤
Ｖ−65（和光純薬工業(株)製）0.6ｇを加え、N₃ガ
ス雰囲気下、70℃で４時間封管重合を行つた。重合反応により得た水不溶性のゲル状物を、充
分に水洗した後、乾燥を行つた。その収量は9.2
ｇであり、仕込み単量体に対する収率は75％であ
る。上記で得たゲル状物を粉砕し、20〜48meshに
分級した。この粉砕物5.0ｇを35％塩酸10ｇ及び脱塩水10
ｇよりなる水溶液中に分散させ、80℃で４時間加
水分解反応を行い、ホルムアミド基をアミノ基に
変換した。この様にして得た樹脂を、酸水溶液、アルカリ
水溶液及び脱塩水を用いてコンデイシヨニング
し、5.2ｇ（収率92.9％）のポリビニルアミン架
橋物を得た。実施例２単量体(A)（Ｎ−ビニルホルムアミドモノマー）
10.0ｇ及びＮ，N′−メチレン−ビス−アクリルア
ミド〔架橋性単量体の(D)〕2.2ｇを30ｇの脱塩水
に溶解させ、ラジカル重合開始剤（実施例１で使
用したものと同じ）を共存させた後、200mlのエ
チレンダイクロライド中に分散した。30分間撹拌
して充分に分散させた後、N₂雰囲気下、60℃で
10時間懸濁重合を行うことにより、水不溶性の球
状のゲルを得た。このゲルを充分に水洗した後、
乾燥を行つた。得られたゲル状物の収量は10.9ｇ
であり、仕込みモノマーに対する収率は89.3％で
あつた。この球状のゲル5.0ｇを、35％塩酸10ｇ及び脱
塩水30ｇよりなる水溶液中に分散させ、75℃で６
時間加水分解を行い、ホルムアミド基をアミノ基
に変換した。この様にして得た樹脂を酸水溶液、次いでアル
カリ水溶液を用いてコンデイシヨニングし、5.1
ｇ（収率91.1％）のポリビニルアミン架橋物を得
た。比較例１アクリルアミドモノマー10.0ｇ及び工業規格の
ジビニルベンゼン（純分56.7％、実施例１で使用
したものと同じ）2.3ｇを、ジメチルホルムアミ
ド12mlに溶解させ、ラジカル重合開始剤Ｖ−65
（和光純薬工業(株)製）0.6ｇを加え、N₂雰囲気下、
70℃で４時間封管重合を行つた。この重合反応により得た水不溶性のゲル状物を
充分に水洗した後、乾燥を行つたところ、その収
量は8.9ｇであり、仕込みモノマーに対する収率
は72.4％であることが分かつた。上記で得たゲル状物を粉砕し20〜48meshに分
級した。この粉砕物5.0ｇを、次亜塩素酸ソーダ6.0ｇを
含む2.2規定の水酸化ナトリウム水溶液100mlに分
散させ、０℃で24時間ホフマン反応を行つてアミ
ノ基を生成した。この様にして得た樹脂を、酸水溶液、アルカリ
水溶液、脱塩水を用いてコンデイシヨニングし、
5.0ｇをキレート樹脂としてポリビニルアミン架
橋物を得た。実施例３実施例１、２及び比較例１で得られたポリビニ
ルアミン架橋物それぞれの乾燥状態で2.0ｇを、
１規定の塩酸200mlを入れた各三角フラスコ中へ
それぞれ添加した。上記架橋物添加後の各三角フラスコを室温で１
日放置した後、各三角フラスコ中の上澄液の塩酸
濃度を、１規定のアルカリ溶液を用いフエノール
フタレイン法により滴定した。この様にして、上記ポリビニルアミン架橋物の
それぞれに吸着された塩酸量を求めることによ
り、当該各架橋物の分子中に存在するアミノ基量
を測定し、ホルムアミド基の加水分解率を求め
た。それらの結果をまとめて下記表−１に示す。 (Industrial Application Field) The present invention relates to a novel method for producing a crosslinked polyvinylamine product. Polyvinylamine is a water-soluble polymer with a high density of cationic functional groups that are bonded adjacent to a main chain consisting of carbon-carbon bonds. That is,
The performance of polyvinylamine is that its aqueous solution exhibits strong basicity due to the microscopic or macroscopic interaction of the amino groups that are densely bonded adjacent to the main chain consisting of carbon-carbon bonds. ,
In addition, the steric arrangement of the amino group allows for various metal ions,
In particular, it occupies a position suitable for chelate formation with transition metal ions such as copper ions and iron ions, and is known to have strong chelate formation ability. If it were possible to easily obtain a crosslinked polyvinylamine that is crosslinked and made insoluble in water while making full use of the structure of polyvinylamine that exhibits such performance, it would be possible to obtain excellent anion exchange resins and chelate resins, as well as other materials. The range of applications can be expanded to include antistatic agents, paints, cosmetics, paper manufacturing, medical polymer materials, etc. (Prior art) Conventionally, in order to produce a crosslinked polyvinylamine product, a water-insoluble crosslinked product is obtained by copolymerizing an acrylamide monomer and divinylbenzenes, and then a crosslinked polyvinylamine product is obtained by a Hoffman reaction. method is used. (Problems to be Solved by the Invention) However, in this conventionally known production method, in addition to performing the Hofmann reaction using a water-insoluble polymer after crosslinking, the conversion rate of the Hofmann reaction is generally low or Due to the carboxylic acid produced as a by-product during the Hofmann reaction, it is not only impossible to obtain a polyvinylamine crosslinked product with a high amino group content, but also it is impossible to obtain a polyvinylamine crosslinked product consisting only of amino groups. It is. (Means for solving the problems) The present inventors have solved the drawbacks of the above conventional method,
