MXPA00006813A - Adhesives and resins, and processes for their production - Google Patents

Abstract

Additives for addition to starting materials in cellulose based products for imparting strength and crepe. Additives for use in paper production which impart strength to the product and which can be used in creping adhesives. Enzyme activated resins for use in paper production. Enzyme-activated adhesives for use in paper production. Paper products comprising the aforementioned additives or resins. Methods for imparting strength or crepe to paper products.

Description

ADHESIVES AND RESINS, AND PROCEDURES FOR THEIR PRODUCTION BACKGROUND OF THE INVENTION 1. FIELD OF THE INVENTION This invention relates to adhesives and resins and to processes for their preparation. More particularly, this invention relates to resin compositions and adhesives that can be used especially in the manufacture of cellulose-based products, and more particularly paper products. The resins and adhesives of the present invention are produced by the combination of a water-soluble polymeric material comprising a nucleophile, a phenolic material and a component which serves to activate the phenolic material to render it reactive with the polymer nucleophile. 2. BACKGROUND OF THE INVENTION AND RELATED INFORMATION Many compositions for resins and adhesives are known in the art. Most of these compositions, however, include components that can be considered as environmentally "unfriendly", or even toxic. In addition, some existing adhesives and resins are, in themselves, environmentally "unfriendly" or toxic. That is, there is therefore a need for resins and adhesives that are non-toxic and that are produced from non-toxic components. The papermaking industry has had concerns for a long time in the sense of increasing the strength of wet paper. The paper constructed without additional reinforcing agents often melts when rewetting. A paper that maintains its strength when wetted is desirable in many applications, including toilet paper, paper towels, napkins, and the like. In addition, additives that increase the wet paper strength also frequently increase the dry strength of such paper. Many of the additives known in the art that can be used to increase the wet strength of paper are based on the chemical structure of the cellulose found there. Cellulose found in paper products often has carboxylate and hydroxyl portions exposed along its chain. Through the use of reactive additives, crosslinks can be formed between these portions in the cellulose chains in the paper, thereby increasing the strength of the paper. Alternatively, some additives do not react with cellulose, but increase the strength of the paper through other unknown mechanisms. In any case, the additives that are usually chosen due to their ability to adhere to the pulp and their ability to form a structural network that can suppress the swelling of cellulose fibers thus inhibiting the separation of fiber-fiber contacts when moistened . Some of the above wet strength resins were condensation products of urea and formaldehyde, with the addition of polyamines to make the resin cationic. Such resins appear to provide only a wet strength through self-crosslinking. However, resins formed from melamine and formaldehyde appear to directly cross-link cellulose. Polyamide and epichlorohydrin form resins that react with the carboxylate groups of cellulose. At higher concentrations, the polyamide / epichlorohydrin resins appear to form crosslinks as well. Other resins include resins formed by epoxides, which react analogously and also with the hydroxyl groups of cellulose, and those formed from aldehydes, which appear to crosslink cellulose reversibly through hemiacetal bonds, and self-crosslinking in Amide groups. Comments on wet strength resins and their mechanisms appear in "Th.e Mechanism of Wet-Strength.

Paper: A Review "(The mechanism of the development of resistance in the wet state on paper: a review) by Herbert H. ESPY, Tappi Journal, Vol. 78, No. 4, pages 90-97 (April 1995) as well as in "Chemistry of Paper Wet-Strength I. A Survey of Mechanisms of Wet-Strength Development" (Resistance chemistry in the wet state of paper I. A perspective on the mechanisms of resistance development in the wet state), by Lars WESTFELT, Cellulose Chemistry and Technology, Vol. 13, pages 813-825 (1979). According to ESPY, a resistance resin in the wet state must have four fundamental attributes: these resins must first be water soluble, allowing a regular dispersion and an effective distribution in the cellulose fibers. In addition, the resins must have a certain inherent cationic or other character, which facilitates their adsorption on anionic fibers in the pulp. The resins must also be polymeric with high molecular weight polymers apparently forming stronger bonds. Finally, the resins must be reactive, a quality that allows them to be crosslinked both with themselves and with cellulose on paper. Resins comparable to those used to increase paper strength also find application in creping adhesives. In the manufacture of specific paper products such as for example paper tissues for the face, toilet paper, or paper towel, the paper tissue is subjected to a process of creping in order to give the paper product desired characteristics as for example, softness and volume. Typically, the creping process includes the adhesion of the fabric, a cellulose fabric in the case of paper, on a cylinder of rotating creping like for example that used in a Yankee dryer. The adhered tissue is then detached with a blade. The impact of the tissue against the blade disrupts fiber-fiber bonds within the tissue, causing the tissue to wrinkle or crumple. The magnitude of the creping action depends on several factors, including the degree of adhesion between the fabric and the surface of the creping cylinder. Greater adhesion between the fabric and the cylinder results in increased softness, even though generally with a certain loss of strength. In order to increase adhesion, a creping adhesive is often used. In addition, creping adhesives can also reduce wear on a dryer surface, provide lubrication between a blade and a dryer surface, reduce chemical corrosion and control the