MXPA00006279A - Use of oxidation promoting chemicals in the oxidation of oxidizable galactose type of alcohol configuration containing polymer - Google Patents

Abstract

Process for the oxidation of the oxidizable galactose type of alcohol in oxidizable galactose type of alcohol configuration containing polymer, such as guar, with galactose oxidase in the presence of oxidation promoting chemicals.

Description

USE OF CHEMICALS PROMOTERS OF OXIDATION IN THE OXIDATION OF POLYMER CONTAINING CONFIGURATION OF OXIDABLE GALACTOSE TYPE ALCOHOL BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the oxidation of polymer containing oxidizable galactose-type alcohol configuration and more particularly refers to the use of chemical promoters oxidation in said oxidation by galactose oxidase. 2. Description of the Prior Art The product of the oxidation of aqueous solutions of guar gum and other polysaccharides containing galactose using enzyme galactose oxidase was described by F.J. Germino in the US patent. No. 3,297,604. The oxidized products containing aldehyde are separated by precipitation from aqueous solutions used for the enzyme reactions. Germino described the use of rusted products in papermaking. Oxidized products containing aldehyde were also described as suitable for use in the crosslinking of polyamino polymers, polyhydroxy polymers and proteins. C.W. Chiu et al., In the patent of the U.S.A. No. 5,554,745, describes (1) the preparation of polysaccharides containing cationic galactose and (2) the enzymatic oxidation in aqueous solution of polysaccharides containing cationic galactose with galactose oxidase. It is disclosed that oxidized cationic polysaccharides improve the strength characteristics of paper. SUMMARY OF THE INVENTION According to the present invention, there is provided a method for oxidation of the oxidizable galactose type of the alcohol configuration in aldheido in the oxidizable galactose type of polymers containing alcohol configuration, comprising providing the oxidizable galactose type of polymer containing alcohol and galactose oxidase configuration and the oxidation promoting chemical that contains them. DETAILED DESCRIPTION OF THE INVENTION It has surprisingly been found that the use of oxidation promoting chemicals, for example 1,2-benzisothiazolin-3-one, in the oxidation of the oxidizable galactose type of polymers containing alcohol configuration, for example guar, galactose oxidase results in increased levels of oxidation and corresponding increase in paper strength characteristics when the polymer containing galactose oxidase type alcohol configuration is used in the paper production process. In general, an oxidation promoter chemical may be an organic carboxylate compound, organic heterocyclic compound and / or quaternary amine compound. Preferably, the organic carboxylate compound is sorbic acid, salicylic acid, benzoic acid, toluic acid, phthalic acid and their corresponding salts, the organic heterocyclic compound is 1,2-benzisothiazolin-3-one, and / or 2-methyl-4 isothiazolin-3-one, and the quaternary amine compound is cetyltrimethylammonium bromide and / or quaternary epoxy amines. Preferably in particular chemical promoter oxidation is 1,2-benzisothiazolin-3 -one. The oxidizable galactose alcohol type configuration can be described by the following chemical structures: n wherein Rx = is an alkyl group of the formula C (n) H (2n + l) wherein n = 0-20: z = 0.1; R2 = is a linking group which is composed of an alkylene or alkylene aromatic or an alkylene ether, or an alkylene ester or an alkylene amide, or a diradical alkylene urethane. These linking groups have a total number of carbon atoms from 2 to 20: R3 = -H, -OH, -0CH3, -OC2H5, -OC3H7, -OC4H9, -00CR5 (where R5 = alkyl radical from 1 to 5 carbon atoms), -NH2 / -NH-CO-R5; ey = 0, 1. The polymers containing oxidizable galactose-type alcohol configuration can be galactomannan gums or their ether derivatives, arabinogalactan gums or their ether derivatives, other gums or their ether derivatives, galactoglucomannan hemicelluloses or their ether derivatives and modified polymers enzymatic or synthetically Preferred galactomannan gums are guar, carob, tara and fenugreek. Preferred arabinogalactan gums are gum arabic, larch and tragacanth. Enzymatically or synthetically preferred modified polymers are polysaccharides deficient in galactose, polyacrylamides, polyacrylates, polyamides, polyvinyl alcohol and polyvinyl acetate. Particular preference is given to these polymers, starch and polyacrylates. The phrase "galactose deficient" as used in the present application, means that the oxidizable galactose type of polymer containing alcohol configuration, refers to containing less than 20% oxidizable galactose-type alcohol configuration based on the weight of the polymer that contains alcohol configuration of oxidizable galactose type. Other preferred gums are carubine, lichen, tamarind and potato galac. Particularly preferred are polymers containing an oxidizable galactose-type alcohol configuration, guar gum and its ether derivatives such as cationic, anionic, amphoteric, hydroxypropyl, dihydroxypropyl and hydroxyethyl guar. Synthetically or enzymatically modified polymers can be obtained by connecting the oxidizable galactose-type alcohol configuration to polymers