As a result of intensive research to provide a manufacturing method that would easily produce a crosslinked polyvinylamine product with a high content of amino groups, we discovered that we could combine an N-vinylformamide monomer with a crosslinkable monomer that can be copolymerized with the monomer. It was discovered for the first time that the desired crosslinked polyvinylamine with a high amino group content can be easily obtained by polymerizing and further hydrolyzing the formamide groups present in the molecules of the resulting copolymer. , which led to the completion of the present invention. The present invention will be described in detail below. (hereinafter referred to as "monomer (A)") and (B), (C), (D) of the following general formula that can be copolymerized with the monomer (A). ) and (E) (wherein R ¹ is selected as a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a plurality of combinations thereof, and X is selected as a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a plurality of combinations thereof) ), (wherein R ² is selected as a hydrogen atom, a methyl group, or a combination of these, and n is 1
- indicates an integer of 6), (In the formula, R ³ is selected as a hydrogen atom, a methyl group, or a plurality of combinations thereof, and m is 1
(indicates an integer of ~6) and (wherein, R ⁴ is selected as a hydrogen atom, a methyl group, or a combination of two or more of these). (A)) It usually consists of two steps: a first step of obtaining a crosslinked product, and a second step of hydrolyzing the formamide groups present in the molecules of the obtained crosslinked product to convert them into amino groups. (Function) The monomer (A) used as the main raw material above easily undergoes radical copolymerization with the crosslinking monomer or various other monomers. Further, the formamide group present in the molecule of the water-insoluble crosslinked product obtained by the above copolymerization can be easily hydrolyzed and converted into an amino group. The crosslinkable monomer used for copolymerization with monomer (A) in the method of the present invention is one that is copolymerizable with monomer (A) and is inert during hydrolysis of formamide groups. If so, it can be used. Specific examples of such crosslinkable monomers include aromatic polyvinyl compounds (referred to as "monomers") such as divinylbenzene, divinyltoluene, and divinylxylene, N,N'-
N,N'-methylene (or polymethylene)-bis-acrylamide or -methacrylamide such as methylene-bis-acrylamide or -methacrylamide (referred to as "monomer (D)"), ethylene glycol di-acrylate or Polyethylene glycol-di-acrylate or -methacrylate such as methacrylate or diethylene glycol-di-acrylate or -methacrylate (referred to as "monomer (C)"), trimethylolethane-
Tri-acrylate or -methacrylate, trimethylolpropane-tri-acrylate or -
Tri-acrylates such as methacrylate or -methacrylates (referred to as "monomer (E)"), and the like. In addition to the crosslinkable monomers mentioned above, monomer (A) and other monomers copolymerizable with the crosslinkable monomer are also monomers used as main raw materials in the present invention. Although it can be used in copolymerization with (A), the amount of this monomer used is optimized depending on the application. Specific examples of such monomers other than crosslinkable monomers include aliphatic vinyl compounds such as ethylene, propylene, butylene, acrylic esters, and methacrylic esters, and aromatic vinyl compounds such as styrene and vinyltoluene. It will be done. The amount of monomer used in the copolymerization reaction of the method of the present invention is optimized depending on the properties of the monomer used or the purpose of use of the obtained crosslinked polyvinylamine product, but generally the main raw material monomer (A)
The usage ratio of the crosslinking monomer to the total monomers is 10 mol% to 99.5 mol%, and the usage ratio of the crosslinking monomer to the total monomers is 90 mol% to 0.5 mol%. The above copolymerization reaction may be carried out by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. in the presence of a radical initiator, depending on the properties of the monomers used or the intended use of the resulting polyvinylamine crosslinked product. Do it by method. For example, when copolymerizing monomer (A) and divinylbenzene [crosslinkable monomer (B)],
A bulk polymerization method or a solution polymerization method is carried out under the conditions of the above molar ratio in the presence of a radical initiator.