magnitude of the creping. Ideally, a creping adhesive adheres to the sheet sufficiently tightly on the drum to produce a good creping, providing absorbency and softness to the final product, with a minimum loss of paper strength. However, if the adhesion of the fabric on the dryer drum is too strong, the sheet can even "stick", that is, pass under the blade, and wrap around the dryer drum. On the other hand, if the adhesion is too weak, the sheet will rise too easily and will present little crease. Examples of creping agents appear in U.S. Patent Nos. 5,187,219 to FURMAN, 5,246, 544, to HOLLENBERG et al., 5,388,807 to ESPY et al., And 5,374,334 to SOMNESE et al. Other examples of creping agents appear in U.S. Patent Nos. 4,684,439, 4,788,243, 4,501,640 and 4,528,316, all from SOERENS. The present invention advances the field of resin compositions for use in papermaking. Many of the resin compositions known in the art are toxic to animals, or they can be harmful to the environment. The present invention offers an "environmentally friendly" alternative to known adhesives and resins. Modalities of the present invention are essentially chemically benign, employing a biocatalytic process to induce crosslinking in a paper product. The use of a biocatalytic process to induce the polymerization of phenols is known in the art. DORDICK et al., describes the production of polymers produced by the coupling of phenols catalyzed by sour horseradish peroxidase in "Polymerization of Phenols Catalyzed by Peroxidase in Nonaqueus Media" (Polymerization of phenols catalyzed by peroxidase in non-aqueous media), Biotechnology and Bioengineering, vol. 30, pages 31-36 (1987). POKORA et al., Describe the use of such catalytic processes in the production of developing resins in US Patent No. 4,647,952 ('952) and broad processes in Patents Nos. 4,900,671 (' 671) and 5,153,298 ('298). POKORA also describes the use of polyphenol resins in paper production in US Patent No. 5,110,740 ('740), DORDICK et al., And POKORA et al. The use of enzymes to catalyze the polymerization of phenols in monolayers is described by AKKARA et al., In US Patent No. 5,143,828 and in "Synthesis and Characterization of Polyphenols from Peroxidase-Catalyzed Reactions" (Synthesis and characterization of polyphenols from reactions catalyzed by peroxidase), Enzyme Microb. Technol., Vol. 13, page 521 (June 1991), as well as in BRUNO et al., "Enzyme Catalyzed 2-D Polymerization of Phenol Derivatives on a Langmuir-Blodgett Trough " (2-D polymerization catalyzed by enzymes of phenol derivatives in the Langmuir-Blodgett channel), Polymer Reprints, vol. 32, no. 1, pages 232-233 (1991). The enzyme-catalyzed formation of polyesters is described in the patent. North American No. 5,147,791, by MORROW et al. The present invention offers adhesive compositions, resins and novel and "environmentally friendly" methods. Such compositions are especially useful in the papermaking process. The present invention focuses on processes for the production of adhesives and resins, and products made with them. The present invention focuses on processes for the production of resins and adhesives activated by oxidation, and products made by them. COMPENDIUM OF THE INVENTION The present invention focuses on the production of resins and adhesives activated by enzymes and the products made by them. The present invention focuses on methods for the production of adhesive compositions and resin compositions for use in the manufacture of paper, and the products made therefrom. The present invention focuses on methods for supplying materials that can be added to the wet end of paper production, increasing the strength of a paper product. The present invention focuses on the production of articles that employ resins and activated adhesives, including resins and adhesives activated by oxidation. The present invention focuses on methods for providing materials that are chemically benign for the wet end addition of paper production in order to increase the strength of a paper product. The present invention focuses on the production of resins and adhesives, formed of chemically benign materials, which can be used in papermaking processes.

The present invention focuses on the production of a paper product reinforced by a resin formed by the addition of chemically benign materials at the wet end of production. The present invention focuses on the production of an adhesive for use in paper creping. The present invention focuses on the production of a paper product that has been formed through the use of said creping adhesive. These and other aspects of the present invention are achieved by the provision of a composition comprising (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component. Another way to describe the present invention is that a composition is provided comprising (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) a compound capable of converting the compound phenolic in a quinone compound.

Component (c) can be a single component, or a mixture of components, and preferably comprises the aforementioned oxidizing component. For example, the oxidizing component may comprise a member selected from the group consisting of potassium dichromate, potassium permanganate, and mixtures thereof, or the oxidizing component may comprise a mixture of components such as, for example, hydrogen peroxide and a material such as a metal catalyst that can cause hydrogen peroxide to release oxygen. These metal catalysts include, but are not limited to, ferric chloride, cobalt chloride, cupric chloride, and mixtures thereof. In addition, the oxidizing component can comprise an enzyme system. The enzyme system may comprise at least one oxidation enzyme. For example, the oxidation enzyme may comprise an oxidase, which preferably comprises a member selected from the group consisting of laccase, tyrosinase, polyphenoloxidase, and mixtures thereof. Alternatively, the oxidation enzyme may comprise a peroxidase, which preferably comprises a member selected from the group consisting of peroxidases of sour radish, soy peroxidases, haloperoxidases, lactoperoxidases, bacterial peroxidases, and mixtures thereof. More preferably, the peroxidase comprises horseradish peroxidase.