or by polymerizing a monomer containing an oxidizable galactose-type alcohol configuration. The polymer component containing alcohol configuration of the oxidized galactose type of the present invention has at least about 5 mol% of its oxidizable galactose type of alcohol configuration oxidized in aldehyde. Preferably, at least about 25 mol% and more preferably at least about 50 mol% of this alcohol has been oxidized into aldehyde. The polymer containing oxidizable galactose-type alcohol configuration used for oxidation may be over a wide range of molecular weight. It may be high molecular weight, or alternatively it may be a depolymerized polymer (of reduced viscosity). In general, the lower limit of the weight average molecular weight of the oxidizable galactose-type alcohol containing polymer can be about 5,000. The upper limit of the weight average molecular weight of the oxidizable galactose-type alcohol containing polymer can be about 5,000,000. Preferably, the molecular weight range as indicated by the Brookfield viscosity at room temperature is at least about 15 cps to 2 weight percent in solution in water, more preferably at least about 100 cps to 1 weight percent in solution in water Preferably, the Brookfield viscosity at room temperature can be up to about 10,000 cps, more preferably up to about 6,000 cps to weight percent in solution in water, (measured in Brookfield LVT viscometer with a small sample adapter, 25 ° C, spindle 31, speed 3 rpm). Guar is preferred as the polymer containing oxidizable galactose-type alcohol configuration, for use in the present invention. The present application relates to guar gum specifically in certain cases, however the person of ordinary skill in the art will recognize that these teachings apply the polymer containing oxidizable galactose-type alcohol configuration, in general. Galactose oxidase (EC 1.1.3.9) is a copper oxidase that converts the oxidizable galactose-type alcohol configuration into the corresponding aldehyde group (thus producing oxidized galactose) by reducing oxygen in hydrogen peroxide. The copper must be in the correct oxidation state (Cu2 +) to perform this oxidation and the copper ion must be retained in the galactose oxidase. If the galactose oxidase solution is stored anaerobically with any oxidizable substrate, it may become inactive. Galactose oxidase can be reactivated by oxidizing copper with reagents such as potassium ferricyanide. Another way to oxidize copper in galactose oxidase would be by electrochemical oxidation. Galactose oxidase can be obtained by any convenient form, for example when fermenting various wild type and cloned fungi, but usually obtained from Fusarium spp (NRRL 2903). You can also obtain cultures from the American Type Culture Collection (American Tupe Culture Collection) under Dactilium dendroides ATCC 46032 and successfully fermented under the procedure of Tressel and Kosman, Methods in Enzymology, Vol. 89 (1982), p. 163-172. The gene for the active forms of the enzyme has been expressed in E. coli and Aspergillus and this development can lead to more stable and active forms of the enzyme, as well as much higher production levels. The improved gene or forms will also be expressed in plants that can be harvested to give higher levels of enzyme without the threat of destruction of enzyme by proteases in a regenerating broth. The enzyme can also be expressed by other organisms including: Gibberella fujikoroi, Fusarium graminearum and Bettraniella porticensis. The treatment of the oxidizable galactose-type alcohol-containing polymer with galactose oxidase and catalase is the subject of accompanying Application No. 09 / 001,789, filed on December 31, 1997 (File of Hercules No. PCH 5484, "Oxidation in Solid State of Oxidizable Galactose Type of Alcohol Configuration Containing Polymers "(Oxidation in Solid State of Polymers Containing Oxidatable Galactose Type Alcohol Configuration) by RL Brady, RT Leibfried and TT Nguyen), the description of which is incorporated herein by reference. Preferably, the oxidation of polymer containing oxidizable galactose-type alcohol configuration with galactose oxidase is carried out in the presence of means for decomposing the hydrogen peroxide generated during the conversion of the oxidizable galactose-type alcohol configuration into aldehyde. Preferably, the means for decomposing hydrogen peroxide comprises catalase. Other metal complexes and compounds can also be used to decompose the hydrogen peroxide formed in the oxidation reaction. Chemicals that achieve redox chemistry with hydrogen peroxide are iron complexes, for example with polyamines (notably triethylenetetramine) and persulfates. The polymer containing oxidizable galactose-type alcohol configuration can be oxidized in solid form, in the form of sludge or in solution. The oxidation can be carried out enzymatically by galactose oxidase. Preferably cationic or anionic or amphoteric guar guar which has been oxidized by galactose oxidase and catalase, is used in the present invention. Galactose oxidase can be applied to solid forms, of mud or in solution of guar products; for example shredded, powdered, flake and nodule shapes of neutral, cationic, anionic or amphoteric guar. Guar derivatives such as those containing hydroxypropyl groups can also be employed.

