JP3724139B2 - Method for producing haloacetamidomethylated polysulfone - Google Patents

Description

【化２】

ポリスルホンの具体例としては、ユーデルポリスルホンＰー１７００、Ｐー３５００（テイジンアモコ社製）、ウルトラソンＳ３０１０、Ｓ６０１０（ＢＡＳＦ社製）、ビクトレックス（住友化学）、レーデルＡ（テイジンアモコ社製）、ウルトラソンＥ（ＢＡＳＦ社製）等のポリスルホンが挙げられる。
【００１４】
本発明で用いられるハロアセトアミドメチル化ポリスルホンは、好ましくは、次式（Ｉ）
Ｘ−ＣＨ（Ｒ₁）−ＣＯ−Ｎ（Ｒ₂）−ＣＨ₂− （Ｉ）
（式中、Ｘはハロゲン原子、Ｒ₁およびＲ₂は水素原子、低級アルキル基またはベンジル基を示し、Ｒ₁とＲ₂は同一でも異なっていてもよい。）で示される基を繰り返し単位あたり０．００１〜４個有するものである。
【００１５】
かかる式（Ｉ）で示される基としては、２−クロロアセトアミドメチル基、２−クロロプロピルアミドメチル基、２−クロロブチルアミドメチル基、２−ヨードアセトアミドメチル基、２−フルオロアセトアミドメチル基および２−ブロモアセトアミドメチル基などが挙げられるが、これらに限定されるものではない。しかしながら、反応性の高さや取扱の容易さから、αークロロアセトアミドメチル基、２−ヨードアセトアミドメチル基、２−フルオロアセトアミドメチル基および２−ブロモアセトアミドメチル基などが好ましい。
【００１６】
本発明で使用されるハロアセトアミドメチル化ポリスルホンは、基本的には、酸触媒の存在下に、上述の主鎖に芳香環、エーテル基およびスルフォニル基を有するポリスルホンと、次式（II）
Ｘ−ＣＨ（Ｒ₁）−ＣＯ−Ｎ（Ｒ₂）−ＣＨ₂−Ｏ−Ｙ （II）
（式中、Ｘはハロゲン原子、Ｒ₁およびＲ₂は水素原子、低級アルキル基またはベンジル基を示し、Ｒ₁とＲ₂は同一でも異なっていてもよい。Ｙは水素原子、低級アルキル基またはアシル基を示す。）で示されるハロアセトアミドメチル化剤とを反応せしめ製造することができる。
【００１７】
本発明で用いるハロアセトアミドメチル化剤としては、Ｎ−メチロール−２−クロロアセトアミド、Ｎ−メチロール−２−ブロモアセトアミド、Ｎ−メチロール−２−フルオロアセトアミド、Ｎ−メチロール−２−ヨードアセトアミドおよびＮ−メチロール−２−クロロブチルアミドなどのほか、これらのメチルエーテルやアセチルエステルなどが挙げられ、これらに限定されるものではないが、製造が容易で反応性が高く、取扱が容易なＮ−メチロール−２−クロロアセトアミド、Ｎ−メチロール−２−ブロモアセトアミド、Ｎ−メチロール−２−フルオロアセトアミドおよびＮ−メチロール−２−ヨードアセトアミドなどが特に好ましい。
【００１８】
ハロアセトアミドメチル化剤の使用量と導入されるハロアセトアミドメチル基は正の相関にあるため、目標とするハロアセトアミドメチル基の量に応じて、その使用量を増減することができる。
【００１９】
導入されるハロアセトアミドメチル基の量は繰り返し単位あたり０．０１〜４まで可能である。しかしながら、このハロアセトアミドメチル基の量は、溶媒、ポリスルホンおよびポリビニルピロリドン等の親水性高分子物質とともにブレンドしたときに、ポリスルホンとの相溶性をよくするという観点から、好ましくは繰り返し単位あたり０．０１〜２であるが、ホリスルホンの使用用途に応じて導入数を選択すればよい。
【００２０】
本発明で用いられるハロアセトアミドメチル化反応のための触媒としては、塩化亜鉛、塩化アルミニウム、四塩化銅、塩化第二鉄のごときフリーデル・クラフツ触媒、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、メタンスルホン酸、エタンスルホン酸、ブタンスルホン酸、トリフルオロメタンスルホン酸、トリフルオロメタンスルホン酸トリメチルシリルエステルなどのスルホン酸誘導体および硫酸などが挙げられるが、硫酸は、Ｎ−メチロール−α−クロロアセトアミドを容易に溶解する溶媒となり得るので特に好ましく用いられる。