When the enzyme system is used, the reaction can occur in the presence of atmospheric air. However, the enzyme system also preferably comprises at least one source of oxygen. The oxygen source may comprise a member selected from the group consisting of perborates, persulfates, peroxides, and mixtures thereof. In additional embodiments, the enzyme system may comprise an alcohol oxidase and its corresponding alcohol, such as ethanol and ethanol oxidase. Alternatively, the enzyme system may comprise sugar oxidase and its corresponding sugar, such as glucose and glucose or galactose oxidase and galactose oxidase. The oxidizing component may comprise an enzyme system in combination with another oxidant component such as for example an enzyme system in combination with potassium permanganate. In preferred embodiments, the nucleophilic polymer comprises the following general structure: FORMULA I where n is an integer greater than 2, and R1 comprises a hydrocarbyl group. Preferably, the hydrocarbyl group comprises from about 2 to about 20 carbon atoms. Preferably, the hydrocarbyl group comprises from about 6 to about 10 carbon atoms, and more preferably comprises about 6 carbon atoms. Preferably, the hydrocarbyl group comprises an alkyl group having from about 2 to about 20 carbon atoms. Preferably, the alkyl group comprises from about 6 to about 10 carbon atoms, and more preferably comprises about 6 carbon atoms. In formula I, preferably, n is from about 10 to about 200. More preferably n is from about 50 to about 100, and n is more preferably from about 50 to about 80. The nucleophilic polymer may comprise a polyalkylamine or a polycyclic alkylamine. In preferred alternative embodiments, the nucleophilic polymer comprises the following general structure: FORMULA II where n is an integer greater than 2, X comprises a nucleophile, and Y comprises a group that allows solubility in water. In formula II, the nucleophile preferably comprises a member selected from the group consisting of -NH2, -NHR2, -SH, -S00", ArO", and -PR22, wherein R2 comprises a hydrocarbyl group comprising about 1 to about 12 carbon atoms, and Ar comprises a benzenoid, substituted benzenoid or naphthalenoid group. Preferably, the hydrocarbyl group comprises a benzenoid group or an alkyl group comprising from about 1 to about 12 carbon atoms. In formula II, the group that allows solubility in water preferably comprises a cationic, anionic, amphoteric group, or that participates in the hydrogen bond. In formula II, the group that allows solubility in water preferably comprises a member selected from the group consisting of -N3 (R3) 3, -COO ", -0S03 ~, -OP03", -N + (R3) 2 -R3'-C00 ~, -OH, -CONH2, and -B (OH) 2, wherein R3 and R3 'each comprise a hydrocarbyl group having from about 12 carbon atoms, such as, for example, a portion cyclic or a straight string. The nucleophilic polymer may comprise a member selected from the group consisting of polyvinyl alcohols, polyvinyl sulfones, polyacrylamides, polyacrylates, polyacrylonitriles, polyethers, polyesters, polyaryl ethers, polyarylsulphones, polyamides, polyimides, polyalkanes, polyaminoalkanes, polyphenyls, and mixtures thereof. The nucleophilic polymer can be formed through several processes, including a process comprising at least one addition reaction followed by reduction. Preferably, the nucleophilic polymer is formed by a reaction comprising a member selected from the group consisting of nucleophilic displacement, amination, nitration, sulfonation, phosphorylation, and combinations thereof. The nucleophilic polymer can comprise a member selected from the group consisting of -NH2, -NHR, -SH, -SOO ", -PR42, -ArO", and mixtures thereof, wherein R4 comprises a hydrocarbyl group comprising between about 1 and about 12 carbon atoms, and Ar comprises a benzenoid or naphthalenoid group. Preferably, the hydrocarbyl group comprises a benzenoid group or n alkyl group comprising from about 1 to about 12 carbon atoms. The nucleophilic polymer can be formed by the polymerization of a monomer comprising a nucleophile. In preferred embodiments, the nucleophilic polymer comprises a polyvinylamine alcohol preferably comprising from about 0.01% to about 100% amine. More preferably, the polyvinylamine alcohol comprises from about 10% to about 50% amine, and more preferably comprises about 12% amine. The phenolic compound may comprise phenols or polyphenols. In preferred embodiments, the phenolic material comprises the following general chemical structure: FORMULA III where Y comprises -H or -OH and X comprises -OR5, -R5, -Ar, or -NR5R5, where R5 and R5 comprise H or a hydrocarbyl group comprising from about 1 to about 12 carbon atoms and Ar it comprises a benzenoid or naphthalenoid group. Preferably, the hydrocarbyl group comprises an alkyl group comprising from about 1 to about 12 carbon atoms. The phenolic compound may comprise a member selected from the group consisting of polyphenols, substituted polyphenols, substituted phenols, catechols, substituted catechols, hydroquinones, substituted hydroquinones, aminophenols, substituted aminophenols, and mixtures thereof. Preferably, the phenolic compound comprises 1,2-benzenediol. In preferred alternative embodiments, the phenolic compound comprises 1,4-benzenediol. The phenolic compound may comprise a polyphenolic compound, preferably comprising a member selected from the group consisting of phloroglucinol, lignins, catechins, flavonoids, and mixtures thereof. Preferably, a polyphenolic compound of this type is a compound that occurs in nature. Alternatively, the polyphenolic compound may comprise a member selected from the group consisting of polyphenols, resoles, novolak, calixerenes, and mixtures thereof. Preferably, said polyphenolic compound is a synthetic compound. In preferred embodiments, the compositions of the present invention may be combined with cellulosic material, which may comprise paper pulp. These and other aspects of the present invention are further achieved by providing a resin to provide resistance to a paper product, produced by the combination of (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a compound phenolic, and (c) an oxidizing component. Alternatively, component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. In preferred embodiments, the oxidizing component may comprise an enzyme system. This resin can be used in combination with a cellulosic material, such as for example fiber mat, woven fabric, box, board, sheet, wood, particle board, braided wood board, or