In this case, the solvent for solution polymerization is preferably dimethyl sulfoxide, dimethyl formamide,
Alternatively, a solvent such as propionitrile may be used. Furthermore, for example, monomer (A) and N,N'-methylene-bis-acrylamide [crosslinking monomer]
When copolymerizing with (D)] by a suspension polymerization method, an aqueous solution in which the monomers used and a radical polymerization initiator are dissolved is suspended in a water-insoluble organic solvent that is inert to the polymerization reaction. By performing a polymerization reaction, a spherical poly(monomer (A)) crosslinked product, that is, poly(N
- formamide) crosslinked products can be produced. Hydrolysis of the poly(monomer (A)) crosslinked product, that is, the poly(N-formamide) crosslinked product in the method for producing the polyvinylamine crosslinked product of the present invention can be easily carried out under acidic or alkaline conditions. . That is, when hydrolysis is carried out under acidic conditions, an aqueous or alcoholic solution containing a mineral acid in an equimolar to several times the molar amount of the formamide group contained in the molecule of the poly(N-vinylformamide) crosslinked product is used. The reaction temperature is 50°C to 100°C and the reaction time is 1 hour to 30 hours. In addition, when hydrolysis is carried out under alkaline conditions, an aqueous or alcoholic solution containing a basic electrolyte in an amount of one to several equivalents to the formamide group contained in the molecule of the crosslinked poly(N-vinylformamide) is used. The reaction temperature was 60℃~120℃,
The reaction time is 1 hour to 30 hours. In this case, as the basic electrolyte, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, etc. are used. The polyvinylamine crosslinked product produced as described above is washed using an acidic aqueous solution, an alkaline aqueous solution, and demineralized water. (Examples) Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded. In addition,"%"
are based on weight unless otherwise specified. Example 1 Monomer (A) (N-vinylformamide monomer)
10.0 g and 2.3 g of industrial standard divinylbenzene [crosslinking monomer (B)] (purity 56.7%, impurities mainly ethylvinylbenzene) were dissolved in 12 ml of dimethylformamide, and then radical polymerization initiator V-65 was dissolved. (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and sealed tube polymerization was performed at 70° C. for 4 hours in an N ₃ gas atmosphere. The water-insoluble gel obtained by the polymerization reaction was thoroughly washed with water and then dried. Its yield is 9.2
g, and the yield based on the monomer charged was 75%. The gel-like material obtained above was crushed and classified into 20 to 48 mesh. Add 5.0g of this pulverized material to 10g of 35% hydrochloric acid and 10g of demineralized water.
A hydrolysis reaction was carried out at 80° C. for 4 hours to convert formamide groups to amino groups. The thus obtained resin was conditioned using an acid aqueous solution, an alkaline aqueous solution and demineralized water to obtain 5.2 g (yield 92.9%) of a crosslinked polyvinylamine product. Example 2 Monomer (A) (N-vinylformamide monomer)
10.0 g and 2.2 g of N,N'-methylene-bis-acrylamide [crosslinking monomer (D)] were dissolved in 30 g of demineralized water, and a radical polymerization initiator (same as that used in Example 1) was added. were allowed to coexist, and then dispersed in 200 ml of ethylene dichloride. After stirring for 30 min to fully disperse, _the
By carrying out suspension polymerization for 10 hours, a water-insoluble spherical gel was obtained. After washing this gel thoroughly with water,
I did drying. The yield of the gel-like material obtained was 10.9g.
The yield was 89.3% based on the monomer charged. 5.0 g of this spherical gel was dispersed in an aqueous solution consisting of 10 g of 35% hydrochloric acid and 30 g of demineralized water, and the mixture was heated at 75°C for 6 hours.