【００２１】
本発明のハロアセトアミドメチル化反応で使用され反応溶媒としては、塩化メチレン、クロロホルム、Ｎ−メチルピロリドン、ジメチルアセトアミド、テトラヒドロフラン、ジメチルアセトアミド等 が挙げられ、ポリスルホンの良溶媒であれば特に限定されないが、ハロアセトアミドメチル化剤添加時に発熱の少ないニトロベンゼンが特に好ましく用いられる。
【００２２】
本発明のハロアセトアミドメチル化ポリスルホンの製造は、ハロアセトアミドメチル化剤、触媒および溶媒からなる０．１〜２０ｗｔ％のハロアセトアミドメチル化溶液を、０．１〜５０ｗｔ％のポリスルホンの溶液に添加することにより達成される。ハロアセトアミドメチル化溶液の濃度は、ハロアセトアミドメチル化剤をすばやく溶解させ、ハロアセトアミドメチル化溶液の添加量を押さえるという観点から１〜１０ｗｔ％が好ましい。また、ポリスルホン溶液の濃度は、均一に撹拌し、収量を上げるという観点から５〜２０ｗｔ％が好ましい。
【００２３】
この反応際、ハロアセトアミドメチル化剤、触媒および溶媒からなるハロアセトアミドメチル化溶液中にはホルムアルデヒドが副生するが、そのホルムアルデヒドをハロアセトアミドメチル化剤に対し０．５％以下に抑えることにより、製造時にゲル化を抑えることができる。
【００２４】
本発明でいうゲル化とは、目視にて、不透明不均一なかたまりが見られることをいう。現象的には、例えばハロアセトアミドメチル化剤をポリスルホンの溶液に添加したときに、数秒後に固化し、スターラーチップで撹拌した場合は撹拌が止まり、撹拌翼で撹拌した場合は、ゲルが撹拌翼の軸を伝わって上昇してくるような状態をいう。
【００２５】
本発明において、ハロアセトアミドメチル化溶液中のホルムアルデヒド副生を抑制する手段の一として、ハロアセトアミドメチル化溶液の調製温度、およびポリスルホンとハロアセトアミドメチル化剤との反応温度の調整が挙げられる。
【００２６】
ハロアセトアミドメチル化溶液の調製温度は、−２０〜１０℃程度の範囲で可能であるが、ホルムアルデヒドの副生を抑えるという観点から８℃以下にすることが好ましく、０℃以下にすることがより好ましい。
【００２７】
また反応温度は、ハロアセトアミドメチル化液中のホルムアルデヒドをハロアセトアミドメチル化剤に対し０．５％以下に抑えられていれば、０℃〜５０℃の範囲で製造可能であるが、反応中でのホルムアルデヒドの発生を抑制するという観点から０℃〜３０℃で製造するのが好ましく、より好ましくは０℃〜２５℃、さらに好ましくは０℃〜１５℃である。溶媒の融点が高い（例えば、ニトロベンゼンでは５℃）場合は、あらかじめ硫酸などを混合しておいて融点を下げてもよい。反応速度は速く、１０分以内に完了する。
【００２８】
ホルムアルデヒドの定量は、以下のようにして行なった。
【００２９】
ハロアセトアミドメチル化液中のホルムアルデヒド濃度は次のようにして定量を行なった。すなわち、４℃に冷却したｐＨ２〜２．５のリン酸バッファー５ｍｌにハロアセトアミドメチル化液を１０μｌ添加した後、０．１８Ｍの２−アミノー２ーペンテンー４−オンのアセトニトリル溶液を１ｍｌ添加して、ハロアセトアミドメチル化液中のホルムアルデヒドと１０分反応させた。反応溶液はホルムアルデヒド濃度に比例して、黄色を呈するので、４１０ｎｍの波長で吸光度を求めた。ホルムアルデヒド濃度は別に作成した検量線から算出した。
【００３０】
本発明で得られるハロアセトアミドメチル化ポリスルホンは、そのまま、もしくはハロアセトアミドメチル基をアミノ基を有する化合物、カルボン酸、水酸基を有する化合物、チオール基を有する化合物などと反応させて、別の官能基に変換後、ポリスルホンおよびポリビニルピロリドン等の親水性高分子物質とともに、それらの良溶媒に溶解することにより原液を調製し、膜状、繊維状および中空糸状など種々の形態に成形することにより用いられる。官能基の変換は、成型後でも可能である。得られた成形品は、そのまま、もしくは、官能基変換後、人工臓器、細胞培養器具、カテーテルおよび抗菌剤などの用途に利用することができる。