laminates. These and other aspects of the present invention are achieved by providing a paper product comprising such a resin. These and other aspects of the present invention are further achieved by providing a creping adhesive, produced by the combination of (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component. In another form of describing the invention, component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. In preferred embodiments, the oxidizing component comprises an enzyme system. The creping adhesive can be used in combination with cellulosic material such as for example fiber mat, woven fabric, box, board, wood, sheets, particle board, braided or laminated wooden boards. These and other aspects of the present invention are achieved by providing a paper product comprising said creping adhesive. These and other aspects of the present invention are achieved by providing a method for increasing the strength of a paper product, comprising the addition of (a) a water soluble polymeric material comprising at least one nucleophilic polymer, (b) a compound phenolic, and (c) an oxidizing component, to the paper pulp. In another form of describing the invention, component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. In preferred embodiments, the oxidizing component comprises an enzyme system. These and other aspects of the present invention are further achieved by providing a method for giving resistance to a cellulose-based product, comprising the combination of (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component, to cellulosic starting materials. In another form of describing the invention, a component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. In preferred embodiments, the oxidizing component comprises an enzyme system. These and other aspects of the invention are further achieved by providing a set of elements, comprising a polymeric water-soluble material comprising at least one nucleophilic polymer, a phenolic compound, and a component capable of converting the phenolic compound to a quinone compound. . In another form of describing the invention, the component capable of converting the phenolic compound into a quinone compound comprises an oxidizing component. In some embodiments, the set of elements comprises an oxygen source. In another embodiment, the set of elements does not include any oxygen source. DEFINITIONS Some terms and expressions are used repeatedly throughout the specification and claims of this patent. The following definitions of these terms are offered in order to provide consistency and clarity. Base weight - the total weight of a 3000 square foot sheet of paper. Canadian standard of freedom - a measure of the speed of drainage of the pulp. Described in Pulp and Paper, volume 1, James P. Casey, Interscience Publishers, Inc., New York, 1952, page 341. Kraft - method of forming sulphate pulp, in accordance with that described in Pulp and Paper, volume 1 , James P. Casey, Interscience Publishers, Inc., New York, 1952, page 159. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES OF THE INVENTION The present invention focuses on adhesives and resins that can be used in various applications. In preferred embodiments, the present invention focuses on crosslinking systems for use, additives in the papermaking process. In a preferred embodiment, the present invention focuses on methods for improving the creping process in paper production. In other preferred embodiments, the present invention also focuses on methods for improving the wet strength and dry strength of a paper product. The present invention is not limited to uses in papermaking. The present invention also applies to the production of numerous products based on cellulose, including fiber mats, woven cloth, box, board, sheet, wood, particle board, braided wood board, sheets, etc. Products of this type are especially applicable to the present invention because they are produced from cellulosic starting materials. In accordance with the present invention, strength can be provided to these products through the addition of (a) water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component, to the cellulosic starting materials. In another form of describing the invention, a component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. Preferably, when used as an additive to improve the strength of the paper, the crosslinking system of the present invention is added to the pulp at the wet end of the process. The ingredients may also be added at the dry end in the form of a pre-mixed substance, or as separate streams of ingredients. Preferably, when used as a creping adhesive, the additives can also be introduced into the wet end of the process. Alternatively, it is also preferred to introduce a resin, produced in accordance with the present invention, directly into the creping cylinder before the adhesion of the fabric on the drum. As a crease adhesive, the material is preferably prepared in the form of a pre-mixed substance, where all the ingredients are mixed and allowed to develop into an adhesive constituent before application to the creping cylinder. The adhesives and resins of the present invention comprise: (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component. In another form of describing the invention, a component (c) may comprise a component capable of converting the phenolic compound to a quinone compound. When we refer to components in this application, unless otherwise indicated, the reference to a singular component also includes combinations of the components. For example, as used herein, the term "water-soluble polymeric material" comprising at least one nucleophilic polymer includes water-soluble polymers comprising nucleophiles, alone and / or in combination. As used herein, the term "phenolic compound" includes phenolic compounds, alone and / or in combination. In addition, as used herein, an oxidizing component includes oxidizing components, alone and / or in combination. As used herein, the term "hydrocarbyl" includes "aliphatic," "cycloaliphatic," and "aromatic." The hydrocarbyl groups include alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. In addition, "hydrocarbyl" includes both unsubstituted hydrocarbyl groups and substituted hydrocarbyl groups, the latter referring to the hydrocarbon portion bearing additional substituents, in addition to carbon and hydrogen. In more detail, the water-soluble polymer comprising a nucleophile can be selected from any water-soluble polymer