Time hydrolysis was performed to convert formamide groups to amino groups. The resin thus obtained was conditioned using an acid aqueous solution and then an alkali aqueous solution.
g (yield: 91.1%) of a crosslinked polyvinylamine product was obtained. Comparative Example 1 10.0 g of acrylamide monomer and 2.3 g of industrial standard divinylbenzene (purity 56.7%, same as that used in Example 1) were dissolved in 12 ml of dimethylformamide, and radical polymerization initiator V-65 was dissolved.
(manufactured by Wako Pure Chemical Industries, Ltd.) 0.6g was added, and under an _N2 atmosphere,
Seal tube polymerization was carried out at 70°C for 4 hours. When the water-insoluble gel obtained by this polymerization reaction was thoroughly washed with water and then dried, it was found that the yield was 8.9 g, and the yield was 72.4% based on the monomers charged. The gel-like material obtained above was crushed and classified into 20 to 48 mesh. 5.0 g of this pulverized material was dispersed in 100 ml of a 2.2N aqueous sodium hydroxide solution containing 6.0 g of sodium hypochlorite, and a Hofmann reaction was performed at 0° C. for 24 hours to generate amino groups. The resin thus obtained is conditioned using an acid aqueous solution, an alkaline aqueous solution, and demineralized water.
A polyvinylamine crosslinked product was obtained by using 5.0 g as a chelate resin. Example 3 2.0 g of each of the polyvinylamine crosslinked products obtained in Examples 1 and 2 and Comparative Example 1 in a dry state was
The mixture was added to each Erlenmeyer flask containing 200 ml of 1N hydrochloric acid. After adding the above crosslinked product, each Erlenmeyer flask was heated at room temperature.
After being left in the sun, the hydrochloric acid concentration of the supernatant liquid in each Erlenmeyer flask was titrated by the phenolphthalein method using a 1N alkaline solution. In this manner, by determining the amount of hydrochloric acid adsorbed on each of the crosslinked polyvinylamine products, the amount of amino groups present in the molecules of each crosslinked product was measured, and the rate of hydrolysis of formamide groups was determined. The results are summarized in Table 1 below.

【表】（発明の効果）上記表−１の結果からも分かるように、従来の
ホフマン反応を用いる方法による比較例１の場合
に比べ、本発明の方法による実施例の場合は、ホ
ルムアミド基の加水分解率、即ちアミノ基含有率
が格段に高くなつて理論含有率に近づき、従来に
なく優れた性能を有するポリビニルアミン架橋物
が極めて容易に得られるものと認められる。[Table] (Effects of the invention) As can be seen from the results in Table 1 above, compared to Comparative Example 1 using the conventional Hofmann reaction method, in the case of the example according to the method of the present invention, the formamide group It is recognized that the hydrolysis rate, that is, the amino group content is much higher and approaches the theoretical content, and a crosslinked polyvinylamine product having unprecedentedly excellent performance can be obtained extremely easily.

Claims

[Claims] 1 Formula (A) N-vinylformamide monomer (hereinafter referred to as "monomer (A)") represented by (B), (C), (D) of the following general formula that can be copolymerized with monomer (A) (E) (wherein R ¹ is selected as a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a plurality of combinations thereof, and X is selected as a hydrogen atom, a chlorine atom, a bromine atom, an iodine atom, or a plurality of combinations thereof) ), (wherein R ² is selected as a hydrogen atom, a methyl group, or a combination of these, and n is 1
- indicates an integer of 6), (In the formula, R ³ is selected as a hydrogen atom, a methyl group, or a plurality of combinations thereof, and m is 1
(indicates an integer of ~6) and (In the formula, R ⁴ is selected as a hydrogen atom, a methyl group, or a combination of two or more of these) or copolymerization with a monomer selected from crosslinkable monomers respectively represented by the following: and other monomers copolymerizable with the crosslinkable monomer and copolymerization with the crosslinkable monomer to obtain a water-insoluble gel,
A method for producing a crosslinked polyvinylamine product, which further comprises generating amino groups by hydrolyzing formamide groups present in the molecules of the gel. 2 Monomer (A) and one or two selected from (B), (C), (D) and (E) of the crosslinkable monomers copolymerizable with monomer (A). Using the above, the amount ratio of monomer (A) to the total monomers is 10 mol% to 99.5 mol%.
The usage ratio of (B), (C), (D), and (E) to the total monomer is 90
The method for producing a crosslinked polyvinylamine product according to claim 1, characterized in that the content is from mol% to 0.5 mol%.