【００３１】
【実施例】
（実施例１）
７．１３ｗｔ％に調製したユーデルポリスルホンＰ３５００（アモコ社製）のニトロベンゼン溶液１７．５３ｇを８℃に冷却し、これに別に−５℃で３０分間撹拌することにより調製した５．３０ｗｔ％のＮ−メチロール−２−クロロアセトアミドの硫酸溶液を３．３０ｇ添加し反応を８℃で行なった。このとき使用したＮ−メチロール−２−クロロアセトアミドの硫酸溶液中のホルムアルデヒド濃度は２００ｐｐｍ（Ｎ−メチロール−２−クロロアセトアミドに対し０．４％）であった。反応はゲル化せず進行し１０分で終了したが、この反応状態で２時間以上たってもゲル化は起こらなかった。
【００３２】
（比較例１）
７．１３ｗｔ％に調製したユーデルポリスルホンＰ３５００（アモコ社製）のニトロベンゼン溶液１７．５３ｇを８℃に冷却し、これと別に５℃で１時間撹拌することにより調製した５．３０ｗｔ％のＮ−メチロール−２−クロロアセトアミドの硫酸溶液を３．３０ｇ添加し反応を８℃で行なった。このときのＮ−メチロール−２−クロロアセトアミドの硫酸溶液中のホルムアルデヒド濃度は４００ｐｐｍ（Ｎ−メチロール−２−クロロアセトアミドに対し０．７％）であった。反応開始後、１分間は攪拌されていたが、その後は、反応中に突然ゲル化が起こって攪拌できなくなった。
【００３３】
（実施例２）
７．１３ｗｔ％に調製したユーデルポリスルホンＰ３５００（アモコ社製）のニトロベンゼン溶液１７．５３ｇを２５℃に冷却し、これに別に５℃で２０分間撹拌することにより調製した５．３０ｗｔ％のＮ−メチロール−２−クロロアセトアミドの硫酸溶液を３．３０ｇ添加し反応を２５℃で行なった。このとき使用したＮ−メチロール−２−クロロアセトアミドの硫酸溶液中のホルムアルデヒド濃度は２００ｐｐｍ（Ｎ−メチロール−２−クロロアセトアミドに対し０．４％）であった。反応はゲル化せず進行し１０分で終了したが、この反応状態で２時間以上たってもゲル化は起こらなかった。
【００３４】
（実施例３）
７．１３ｗｔ％に調製したユーデルポリスルホンＰ３５００（アモコ社製）のニトロベンゼン溶液１７．５３ｇを８℃に冷却し、これに別に−５℃で１時間撹拌することにより調製した５．３０ｗｔ％のＮ−メチロール−２−クロロアセトアミドの硫酸／ニトロベンゼン（３／１）混合溶液を３．３０ｇ添加し反応を８℃で行なった。このとき使用したＮ−メチロール−２−クロロアセトアミドの硫酸溶液中のホルムアルデヒド濃度は１５０ｐｐｍ（Ｎ−メチロール−２−クロロアセトアミドに対し０．３％）であった。反応はゲル化せず進行し１０分で終了したが、この反応状態で２時間以上たってもゲル化は起こらなかった。
【００３５】
【発明の効果】
本発明により得られるハロアセトアミドメチル化ポリスルホンは、製造時にゲル化が起こらず安定に反応できる点で有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention is an aromatic ring in the main chain, a method of manufacturing a haloacetamide methylated polysulfone down with halo acetamidomethyl group in the side chain of polysulfone having an ether group and a sulfonyl group. More particularly, the present invention relates to a manufacturing method of the haloacetamide methylated polysulfone down with various substances that can bind haloacetamide methyl group in its side chain.