comprising a nucleophile. As used herein, the term "water-soluble polymer" refers to polymers that can be made in a hot or cold aqueous solution in a concentration of at least about 0.01%. Preferably, such a polymer comprises polyalkylamine, polycyclic alkylamine, polyvinyl alcohol, polyvinyl sulfone, polyacrylamide, polyacrylate, polyacrylonitrile, polyether, polyester, polyaryl ether, polyarylsulphone, polyamide, polyimide, polyalkane, polyaminoalkane, and / or polyphenyl. More preferably, the polymer comprises polyvinylamine alcohol. Preferably, the polyvinylamine alcohol comprises from about 0.01% to about 100% amine; more preferably it comprises from about 10% to about 50% amine; and especially comprises about 12% amine. The nucleophile may be any known nucleophile, and preferably comprises -NH2, -NHR4, -SH, -SOO ", -PR42, and -ArO" or mixtures thereof, wherein R4 comprises a hydrocarbyl group wherein the number of atoms of carbon is located within a range of about 1 to about 12, and Ar comprises a benzenoid or naphthalenoid group. Preferably, the hydrocarbyl group comprises a benzenoid group or an alkyl group comprising from about 1 to about 12 carbon atoms. The nucleophile can be bound on the polymer structure in any manner known in the art. Preferably, the nucleophile is linked through a process comprising an addition reaction, followed by reduction. Preferably, the nucleophile is linked through nucleophilic displacement, amination, nitration, sulfonation, phosphorylation, or combinations thereof, each followed by reduction. In other preferred embodiments, the nucleophile is part of the monomer that polymerizes to form the polymer. The following formula is a schematic structural representation of the general chemical formula of the water-soluble polymer of an embodiment of the invention where the nucleophile is part of the polymer structure: FORMULA I In formula I, the brackets illustrate that the represented portion is repeated n times. In formula I, n can be any integer greater than 2, and is preferably between 10 and 200. More preferably, in formula I, n is between 50 and 100, and n is especially between 50 and 80. In the Formula I, R1 can be any hydrocarbyl group. Preferably, the hydrocarbyl group comprises from about 2 to about 20 carbon atoms. More preferably, the hydrocarbyl group comprises from about 6 to about 10 carbon atoms, and more preferably comprises about 6 carbon atoms. Preferably, the hydrocarbyl group comprises an alkyl group having from about 2 to about 20 carbon atoms. More preferably, the alkyl group has from about 6 to about 10 carbon atoms. More preferably, in formula I, the alkyl group comprises 6 carbon atoms. Examples of polymers having this general structure include, but are not limited to, polyalkylamine, and polycyclic alkylamine. The following formula is a schematic chemical representation of the general chemical formula of a water-soluble polymer of one embodiment of the invention, wherein the nucleophile is attached to the polymer structure: FORMULA II In formula II, the brackets illustrate that the represented portion repeats n times. In formula II, n can be any integer greater than 2, and is preferably greater than 100. In formula II, X comprises any nucleophile, and preferably comprises -NH2, -NHR2, -SH, -SOO ", -PR22, and ArO ", wherein R2 comprises a hydrocarbyl group having from about 1 to about 12 carbon atoms, and Ar comprises a benzenoid or substituted benzenoid, or naphthalenoid group. Preferably, the hydrocarbyl group comprises a benzenoid group or an alkyl group having from about 1 to about 12 carbon atoms. In formula II, Y comprises any group that allows the solubility of water, and is preferably a cationic, anionic, amphoteric group, or a hydrogen bonding group, such as -N + (R3) 3 (where R3 is any portion having from about 1 to about 12 carbon atoms, such as for example a straight chain C1-C12 or a cyclic portion C1-C12), -COO " -OS03 ~, -OP03", -N + (R3) 2 -R -COO", (where R? And R are any portion having from about 1 to about 12 carbon atoms, such as any straight chain C1-C12 or cyclic portion C1-C12), -OH, -CONH2, and -B (0H) 2. Examples of polymers in which the nucleophile is bonded to the polymer structure include, but are not limited to, polyvinyl alcohols, polyvinyl sulfones, polyacrylamides, polyacrylates, polyacrylonitriles, polyethers, polyesters, polyaryl ethers, polyarylsulphones, polyamides, polyimides, polyalkanes, polyaminoalkanes, polyphenyls. , and mixtures thereof. The phenolic compound for use in the present invention may comprise polyphenols, substituted polyphenols, catechols, substituted catechols, hydroquinones, substituted hydroquinones, aminophenols, substituted aminophenols, and / or mixtures thereof. The following formula schematically represents the general chemical structure of a preferred phenolic compound according to the invention: FORMULA III In formula III, X preferably comprises -OR3, -R3, -NR3R3, or -Ar, where R3 and R3 comprise H or a hydrocarbyl group comprising from about 1 to about 12 carbon atoms, and Ar comprises a group benzenoid or naphthalenoid. Preferably, the hydrocarbyl group comprises an alkyl group having from about 1 to about 12 carbon atoms. In formula III, Y preferably comprises -OH or -H.

Examples of phenolic compounds that exhibit this general structure include, but are not limited to,, phenol, catechol, hydroquinone, and aminophenol. More preferably, the phenolic material comprises 1,2-benzenediol and / or 1,4-benzenediol. In other preferred embodiments, the phenolic compound may comprise a polyphenolic compound which may be of natural or synthetic origin. Preferred natural polyphenolic compounds include, but are not limited to, phloroglucinol, lignin, catechins, flavonoids, and mixtures thereof. Preferred synthetic polyphenolic compounds include, but are not limited to, polyphenol, resol, novolak, calixerenes, and mixtures thereof. The present invention includes a component capable of converting the phenolic compound to a quinone compound. In another form of describing the invention, this component can be an oxidizing component. The oxidizing component may comprise potassium dichromate, potassium permanganate, or mixtures thereof. The oxidizing component may comprise mixtures such as for example hydrogen peroxide and a material such as for example a metal catalyst capable of causing hydrogen peroxide to release oxygen. Metal catalysts include, but are not limited to, ferric chloride, cobalt chloride, cupric chloride, and mixtures thereof.