The lower limit of the oxidation promoting chemical may be about 0.1%, based on the weight of the oxidizable galactose-type alcohol-containing polymer. Preferably, the lower limit of the chemical promoter of oxidation is 0.5% and in particular is 1%. The upper limit of the oxidation promoter chemical may be about 5%, based on the weight of polymer containing oxidizable galactose-type alcohol configuration, preferably about 3% and particularly preferably about 2%. When the oxidizable galactose-type alcohol-containing polymer is contacted with galactose oxidase in aqueous medium, the lower limit of the oxidizable galactose-type alcohol-containing polymer configuration can be about 0.001%, preferably about 0.2% and particularly about 8% . In this case, the upper limit of the oxidizable galactose-type alcohol containing polymer configuration may be about 50%, preferably about 30% and in particular about 20%, all based on the weight of the composition. When the polymer containing oxidizable solid galactose type alcohol configuration is contacted with solid galactose oxidase, the lower limit of the oxidizable galactose type alcohol configuration can be about 50% based on the weight of the composition. Preferably, the lower limit is about 70% and more preferably about 85%. When polymer containing oxidizable solid galactose-type alcohol configuration is contacted with galactose oxidase, the upper limit of the oxidizable galactose-type alcohol-containing polymer configuration can be about 100% based on the weight of the composition. Preferably it can be about 98% and in particular about 95%. An International Unit (IU) of galactose oxidase will convert a micro-equivalent of the polymer containing oxidizable galactose-type alcohol configuration into aldehyde per minute at 25 ° C and pH 7.0. The unit can be measured by coupled assays where the by-product H202 is used by peroxidases to oxidize bleacher precursors, releasing a chromophore. The production of the chromophore is measured by light absorbance at a wavelength appropriate to the dye used (o-tolidine, 425 nm; o-dianisidine, 436 nm; 2, 21-azinobis (3-ethylbenzothiazoline-6-sulfonic acid), diammonium salt (ABTS), 405 nm). The method that uses the ABTS dye is used to determine the International Units (IU).

The lower limit of the galactose oxidase may be about 10 IU per gram of polymer containing oxidizable galactose-type alcohol configuration. Preferably, the lower limit is about 25% and more preferably about 35 IU per gram of polymer containing oxidizable galactose-type alcohol configuration. The upper limit of galactose oxidase may be about 3,000 IU per gram of polymer containing oxidizable galactose-type alcohol configuration, preferably about 2,000 and in particular about 1,000 IU per gram of polymer containing oxidizable galactose-type alcohol configuration. The lower limit of catalase may be about 1, preferably about 50, and in particular about 100 IU catalase / lU of galactose oxidase. The upper limit of catalase may be about 10,000, preferably 5,000 and in particular about 1,000 IU catalase / lU of galactose oxidase. One (1) IU of catalase will convert a micromole (10 ~ 6 mol) of hydrogen peroxide into water and oxygen per minute at pH 7.0 and 25 ° C. In the examples, test sheets were made in a Noble and Wood machine (Noble &Wood Machine Co., Hoosick Falls, N.Y.) using standard hard water at a controlled pH of 7.5. Standard hard water (50 ppm alkalinity and 100 ppm hardness) is prepared by mixing deionized water with CaCl2 and NaHCO3. The pH control is achieved using NaOH or H2S04. Leached kraft pulp is beaten to 455 Canadian Standard refined at a consistency of 2.5% by weight. The whipped pulp is added to the dispenser at a controlled level (depending on the final desired base weight) and diluted to 18 liters with standard hard water. For 36.32 kg / 278.70 m2 (80 pounds / 3,000 square feet) basis weight, 4000 ml of pulp mixture was used. Chemical additions and pH adjustments were made to the dispenser as desired and with continuous mixing. A clean and humid 100 mesh screen was placed in the open drum box or frame, which was then closed. Standard hard water and 920 ml of pulp mix from the dispenser were then added to the frame box and passed quickly. The water was then discharged from the box and the sheet removed. The sheet was wet pressed between felts with press weights adjusted to give a solids content of 33-34%. The sheet and sieve were then placed in a drum dryer that was adjusted to a temperature of 108.9-111.1 ° C (228-232 ° F) and yield time of 50-100 seconds, depending on basis weight. The moisture content of the final leaf was 3-5%. Five minimum sheets were tested for each experimental game.