[0002]
[Prior art]
Polysulfone has excellent heat resistance and is used for various separation membranes and films including dialysis membranes. As one of such polysulfones, haloacetamidomethylated polysulfone is known.
[0003]
Conventionally, as a method for producing a haloacetamidomethylated polysulfone, as proposed in Japanese Patent No. 2509085, an aromatic polysulfone polymer and a molded product thereof are prepared by using a specific haloacetamidomethylating agent in the presence of an acid catalyst. The method of reacting with is known. However, in the production of haloacetamidomethylated polysulfone, no detailed examination has been made on gelation during synthesis, despite the high reactivity of the haloacetamidomethyl group. The reaction may be a heterogeneous reaction such as a reaction to a molded product, but in the case of a homogeneous reaction, gelation may occur even if synthesized by a conventional method.
[0004]
When gelation occurs, the reaction solvent cannot be extracted from the gel. Even if the solvent is extracted for a long time to recover the polymer, the polymer only swells in the solvent and does not dissolve. For this reason, film formation from the solution is impossible.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to improve the drawbacks of such prior art and to provide a method for efficiently producing haloacetamidomethylated polysulfone without causing gelation when synthesizing haloacetamidomethylated polysulfone. .
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the method for producing a haloacetamidomethylated polysulfone according to the present invention is characterized in that the formaldehyde concentration produced as a by-product when the polysulfone and the haloacetamidomethylating agent are reacted in the presence of an acid catalyst is reduced. And a method of adjusting the temperature of the haloacetamidomethylation solution to be used as a suitable means for suppressing the formaldehyde by-product, and / or There is a method of adjusting the reaction temperature between polysulfone and haloacetamidomethylating agent.
[0007]
In the present invention, the following preferred embodiments are included.
[0008]
(1) The haloacetamide methylation solution should be prepared and used at a temperature of 10 ° C or lower, more preferably 5 ° C or lower.
[0009]
(2) The reaction is carried out at a temperature of 30 ° C. or lower, more preferably 25 ° C. or lower.
[0010]
(3) As the haloacetamidomethylating agent, the following formula (I)
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ —O—Y (I)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. Y is a hydrogen atom, a lower alkyl group or Use an haloacetamidomethylating agent represented by the following:
[0011]
(4) The haloacetamidomethylated polysulfone has the following formula (II)
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ — (II)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. Have 0.001-4.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
The polysulfone used in the present invention has an aromatic ring, a sulfonyl group and an ether group in the main chain. For example, polysulfone represented by the following chemical formulas (III) and (IV) is preferably used. The invention is not limited to these. N in the formula is an integer such as 50 to 80, for example.
[0013]
[Chemical 1]

[Chemical formula 2]

Specific examples of polysulfone include Udel polysulfone P-1700, P-3500 (manufactured by Teijin Amoco), Ultrason S3010, S6010 (manufactured by BASF), Victrex (Sumitomo Chemical), Radel A (manufactured by Teijin Amoco). And polysulfone such as Ultrason E (manufactured by BASF).
[0014]
The haloacetamidomethylated polysulfone used in the present invention preferably has the following formula (I)
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ — (I)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. It has 0.001-4 pieces.