The oxidizing component preferably comprises an enzyme system. The enzyme system preferably comprises at least one oxidant enzyme component. In preferred embodiments, the enzyme component may comprise an enzyme such as, for example, oxidase or peroxidase. Preferred oxidases and peroxidases include, but are not limited to, lactases, tyrosinases, polyphenol oxidases, sour radish peroxidases, soy peroxidases, haloperoxidases, lactoperoxidases, bacterial peroxidase, and combinations thereof. Other preferred embodiments comprise combinations of different oxidases, combinations of different peroxides, or combinations of oxidases and peroxidases. More preferably, the enzyme component comprises horseradish peroxidase. When the enzyme system is used, the reaction can occur in the presence of atmospheric air. However, the enzyme system also preferably comprises at least one source of oxygen. The source of oxygen can be direct, to the extent that oxygen is present as elemental oxygen and / or indirectly, to the extent that oxygen is released from a more complex molecule. Preferably, the oxygen source comprises a source such as, for example, perborates, persulfates, peroxides, and mixtures thereof. Other preferred enzyme systems comprise a mixture of sugar oxidase and the corresponding sugar, such as for example galactose and galactose oxidase or glucose and glucose oxidase. Other preferred enzyme systems comprise an alcohol oxidase and the corresponding alcohol, such as, for example, ethanol and ethanol oxidase. Preferably, the enzyme system comprises horseradish peroxidase and the reaction occurs in the presence of atmospheric air. Without being limited by theory, it is considered that, in the presence of an oxidizing component, a phenolic compound reacts by conversion to a quinone compound. In the presence of a substrate and a polymeric compound comprising a nucleophilic portion, the activated phenolic compound reacts with the polymer and the substrate to form a crosslinking. The following reaction, reaction I is a schematic chemical representation of the aforementioned reaction as it may occur: V "-o ^ \ S t 'B S T? T © Without further elaboration, it is considered that a person skilled in the art can employ the present invention to its greatest extent by employing the foregoing description. The following preferred specific embodiments are therefore considered as illustrative only and not limitative of the remainder of the disclosure. EXAMPLES EXAMPLES 1-6 - An enzyme-activated polymer system provides paper strength Hand-held paper sheets are made on a Noble and Wood Sheet Machine (Noble and Wood Machine Co., Hoosick Falls, NY) using standard hard water with a pH controlled. 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 and H2S04. The pulp is whipped to the desired freedom at a consistency of 2.5% by weight. The whipped pulp is added to a proportioner at a controlled level (according to the desired final base weight). For a base weight of 80 pounds / 3000 square feet, 4000 ml of whipped pulp is used. In the case of a base weight of 40 pounds / 3000 square feet, 2000 ml of whipped pulp are used. The whipped pulp is diluted to 18 liters with standard hard water. Chemical additions and pH adjustments are made to the proportioner as desired, with continuous mixing. A screen of clean and damp 100 mesh is placed in an open-shaped box, which is then closed. Standard hard water and 920 ml of pulp mixture are then added from the proportioner to the shape box, and applied. The ingredients according to the present invention are added to the shape box, and mixed. The water is then drained from the box, and the sheet is removed. The sheet is squeezed between felts with press weights adjusted to provide a solids content of 33-34%. The sheet and the screen are then placed in a drum dryer that is adjusted to a temperature of about 228-232 ° F, with a step time of 50 to 100 seconds, depending on the basis weight. The final moisture content in the leaf is 3-5%. A single sheet is made from 920 ml of pulp mixture. Five sheets are tested at least for each experimental group. The tensile strength test is carried out on sheets of hand-held paper in accordance with TAPPI's T 494 or -88 method ("TAPPI Test Methods," TAPPI Press, Atlanta, GA). , nineteen ninety six) . For Examples 1-6, the following materials according to the invention are added: polyvinylamine alcohol, molecular weight of approximately 100 Kd, 6% amine (Air Product); catechol, 99% purity (Aldrich Chemical); hydroquinone (Eastman Kodak Chemical); peroxidase (Sigma Chemical); hydrogen peroxide, 3% solution (Baker Chemical). The specific amounts that are added to each batch (920 ml of pulp mixture) are disclosed in table 1. Additives are added as solutions in 10 ml of water. In the case of EXAMPLES 1-6, the paper is manufactured with a base weight of 80 pounds: the 920 ml of pulp mixture provided 5.1 g of pulp (paper weight). Unless otherwise specified, the proportions illustrated in the table are weight / weight. The following abbreviations are used in table 1: polyvinylamine alcohol, PVAA; catechol, CAT; hydroquinone, HQ; peroxidase, PER; and hydrogen peroxide, H202. No addition indicates that no additional chemicals were added. TABLE 1 - EFFECT ON PAPER STRENGTH Example Description Resistance to tensile strength in wet state dry state (pounds / inch) (pounds / inch) 1 no addition 1.6 44.7 2 51 mg PVAA 8.8 59.3 (MW 100K, 6% amine) 3 51 mg PVAA / 5.1 mg 8.8 49.9 CAT (10/1) 4 51 mg PVAA / 5.1 mg 9.9 58.1 CAT / 0.25 mg PER (10/1 / 0.05) 5 51 mg PVAA / 5.1 mg 9.8 56.6 CAT / 0.25 mg PER / 1.25 mg H202 (10/1 / 0.05 / 0.25) 6 51 mg PVAA / 5.1 mg 12.6 74.5 HQ / 0.25 mg PER (10/1 / 0.05) Examples 1-6 are presented as evidence that the modalities of the present invention provide resistance to a paper product. The results presented in Table 1 clearly demonstrate the substantial increase in paper strength that is provided by the present invention. Examples 7-12 - effect of the molecular weight of the polymer on the strength of the paper The paper is made in accordance with the procedures presented in EXAMPLES 1-6 above except that different amounts, different types and types of material were added, in accordance with the invention. The specific amounts that are added to each batch (920 ml of pulp mixture per piece of paper) are presented in table 2. Additives are added as solutions in 10 ml of water. The paper is manufactured with a base weight of 80 pounds: 920 ml of pulp