The tensile test was performed on the test sheets according to the TAPPI Method T 494 om-88 ("TAPPI Test Methods" TAPPI Press, Atlanta, GA 1996). The aldehyde content was measured by iodometric titration or DNS method. The iodometric assay for aldehyde (I2 + CHO? COOH + 21") uses titration of excess I2 with sodium thiosulfate.The DNS @ method uses 3,5-dinitrosalicylic acid to oxidize the aldehyde followed by colorimetric titration as described by Ghose in Puré &Application Chem., 59, pp. 257 (1987) The viscosity was measured with the Brookfield LVT Viscometer equipped with a constant temperature bath (25 ° C) small sample adapter, spindle 31 and speed 3 rpm The scope of this invention as claimed is not limited to the following examples, which are given by way of illustration only All parts and percentages are given by weight unless otherwise indicated.

This example shows the effect of various chemical oxidation promoters on the oxidation of shredded guar. Shredded Guar is oxidized to 0.2% in deionized water by adding 1% of various chemical promoters of oxidation, 540 IU of galactose oxidase (Sigma G7400) / g of guar and 1852 IU of catalase (Sigma C40) / IU of galactose oxidase. The resulting solutions were stirred for 3 days at room temperature. Table I shows the oxidase-promoting chemicals and the results of the iodometric titration for aldehyde at the end of 3 days. A theoretical integral reaction would give 2.06 meq / g for the aldehyde. All the oxidation promoting chemicals help the oxidation in such a way that a higher level of aldehyde content is obtained. Table I - Oxidation of guar with chemical promoter of oxidation. * d Zeneca, Wilmington, Delaware EXAMPLE 2 This example shows the effect of higher levels of Proxel GXL in the oxidation of guar. To a 0.2% aqueous solution of Supercol U neutral guar powder is added to 1% or 10% (based on guar) of 1,2-benzisothiazolin-3-one. Catalase (Sigma C40) is added to 1852 IU / IU of galactose oxidase. Galactose oxidase is added to 108 IU / g of guar. The solutions were stirred for 2 days, after which the solutions were analyzed for aldehyde contents. Table II shows the% conversion to aldehyde, as measured by the DNS method. The use of 10% Proxel GXL resulted in a great improvement in the conversion of aldehyde. Table II - Oxidation of guar guar Supercol U with Proxel GXL EXAMPLE 3 This example shows the improvement in paper strength that can be achieved by using a chemical promoter of oxidation in the oxidation process. Guar shredded neutral is used at 0.2% in water. Proxel GXL is added as indicated to give a 1% 1,2-benzisothiazolin-3-one level based on guar. Catalase (Sigma G7400) at 1852 IU / IU of galactose oxidase (Sigma G7400) at 540 IU / g of guar are added to the solutions. Samples were mixed overnight before titration and paper production. Test sheets were made at a base of 36.32 kg / 278.70 cm2 (80 pounds / 3,000 square feet) with kraft pulp leaching and a level of oxidized guar of 1% based on dry weight of the pulp. Table III shows the results for aldehyde level (iodometric titration) and dry paper tensile strength for oxidized guar with and without Proxel GXL. Using Proxel GXL results in a much higher oxidation level and greatly improved paper properties. Table III - Effect of Proxel GXL on Aldehyde Level and Dry Resistance

Claims (19)

1. CLAIMS 1. A process for the oxidation of an aldehyde-oxidizable galactose-type alcohol configuration in a polymer containing oxidizable galactose-type alcohol configuration, which comprises providing the polymer containing oxidizable galactose-type alcohol configuration and galactose oxidase and the chemical oxidation promoter and contact them, where the oxidizable galactose alcohol type configuration is described by the following chemical structures: p wherein R 1 is an alkyl group of the formula C (n) H (2n + 1) wherein n is 0 to 20; z is 0 or 1; wherein R2 is a linking group composed of alkylene, an aromatic alkylene or alkylene ether, or an alkylene ester, or an alkylene amide, or a diradical alkylene urethane wherein the linking group has a total carbon number from 2 to 20; wherein R3 is -H, -OH, -0CH3, -OC2H5, -OC3H7, -OC4H9, -00CR5 (wherein R5 is an alkyl radical of 1 to 5 carbon atoms), -NH2, -NH-C0-R5; e y is 0 or 1; and wherein the polymers containing oxidizable galactose-type alcohol configuration are selected from the group consisting of galactomannan gums or their ether derivatives, arabinogalactan gums or their ether derivatives, other gums or their ether derivatives, hemicelluloses galactoglucomannan or their ether and polysaccharide derivatives, polyacrylamides, polyacrylates, polyamides, polyvinyl alcohol and polyvinyl acetate deficient in galactose.