[0015]
Examples of the group represented by the formula (I) include 2-chloroacetamidomethyl group, 2-chloropropylamidomethyl group, 2-chlorobutamidomethyl group, 2-iodoacetamidomethyl group, 2-fluoroacetamidomethyl group and 2 -A bromoacetamidomethyl group etc. are mentioned, However, It is not limited to these. However, α-chloroacetamidomethyl group, 2-iodoacetamidomethyl group, 2-fluoroacetamidomethyl group, 2-bromoacetamidomethyl group and the like are preferable because of high reactivity and easy handling.
[0016]
The haloacetamidomethylated polysulfone used in the present invention is basically a polysulfone having an aromatic ring, an ether group and a sulfonyl group in the main chain in the presence of an acid catalyst, and the following formula (II):
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ —O—Y (II)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. Y is a hydrogen atom, a lower alkyl group or It can be produced by reacting with a haloacetamidomethylating agent represented by the following:
[0017]
Examples of the haloacetamide methylating agent used in the present invention include N-methylol-2-chloroacetamide, N-methylol-2-bromoacetamide, N-methylol-2-fluoroacetamide, N-methylol-2-iodoacetamide, and N- In addition to methylol-2-chlorobutyramide and the like, these methyl ethers and acetyl esters may be mentioned, but are not limited to these. N-methylol which is easy to manufacture, has high reactivity and is easy to handle 2-chloroacetamide, N-methylol-2-bromoacetamide, N-methylol-2-fluoroacetamide, N-methylol-2-iodoacetamide and the like are particularly preferable.
[0018]
Since the amount of the haloacetamidomethylating agent used and the introduced haloacetamidomethyl group are positively correlated, the amount used can be increased or decreased depending on the target amount of haloacetamidomethyl group.
[0019]
The amount of haloacetamidomethyl group introduced can be from 0.01 to 4 per repeating unit. However, the amount of the haloacetamidomethyl group is preferably 0.01 per repeating unit from the viewpoint of improving compatibility with polysulfone when blended with a solvent, a hydrophilic polymer such as polysulfone and polyvinylpyrrolidone. Although it is -2, what is necessary is just to select the number of introduction | transduction according to the use application of polysulfone.
[0020]
As the catalyst for the haloacetamidomethylation reaction used in the present invention, Friedel-Crafts catalyst such as zinc chloride, aluminum chloride, copper tetrachloride, ferric chloride, benzenesulfonic acid, p-toluenesulfonic acid, methane Examples include sulfonic acid derivatives such as sulfonic acid, ethanesulfonic acid, butanesulfonic acid, trifluoromethanesulfonic acid, trimethylsilyl ester of trifluoromethanesulfonic acid, and sulfuric acid, but sulfuric acid easily dissolves N-methylol-α-chloroacetamide. It is particularly preferably used because it can be a solvent to be used.
[0021]
Examples of the reaction solvent used in the haloacetamidomethylation reaction of the present invention include methylene chloride, chloroform, N-methylpyrrolidone, dimethylacetamide, tetrahydrofuran, dimethylacetamide, and the like. Nitrobenzene, which generates little heat when the haloacetamidomethylating agent is added, is particularly preferably used.
[0022]
In the production of the haloacetamidomethylated polysulfone of the present invention, a 0.1-20 wt% haloacetamidomethylation solution comprising a haloacetamidomethylating agent, a catalyst and a solvent is added to a 0.1-50 wt% polysulfone solution. Is achieved. The concentration of the haloacetamidomethylation solution is preferably 1 to 10 wt% from the viewpoint of quickly dissolving the haloacetamidomethylation agent and suppressing the addition amount of the haloacetamidomethylation solution. The concentration of the polysulfone solution is preferably 5 to 20 wt% from the viewpoint of stirring uniformly and increasing the yield.
[0023]
During this reaction, formaldehyde is by-produced in the haloacetamidomethylation solution composed of the haloacetamidomethylating agent, catalyst and solvent, but by suppressing the formaldehyde to 0.5% or less with respect to the haloacetamidomethylating agent, Gelation can be suppressed during production.