mixture provided 5.1 g of pulp (paper weight). The following new abbreviations were introduced for use in Table 2: polyvinylamine alcohol (molecular weight approximately 100 Kd, 6% amine), PVAA1; polyvinylamine alcohol (molecular weight approximately 30 Kd, 12% amine), PVAA2. TABLE 2 - EFFECT OF THE MOLECULAR WEIGHT OF THE POLYMER Example Description Resistance to Tension resistance in tension in wet state dry state [pounds / inch] (pounds / inch) 7 no addition 1.8 48.3 8 51 mg PVAA1 13.2 63.9 9 51 mg PVAA2 9.8 59.7 10 51 mg PVAA1 / 5.1 mg 16.7 78.2 CAT / 1.25 mg PER (10/1 / 0.05) 11 51 mg PVAA2 / 5.1 mg 10.8 63.5 CAT / 1.25 PER (10/1 / 0.25) 12 51 mg PVAA2 / 5.1 mg 14.8 68.2 HQ / 1.25 mg PER (10/1 / 0.05) Since the molecular weight of the polymer employed in the present invention may have an effect on the strength provided to the paper product, EXAMPLES 7-12 are provided to demonstrate this effect. Two different molecular weights of polymer were tested, 100 Kd and 30 Kd. From the results presented in Table 2, it is clear that the 100 Kd polymer has a better performance than the 30Kd polymer. EXAMPLES 13-18 - Effect of the pH of the conditions for making the paper The paper is made in accordance with the procedure presented in EXAMPLES 1-6 above, except that different quantities and different types of materials were added, in accordance with the invention, and the base weight for the paper is 40 pounds. The weight per piece of paper is 2.5 g. The quantities and types of materials used specifically appear in table 3. TABLE 3 - EFFECT OF THE PH OF THE CONDITIONS OF ELABORATION OF PAPER Ex. pH description resistance to tensile strength in tension in wet state dry state pounds / inch (pounds / inch) 13 7.5 no addition 0.7 20.2 14 7.5 25 mg PVAA 5.3 27.4 (MW 100K, 6% amine) 15 7.5 25 mg PVAA / 5.4 28.8 0.6 mg PER (10 / 0.25) 16 7.5 25 mg PVAA / 7.3 36.7 0.25 mg CAT / 0.6 mg PER (10/1 / 0.05) 17 5.5 25 mg PVAA / 4.9 29.1 0.6 mg PER (10 / 0.25) 18 5.5 25 mg PVAA / 7.0 34.5 2.5 mg CAT / 0.6 mg PER (10/1 / 0.25) Since the pH of an enzymatic reaction can have an effect on the reaction itself, examples 13-18 are provided to demonstrate this effect. The results presented in Table 3 demonstrate that the reaction according to the present invention has a slightly better performance at a pH of 7.5 than at a pH of 5.5. EXAMPLES 19-23 - Effect of diamine and phenol compounds on paper strength Paper is made in accordance with the procedure presented in EXAMPLES 1-6 above, except that different quantities and different types of materials are added, in accordance with the invention The quantities and types of materials used specifically appear in Table 4. The following new abbreviations are introduced for use in Table 4: ethylenediamine, molecular weight approximately 600, ED-600; ethylenediamine, molecular weight approximately 2000, ED-2001; phenol, PHE; hydrogen peroxide, H202. TABLE 4 - EFFECT OF DIAMIN AND PHENOL COMPOUNDS Example Description Resistance in Wet state Resistance (pounds / inch) (pounds / inch) 19 no added 1.7 51.0 20 51 mg PVAA / 2.8 mg 11.5 61.5 CAT / 0.51 mg PER (10 / 0.56 / 0.1) 21 51 mg PVAA / 2.8 mg 13.0 65.1 PHE / 0.7 mg PER / 0.7 mg H202 (10 / 0.56 / 0.14 /0.14) 22 51 mg PVAA / 15 mg ED- 11.6 60.0 600 / 5.5 mg CAT / 1.4 mg PER (10/3 / 1.07 / 0.27) 23 51 mg PV7? A / 15 mg ED- 11.9 57.9 2001 / 5.5 mg CAT /1.4 mg PER (10/3 / 1.07 / 0.27) These examples are presented to show that diamine compounds can be successfully mixed into the formulation. From the above descriptions, a person skilled in the art can easily determine the essential characteristics of this invention and without departing from the spirit and scope thereof, can make various changes and modifications to the invention to adapt it to various uses and conditions.

Claims (56)

1. CLAIMS A composition comprising (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) a component capable of converting the phenolic compound to a quinone compound. A composition comprising (a) a water-soluble polymeric material comprising at least one nucleophilic polymer, (b) a phenolic compound, and (c) an oxidizing component. The composition according to claim 2 or according to claim 3, wherein the oxidizing component comprises a member selected from the group consisting of potassium dichromate, potassium permanganate, and mixtures thereof. The composition according to claim 2, wherein the oxidizing component comprises a metal catalyst and hydrogen peroxide. The composition according to claim 4, wherein the metal catalyst is selected from the group consisting of ferric chloride, cupric chloride, cobalt chloride, and mixtures thereof. The composition of any of claims 2 to 5, wherein the oxidizing component comprises an enzyme system. The composition according to claim 6, wherein the at least one nucleophilic polymer comprises the following general structure: where n is an integer greater than 2, and R1 comprises a hydrocarbyl group comprising from about 2 to about carbon atoms. The composition according to claim 7, wherein the hydrocarbyl group comprises an alkyl group. 9. The composition according to claim 8, wherein the alkyl group comprises from about 6 to about 10 carbon atoms. The composition of any of claims 7 to 9, wherein n is from about 10 to about 200. 11. The composition according to claim 10, wherein n is from about 50 to about 80. 12, The composition in accordance with any of claims 7 to 11, wherein the at least one nucleophilic polymer comprises a member selected from the group consisting of polyalkylamine, polycyclic alkylamine, and mixtures thereof. The composition according to claim 6, wherein the at least one nucleophilic polymer comprises the following general structure: where n is an integer greater than 2, X comprises a nucleophile, and Y comprises a group that allows solubility in water. The composition according to claim 13, wherein the nucleophile comprises a member selected from the group consisting of -NH2, -NHR2, -SH, -SOO ", -ArO", and -PR22, wherein R2 comprises a group hydrocarbyl comprising from about 1 to about 12 carbon atoms, and Ar comprises a benzenoid, substituted benzenoid, or naphthalenoid group. 15. The composition according to claim 14, wherein the hydrocarbyl group comprises a benzenoid group or an alkyl group. 