Paper making and fiber liberation – Processes and products – Synthetic fiber
Reexamination Certificate
2001-01-04
2003-05-13
Fortuna, Jose A. (Department: 1731)
Paper making and fiber liberation
Processes and products
Synthetic fiber
C162S009000, C008S108100
Reexamination Certificate
active
06562195
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to paper comprising aldehyde modified cellulose pulp or fiber and further to the method of preparing aldehyde modified cellulose and cellulose pulp or fiber using selected oxidation conditions to generate aldehyde functionality. More particularly, this invention involves paper made from cellulose pulp having a defined amount of aldehyde content. A method for preparing the selected aldehyde modified cellulose and cellulose pulp involves using a nitroxyl radical mediated oxidation with a limited amount of oxidant and defined reaction conditions. This aldehyde modified pulp is used in the production of tissue/towel and other paper products which exhibit unexpected high wet strength, temporary wet strength and dry strength properties and high wet strength/dry strength ratios without the use of other additives.
The term “paper” as used herein, includes sheet-like masses and molded products made from pulp or fibrous cellulosic material which may be derived from natural sources. Paper may also be made from synthetic cellulosic fibers and regenerated cellulose as well as recycled waste paper. In addition, paper made from combinations of cellulosic and synthetic materials are applicable herein. Paperboard is included within the broad term “paper”.
Papermaking, as it is conventionally known, is a process of introducing an aqueous slurry of pulp or wood cellulosic fibers (which have been beaten or refined to achieve a level of fiber hydration and to which a variety of functional additives can be added) onto a screen or similar device in such a manner that water is removed, thereby forming a sheet of the consolidated fibers, which upon pressing and drying can be processed into dry roll or sheet form. Typically in papermaking, the feed or inlet to a papermaking machine is an aqueous slurry or water suspension of pulp fibers which is provided from what is called the “wet end” system. In the wet end, the pulp along with other additives are mixed in an aqueous slurry and subject to mechanical and other operations such as beating and refining. Various additives are commonly added to help provide different properties in the paper product.
The preparation of aldehyde containing starches and the use of such aldehyde derivatives in the paper industry as wet and dry strength additives is well known. Both oxidative and non-oxidative methods are known for introducing aldehyde groups into starch. Use of these products in papermaking to provide wet and dry strength properties involves the addition of this separate starch additive component.
The use of nitroxyl radicals and nitrosonium salts in organic chemistry as an oxidative route to produce aldehydes and carboxylic acids from primary and secondary alcohols is disclosed in an article entitled “Organic Nitrosonium Salts As Oxidants in Organic Chemistry” by J. M. Bobbitt and C. L. Flores, in
Heterocycles
, Vol. 27, No. 2, 1988, pp. 509-533. Recently, application of this chemistry was extended to the selective oxidation of primary alcohols in various carbohydrates to carboxylic acids in an article entitled “Selective Oxidation of Primary Alcohols Mediated by Nitroxyl Radical in Aqueous Solution. Kinetics and Mechanism” by A. E. J. de Nooy and A. C. Bessemer, in
Tetrahedron
, Vol. 51, No. 29, 1995, pp. 8023-8032. Patent publication WO 95/07303 dated Mar. 16, 1995 further discloses the use of this technology where carbohydrates having a primary hydroxyl group are oxidized under aqueous conditions to form products having a high content of greater than 90% carboxyl groups. This art involving the oxidation of primary alcohols generally describes the preparation of polyglucuronic acids with high carboxylic acid content. Similarly, the process of oxidation has been used to prepare various polysaccharides with high carboxyl content as described in “Oxidation of Primary Alcohol Groups of Naturally Occurring Polysaccharides with 2,2,6,6-Tetramethyl-1-piperidine Oxoammonium Ion” by P. S. Chang and J. F. Robyt in
J. Carbohydrate Chemistry,
15(7), 1996, pp. 819-830. It should be noted that in some applications high carboxylic acid content is undesirable.
Recent patent publications WO 99/23240 and 99/23117, both dated May 14, 1999, respectively disclose methods of oxidizing starch and cellulose using an oxoammonium ion producing reagent in the presence of an enzyme oxidizing agent.
Despite the various methods described above, there still is the need for cellulose pulp which is suitable for use in paper applications to provide the desired high degree of wet strength, temporary wet strength and dry strength properties and does not involve the use of separate additive components.
SUMMARY OF THE INVENTION
This invention is directed to paper having wet strength, temporary wet strength and dry strength properties and comprising aldehyde modified cellulose pulp wherein the pulp has from 1 to 20 mmoles of aldehyde per 100 g of cellulose.
Another embodiment of this invention involves the selective preparation of cellulose aldehyde and cellulose pulp aldehyde under defined oxidation conditions using a nitroxyl radical mediated aqueous oxidation procedure to provide derivatives with effective aldehyde content particularly useful in papermaking. More particularly, this invention involves the oxidation of cellulose or cellulose pulp in an aqueous solution with an oxidant having an equivalent oxidizing power of up to 5.0 g of active chlorine per 100 g of cellulose and an effective mediating amount of nitroxyl radical, the reaction being carried out at a pH of about 8.0 to 10.5, and a temperature of from about 5 to 50° C., the resulting product having an aldehyde content of about 1 to 20 mmole/100 g of pulp.
This invention further involves aldehyde modified cellulose or cellulose pulp having defined aldehyde content.
Still another embodiment involves the method of preparing paper having wet strength, temporary wet strength and dry strength properties comprising using the cellulose aldehyde pulp prepared by the selective oxidation procedure as described above, as the paper or pulp stock or a component thereof.
DETAILED DESCRIPTION OF THE INVENTION
The cellulose or cellulose pulp aldehyde derivatives of this invention have effective aldehyde functionality or content of from about 1 to 20 and preferably from about 5 to 20 mmoles/100 g of cellulose material, i.e., cellulose or cellulose pulp.
The cellulose aldehyde derivatives of this invention can be prepared by a method which involves the selective oxidation of cellulose and cellulose pulp or fiber using a limited amount of oxidant mediated with a nitroxyl radical under defined conditions to provide derivatives with effective aldehyde content making them particularly suitable for use in providing paper with desired wet strength, temporary wet strength and dry strength properties.
The nitroxyl radical mediator used herein is a di-tertiary alkyl nitroxyl radical having one of the following formulas:
where A represents a chain of preferably two or three atoms, in particular carbon atoms or a combination of one or two carbon atoms with an oxygen or nitrogen atom, and the R groups represent the same or different alkyl groups. Chain A may be substituted by one or more groups such as alkyl, alkoxy, aryl, aryloxy, amino, amido or oxo groups, or by a divalent group or multivalent group which is bound to one or more other groups having formula I. Particularly useful nitroxyl radicals are di-tertiary alkyl nitroxyl radicals having the formula:
where Y is either H, OH or
and each of the R groups represent the same or different alkyl groups of 1 to 18 carbon atom and more particularly methyl groups. Nitroxyl radicals of this type include those where a) the R groups are all methyl (or alkyl of 1 carbon atom) and Y is H, i.e., 2,2,6,6-tetramethyl-1-piperdinyloxy (TEMPO); b) R groups are methyl and Y is OH and identified as 4-hydroxy TEMPO; and c) R groups are methyl and X is
and identified as 4-acetamido-TEMPO. The preferred nitroxyl radical is TEMPO or 4-acetamido-TEMPO. The nitroxyl radi
Cimecioglu A. Levent
Harkins Danielle E.
Fortuna Jos'e A.
LeCroy, Esq. David P.
National Starch and Chemical Investment Holding Corporation
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