[0024]
The gelation as used in the present invention means that an opaque non-uniform lump is seen with the naked eye. Phenomenologically, for example, when a haloacetamidomethylating agent is added to a polysulfone solution, it solidifies after a few seconds, and when stirring with a stirrer chip, stirring stops, and when stirring with a stirring blade, the gel is mixed with the stirring blade. A state that rises along the axis.
[0025]
In the present invention, as a means for suppressing formaldehyde by-product in the haloacetamidomethylation solution, adjustment of the preparation temperature of the haloacetamidomethylation solution and the reaction temperature of polysulfone and the haloacetamidomethylating agent can be mentioned.
[0026]
The preparation temperature of the haloacetamidomethylation solution can be in the range of about −20 to 10 ° C., but it is preferably 8 ° C. or less and more preferably 0 ° C. or less from the viewpoint of suppressing by-product formation. preferable.
[0027]
The reaction temperature can be produced in the range of 0 ° C to 50 ° C as long as the formaldehyde in the haloacetamide methylating solution is suppressed to 0.5% or less with respect to the haloacetamide methylating agent. From the viewpoint of suppressing the generation of formaldehyde, it is preferably produced at 0 ° C. to 30 ° C., more preferably 0 ° C. to 25 ° C., further preferably 0 ° C. to 15 ° C. When the melting point of the solvent is high (for example, 5 ° C. for nitrobenzene), the melting point may be lowered by mixing sulfuric acid or the like in advance. The reaction rate is fast and is completed within 10 minutes.
[0028]
The quantitative determination of formaldehyde was performed as follows.
[0029]
The formaldehyde concentration in the haloacetamidomethylation solution was quantified as follows. That is, after adding 10 μl of haloacetamide methylation solution to 5 ml of phosphate buffer of pH 2 to 2.5 cooled to 4 ° C., 1 ml of 0.18M 2-amino-2-penten-4-one acetonitrile solution was added, The reaction was carried out with formaldehyde in the haloacetamidomethylation solution for 10 minutes. Since the reaction solution was yellow in proportion to the formaldehyde concentration, the absorbance was determined at a wavelength of 410 nm. The formaldehyde concentration was calculated from a separately prepared calibration curve.
[0030]
The haloacetamidomethylated polysulfone obtained in the present invention can be used as it is or by reacting a haloacetamidomethyl group with a compound having an amino group, a carboxylic acid, a compound having a hydroxyl group, a compound having a thiol group, etc. After the conversion, it is used by preparing a stock solution by dissolving it in a good solvent together with hydrophilic polymer substances such as polysulfone and polyvinylpyrrolidone, and forming it into various forms such as membranes, fibers and hollow fibers. Conversion of the functional group is possible even after molding. The obtained molded product can be used for applications such as artificial organs, cell culture instruments, catheters and antibacterial agents as they are or after functional group conversion.
[0031]
【Example】
(Example 1)
7.53 g of nitrobenzene solution of Udelpolysulfone P3500 (Amoco) prepared to 7.13 wt% was cooled to 8 ° C., and separately stirred at −5 ° C. for 30 minutes, 5.30 wt% N prepared -3.30 g of methylol-2-chloroacetamide in sulfuric acid was added and the reaction was carried out at 8 ° C. The formaldehyde concentration in the sulfuric acid solution of N-methylol-2-chloroacetamide used at this time was 200 ppm (0.4% with respect to N-methylol-2-chloroacetamide). The reaction proceeded without gelation and was completed in 10 minutes, but no gelation occurred even after 2 hours in this reaction state.
[0032]
(Comparative Example 1)
7.53 g of nitrobenzene solution of Udelpolysulfone P3500 (Amoco) prepared to 7.13 wt% was cooled to 8 ° C. and separately stirred at 5 ° C. for 1 hour, 5.30 wt% N- 3.30 g of methylol-2-chloroacetamide in sulfuric acid was added and the reaction was carried out at 8 ° C. The formaldehyde concentration in the sulfuric acid solution of N-methylol-2-chloroacetamide at this time was 400 ppm (0.7% with respect to N-methylol-2-chloroacetamide). The reaction was stirred for 1 minute after the start of the reaction, but after that, gelation suddenly occurred during the reaction, and stirring became impossible.