16. A composition of any of claims 13 to 15, wherein the group permitting solubility in water comprises a member selected from the group consisting of cationic, anionic, amphoteric, hydrogen bonding participation groups, and mixtures thereof. . The composition according to claim 13, wherein the group allowing water solubility comprises a number selected from the group consisting of -N + (R3) 3, -COO ", -0S03-, -OP03", - N + (R3) 2-R3'-COO ", -OH, -CONH2, -B (OH) 2, and mixtures thereof, wherein R3 and R3 'comprise any portion having from about 1 to about 12 carbon atoms 18. The composition of any of claims 2 to 17, wherein the at least one nucleophilic polymer comprises a member selected from the group consisting of polyvinyl alcohols, polyvinyl sulfones, polyacrylamides, polyacrylates, polyacrylonitriles., polyethers, polyesters, polyaryl ethers, polyarylsulphones, polyamides, polyimides, polyalkanes, polyaminoalkanes, polyphenyls, and mixtures thereof. The composition of any of claims 2 to 17, wherein the at least one nucleophilic polymer is formed through a process further comprising an addition reaction followed by reduction. The composition of any of claims 2 to 17, wherein the at least one nucleophilic polymer comprises a member selected from the group consisting of -NH2, -NHR4, -SH, -SOO ", -PR42, -ArO", and mixtures thereof, wherein R4 comprises a hydrocarbyl group comprising between about 1 to about 12 carbon atoms, and Ar comprises a benzenoid group or a naphthalenoid group. The composition according to claim 20, wherein the hydrocarbyl group comprises a benzenoid group or an alkyl group. 22. The composition of any of claims 2 to 17, wherein the at least one nucleophilic polymer is formed by the polymerization of a monomer comprising a nucleophile. 23. The composition of any of claims 2 to 17, wherein the at least one nucleophilic polymer comprises polyvinylamine alcohol. The composition according to claim 23, wherein the polyvinylamine alcohol comprises from about 0.01% to about 100% amine. The composition according to claim 24, wherein the polyvinylamine alcohol comprises from about 10% to about 50% amine. The composition of any of claims 2 to 25, wherein the phenolic compound comprises a polyphenolic compound. The composition according to claim 26, wherein the polyphenolic compound comprises a member selected from the group consisting of phloroglucinol, lignins, catechins, flavonoids, and mixtures thereof. The composition according to claim 26, wherein the polyphenolic compound comprises a member selected from the group consisting of polyphenols, resoles, novolaks, calixerenes, and mixtures thereof. The composition of any of claims 2 to 25, wherein the phenolic compound comprises the following general chemical structure: where Y comprises -H or -OH, and X comprises -OR5, -R5, -Ar, or -NR5R5, where R5 and R5 comprise H or a hydrocarbyl group comprising from about 1 to about 12 carbon atoms, and Ar comprises a benzenoid or naphthalenoid group. 30. The composition according to claim 29, wherein the hydrocarbyl group comprises an alkyl group. 31. The composition according to any of claims 2 to 25, wherein the phenolic compound comprises a member selected from the group consisting of polyphenols, substituted polyphenols, phenols, substituted phenols, catechols, substituted catechols, hydroquinones, substituted hydroquinones, aminophenols, aminophenols substituted, and mixtures thereof. 32. The composition according to claim 31, wherein the phenolic material comprises 1,2-benzenediol. 33. The composition according to claim 31, wherein the phenolic material comprises 1,4-benzenediol. 34. The composition according to any of claims 6 to 25, wherein the enzyme system comprises at least one oxidation enzyme. 35. The composition according to claim 34, wherein the at least one oxidation enzyme comprises an oxidase. The composition of claim 34, wherein the at least one oxidation enzyme comprises a peroxidase. The composition according to claim 36, wherein the peroxidase comprises a member selected from the group consisting of peroxidases of sour radish, soy peroxidases, haloperoxidases, lactoperoxidases, bacterial peroxidases, and mixtures thereof. The composition according to claim 35, wherein the oxidase comprises a member selected from the group consisting of laccase, tyrosinase, polyphenoloxidase, and mixtures thereof. The composition according to claim 36, wherein the peroxidase comprises horseradish peroxidase. The composition of any of claims 6 to 25, wherein the enzyme system comprises at least one source of oxygen. The composition according to claim 40, wherein the oxygen source comprises a member selected from the group consisting of perborates, persulfates, peroxides, and mixtures thereof. The composition of any of claims 6 to 25, wherein the enzyme system comprises an alcohol oxidase and its corresponding alcohol. 43. The composition according to claim 42, wherein the enzyme system comprises ethanol and ethanol oxidase. 44. The composition of any of claims 6 to 25, wherein the enzyme system comprises sugar oxidase and its corresponding sugar. 45. The composition according to claim 44, wherein the enzyme system comprises glucose and glucose oxidase or galactose and galactose oxidase. 46. A composition comprising the composition of any of claims 2 to 45, in combination with a cellulosic material. The composition according to claim 46, wherein the cellulosic material comprises paper pulp. The composition according to claim 46, wherein the cellulosic material comprises a member selected from the group consisting of fiber mat, woven cloth, box, board, sheet, wood, particle board, wooden braid board, and sheets . 49. A resin for providing resistance to a paper product, comprising the composition of any of claims 1 to 45. 50. A creping adhesive comprising the composition of any of claims 1 to 45. 51. A paper product comprising a cellulosic material and the resin according to claim 49. 52. A paper product comprising a cellulosic material and the creping adhesive according to claim 50. 53. A method for providing resistance to a product based on cellulose, comprising the addition of the composition of any one of claims 1 to 48 to cellulosic starting materials. 54. A method for increasing the strength of a paper product, comprising adding the composition of any of claims 1 to 48 to the paper pulp. 55. A set of elements comprising a polymeric material soluble in water, comprising (a) at least one nucleophilic polymer, (b) a phenolic compound, and (c) a component capable of converting the phenolic compound to a quinone compound. 56. A composition comprising a polyvinylalkylamine, a benzenediol, and horseradish peroxidase.