2. 2. The process according to claim 1, characterized in that the oxidation promoter chemical is selected from the group consisting of organic carboxylate compounds, organic heterocyclic compounds and quaternary amine compounds.
3. The process according to claim 1, characterized in that the lower limit of the polymer containing oxidizable galactose-type alcohol configuration is approximately 0.001% based on the total weight of polymers containing oxidizable galactose-type alcohol configuration, chemical promoter of oxidation and galactose oxidase and the lower limit of galactose oxidase is approximately 10 IU / g of polymers containing oxidizable galactose-type alcohol configuration and the lower limit of chemical promoter of oxidation is approximately 0.1% based on the total weight of polymers containing oxidizable galactose-type alcohol, galactose oxidase, and oxidizing promoter chemical configuration.
4. 4. The process according to claim 1, characterized in that the upper limit of polymer containing oxidizable galactose-type alcohol configuration is about 99% based on the total weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and chemical oxidation promoter, the upper limit of galactose oxidase is approximately 3,000 IU / g of polymer containing oxidizable galactose-type alcohol configuration and the upper limit of chemical promoter of oxidation is approximately 5% based on total polymer weight containing oxidizable galactose-type alcohol configuration, galactose oxidase and oxidizing promoter chemical.
5. The process according to claim 1, characterized in that it comprises the addition of means that can decompose hydrogen peroxide, wherein the oxidation of the alcohol-type galactose-oxidizable-aldehyde-like configuration in the polymer containing galactose-type alcohol configuration oxidizable, it is carried out in the presence of the means that can decompose hydrogen peroxide.
6. The process according to claim 5, characterized in that the means for decomposing the hydrogen peroxide are chosen from the group consisting of catalase, iron complexes and persulfates.
7. The process according to claim 5, characterized in that the means for decomposing hydrogen peroxide comprise catalase in an amount of at least about 1 IU of catalase per unit of galactose oxidase.
8. 8. The method according to claim 5, characterized in that the means for decomposing the hydrogen peroxide comprises catalase in an amount of up to about 10,000 IU of catalase per unit of galactose oxidase.
9. The process according to claim 2, characterized in that the polymer containing oxidizable galactose-type alcohol configuration is selected from the group consisting of galactomannan gums or their ether derivatives, arabinogalactan gums or their ether derivatives, other gums or their ether derivatives , galactoglucomannan hemicelluloses or their ether derivatives and synthetically or enzymatically modified polymer, the lower limit polymer contains alcohol configuration galactose type oxidizable is about 0.001% based on the total weight of the polymer containing alcoholic configuration oxidizable galactose type, galactose oxidase and oxidation promoter chemical, the lower limit of galactose oxidase is about 10 IU / g of polymer containing oxidizable galactose-type alcohol configuration and the lower limit of oxidation promoting chemical is about 0.1% based on the total weight of polymer containing alcohol configuration of the oxidizable galactose type, galactose oxidase and oxidation promoter chemical, the upper limit of polymer containing alcohol configuration galactose type oxidizable is about 99% based on the total weight of the polymer containing alcohol configuration of the oxidizable galactose type, galactose oxidase and product chemical oxidation promoter, the upper limit of galactose oxidase is about 3,000 IU / g of polymer containing alcoholic configuration oxidizable galactose type and the upper limit chemical oxidation promoter is about 5% based on the weight total polymer contains alcohol configuration oxidizable galactose type, galactose oxidase and product chemical oxidation promoter, means to decompose hydrogen peroxide is added and the means to decompose hydrogen peroxide are catalase in an amount of at least about 1 IU per IU of galactose oxidase and up to about 10,000 IU per unit of galactose oxidase.