[0033]
(Example 2)
7.53 g of nitrobenzene solution of Udelpolysulfone P3500 (Amoco) prepared to 7.13 wt% was cooled to 25 ° C. and separately stirred at 5 ° C. for 20 minutes, and 5.30 wt% N— 3.30 g of methylol-2-chloroacetamide in sulfuric acid was added and the reaction was carried out at 25 ° C. The formaldehyde concentration in the sulfuric acid solution of N-methylol-2-chloroacetamide used at this time was 200 ppm (0.4% with respect to N-methylol-2-chloroacetamide). The reaction proceeded without gelation and was completed in 10 minutes, but no gelation occurred even after 2 hours in this reaction state.
[0034]
(Example 3)
7.53 wt% N prepared by cooling 17.53 g of a nitrobenzene solution of Udelpolysulfone P3500 (Amoco) prepared to 7.13 wt% to 8 ° C., and separately stirring at −5 ° C. for 1 hour. -3.30 g of a mixed solution of methylol-2-chloroacetamide in sulfuric acid / nitrobenzene (3/1) was added, and the reaction was carried out at 8 ° C. The formaldehyde concentration in the sulfuric acid solution of N-methylol-2-chloroacetamide used at this time was 150 ppm (0.3% with respect to N-methylol-2-chloroacetamide). The reaction proceeded without gelation and was completed in 10 minutes, but no gelation occurred even after 2 hours in this reaction state.
[0035]
【The invention's effect】
The haloacetamidomethylated polysulfone obtained by the present invention is useful in that gelation does not occur during production and the reaction can be performed stably.

Claims (9)

 A haloacetamidomethyl characterized by reacting polysulfone with a haloacetamidomethylating agent in the presence of an acid catalyst with a by-product formaldehyde concentration of 0.5% or less based on the haloacetamidomethylating agent. A process for producing a modified polysulfone. C b acetamidomethyl agent The process of claim 1 halo acetamidomethyl polysulfone, wherein suppressing the by-production of formaldehyde by adjusting the temperature of halo acetamidomethyl solution containing the catalyst and solvent. Claim 2 method for producing a halo acetamidomethyl polysulfone, wherein the a c b acetamidomethyl solution, prepared at 10 ° C. below the temperature used. The method for producing a haloacetamidomethylated polysulfone according to claim 2, wherein the haloacetamidomethylated solution is prepared and used at a temperature of -5 ° C or lower and -20 ° C or higher. A haloacetamidomethylation solution should be prepared and used at a temperature of 5 ° C. or lower and a temperature exceeding −5 ° C. for a time of 20 minutes or shorter, a temperature of −5 ° C. or lower and a temperature of −20 ° C. or higher for 60 minutes or shorter. The method for producing a haloacetamidomethylated polysulfone according to claim 2, Method for producing a halo acetamidomethyl polysulfone according to any one of claims 1-5, characterized in that to suppress the by-production of formaldehyde by the adjustment of the anti応温degree. Method for producing a halo acetamidomethyl polysulfone according to any of claims 1 to 6, characterized by performing reaction at 30 ° C. or lower. C b acetamidomethyl agent has the following formula (I)
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ —O—Y (I)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. Y is a hydrogen atom, a lower alkyl group or The method for producing a haloacetamidomethylated polysulfone according to any one of claims 1 to 7 , which is an haloacetamidomethylating agent represented by the following formula: C b acetamidomethyl polysulfone has the following formula (II)
X—CH (R ₁ ) —CO—N (R ₂ ) —CH ₂ — (II)
Wherein X is a halogen atom, R ₁ and R ₂ are a hydrogen atom, a lower alkyl group or a benzyl group, and R ₁ and R ₂ may be the same or different. method for producing a halo acetamidomethyl polysulfone according to any of claims 1-8, characterized in that it comprises 0.001 to pieces.