JP2005320391A - Organic peracid polymer and its preparation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic peracid polymer which shows a good stability, is odorless and sufficiently soluble to water and is suitably used as a disinfectant, a bleaching agent, an epoxidizing agent, etc. <P>SOLUTION: The organic peracid polymer is a polymer having carboxy groups within its structural unit (e.g. polyacrylic acid, polymethacrylic acid, polymaleic acid, acrylic acid/maleic acid copolymer, acrylic acid/acrylamide copolymer, etc.), wherein the carboxy groups are partially replaced by peroxycarboxy groups. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an organic peracid polymer having a peroxycarboxyl group.

Conventional organic peracids include formic acid, peracetic acid, perpropionic acid, perbutyric acid, permalonic acid, persuccinic acid, perglutaric acid, peradipic acid, pertartaric acid, percitric acid, perbenzoic acid, perphthalic acid Etc. are known (see Non-Patent Document 1). These peracids are useful in applications such as bactericides, bleaches, epoxidizing agents and the like. However, these organic peracids are not always satisfactory in terms of stability, odor, water solubility and the like.
Organic peroxide chemical industry 1972

  An object of the present invention is to provide an organic peracid that has good stability, does not smell, and has sufficient water solubility.

  As a result of intensive studies on the above problems, the present inventors have found an organic peracid polymer having a partly peroxycarboxyl group in the structural unit. That is, the present invention relates to an organic peracid polymer characterized in that it is a polymer having a carboxyl group in a structural unit and has a structure in which a part of the carboxyl group is replaced with a peroxycarboxyl group.

  Furthermore, by reacting a polymer having a carboxyl group in the structural unit with hydrogen peroxide, an organic peroxide having a structure in which a part of the carboxyl group is replaced with a peroxycarboxyl group in the polymer having a carboxyl group in the structural unit. A method for producing an acid polymer.

  The organic peracid polymer of the present invention has good stability, does not smell, has sufficient water solubility, and is suitably used as a bactericide, a bleaching agent, an epoxidizing agent and the like.

  The polymer having a carboxyl group in the structural unit referred to in the present invention is not particularly limited as long as it is an organic acid polymer having a carboxyl group in the structural unit. Specific examples include polyacrylic acid, polymethacrylic acid, polymaleic acid, acrylic acid maleic acid copolymer or acrylic acid acrylic acid amide copolymer, or metal salts thereof. An example of the metal salt is a sodium salt. The organic peracid polymer of the present invention has a structure in which a part of the carboxyl groups of the organic acid polymer is replaced with a peroxycarboxyl group, but there is no particular limitation on the substitution ratio, and a desired ratio can be obtained as necessary. do it. The substitution ratio is, for example, 1 to 90% (if it is low, the effect as a peracid does not appear, and a high ratio cannot be produced).

  The organic peracid polymer of the present invention can be obtained by mixing a polymer having a carboxyl group in a structural unit with hydrogen peroxide, and controlling the substitution ratio of the carboxyl group to the percarboxyl group by the mixing ratio. Is possible. The substitution ratio is, for example, 1 to 90%. As the hydrogen peroxide, a commercially available hydrogen peroxide of 3 to 90% by weight can be used. For example, in the case of polyacrylic acid, the mixing ratio is 1 part by weight of polyacrylic acid and 2 parts by weight of hydrogen peroxide (35% by weight hydrogen peroxide). In addition, a catalyst may be added during mixing to promote the reaction as necessary. Specific examples of the catalyst include sulfuric acid, and the addition amount is about 2% by weight. A stabilizer may be added to improve the stability. Specific examples of the stabilizer include orthophosphoric acid, and the addition amount is about 1% by weight.

Example 1
[Perpolyacrylic acid]
To 2 g of polyacrylic acid (molecular weight 5000, manufactured by Wako Pure Chemical Industries, Ltd.) was added 4 ml of 35% by weight hydrogen peroxide water (manufactured by Mitsubishi Gas Chemical) and 0.1 ml of sulfuric acid to dissolve the polyacrylic acid, and the mixture was allowed to stand at room temperature. As a result of measuring 13C-NMR with a heavy water solvent after 9 days (FIG. 1), a peak of carbon of carboxyl group at 182 ppm and a carbon of peroxycarboxyl group at 178 ppm were confirmed (reference substance: sodium 3- (trimethylsilyl) propionate). . Further, the concentration of hydrogen peroxide (potassium permanganate titration) and the concentration of peroxycarboxyl group (iodometry) in the product solution were determined. Table 1 shows changes with time in the concentrations of hydrogen peroxide, carboxyl groups, and peroxycarboxyl groups. As for the odor, there is no irritating odor like peracetic acid.

Example 2
[Perpolyacrylic acid]
To polyacrylic acid (molecular weight 2000, Aldrich 2.5 g) was added 35 wt% hydrogen peroxide solution (Mitsubishi Gas Chemical Co., Ltd.) 5 ml and sulfuric acid 0.1 ml to dissolve the polyacrylic acid and left at room temperature. Table 2 shows changes with time in the concentrations of hydrogen peroxide, carboxyl groups, and peroxycarboxyl groups. As for the odor, it smells a little, but there is no pungent odor like peracetic acid.

Example 3
[Male acrylate copolymer]
Add maleic acrylate copolymer (50% aqueous solution, molecular weight 3000, 2.5 ml made by Aldrich) to 2.5 ml 35% hydrogen peroxide (Mitsubishi Gas Chemical) and 0.1 ml sulfuric acid to dissolve the maleic acrylate copolymer at room temperature. Left at rest. Table 3 shows changes with time in the concentrations of hydrogen peroxide, carboxyl groups, and peroxycarboxyl groups. As for the odor, it smells a little, but there is no pungent odor like peracetic acid.

13C-NMR measurement result of Example 1

Claims (4)

  An organic peracid polymer having a carboxyl group in a structural unit and having a structure in which a part of the carboxyl group is replaced with a peroxycarboxyl group.   2. The organic peracid polymer according to claim 1, wherein the polymer having a carboxyl group is polyacrylic acid, polymethacrylic acid, polymaleic acid, maleic acrylate copolymer or acrylic amide acrylate copolymer, or a metal salt thereof.   The method for producing an organic peracid polymer according to claim 1, wherein a polymer having a carboxyl group in a structural unit is reacted with hydrogen peroxide.   The method for producing an organic peracid polymer according to claim 3, wherein the reaction is carried out in the presence of a catalyst.

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