10. The process according to claim 9, characterized in that the organic carboxylate compound is selected from the group consisting of sorbic acid, salicylic acid, benzoic acid, tonic acid, phthalic acid and their corresponding salts, the organic heterocyclic compound is selected from the group consisting of group consisting of 1, 2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one and the quaternary amine compound is selected from the group consisting of cetyl trimethyl ammonium bromide and epoxy quaternary amines.
11. The method according to claim 9, characterized in that the galactomannan gum is selected from the group consisting of guar, carob, tara and fenugreek gum, or its ether derivatives; the arabinogalactan gum is selected from the group consisting of arabic, larch and tragacanth, or its ether derivatives, the other gum is selected from the group consisting of carubine, lichen and galactane gum of potato or its ether derivatives and the modified polymer in synthetic form or enzymatic, is selected from the group consisting of polysaccharides deficient in galactose, polyacrylates, polyacrylamides, polyvinyl alcohol and polyvinyl acetate.
12. The process according to claim 9, characterized in that the lower limit of polymer containing oxidizable galactose-type alcohol configuration is about 0.2% based on the total weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and chemical oxidation promoter, the lower limit of galactose oxidase is about 25 IU / g of polymer containing oxidizable galactose-type alcohol configuration, the lower limit of chemical promoter of oxidation is about 0.5% based on the total weight of the polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and the oxidation promoter chemical and the lower limit of catalase is approximately 50 IU per unit of galactose oxidase.
13. The process according to claim 9, characterized in that the upper limit of polymer containing oxidizable galactose-type alcohol configuration is about 98% based on the total weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and chemical oxidation promoter, the upper limit of galactose oxidase is approximately 2,000 IU / g of polymer containing oxidizable galactose-type alcohol configuration, the upper limit of oxidation-promoting chemical is approximately 3% based on total polymer weight containing oxidizable galactose-type alcohol configuration, galactose oxidase and oxidation-promoting chemical and the upper limit of catalase is approximately 5,000 IU per IU of galactose oxidase.
14. The process according to claim 9, characterized in that the oxidation promoter chemical is 1,2-benzisothiazolin-3-one.
15. 15. The process according to claim 9, characterized in that the polymer containing oxidizable galactose-type alcohol configuration is selected from the group consisting of guar gum and its ether derivatives.
16. The process according to claim 9, characterized in that the lower limit of polymer containing oxidizable galactose-type alcohol configuration is about 8%, based on the total weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and oxidation promoter chemical, the lower limit of galactose oxidase is about 35 IU / g of polymer containing oxidizable galactose-type alcohol configuration and the lower limit of oxidation-promoting chemical is about 1% based on the total weight of guar, galactose oxidase and oxidation promoter chemical and the lower limit of catalase is approximately 100 IU per IU of galactose oxidase.
17. 17. The process according to claim 9, characterized in that the upper limit of polymer containing oxidizable galactose-type alcohol configuration is about 95%, based on the total weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and chemical oxidation promoter, the upper limit of galactose oxidase is about 1000 IU / g of polymer containing oxidizable galactose-type alcohol configuration, the upper limit of chemical promoter of oxidation is about 2%, based on the weight of polymer containing oxidizable galactose-type alcohol configuration, galactose oxidase and oxidation-promoting chemical, and the upper limit of catalase is about 1,000 IU per IU of galatose oxidase.
18. 18. The process according to claim 1, characterized in that the polymer containing oxidizable galactose-type alcohol configuration is in the solid state.
19. 19. The process according to claim 1, characterized in that the configuration of oxidizable galactose-type alcohol containing polymer is in solution.