US3087775A - Production of alkali-soluble cellulosic textile materials by the nitric acid treatment of partially etherified cottons - Google Patents

Production of alkali-soluble cellulosic textile materials by the nitric acid treatment of partially etherified cottons Download PDF

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US3087775A
US3087775A US33350A US3335060A US3087775A US 3087775 A US3087775 A US 3087775A US 33350 A US33350 A US 33350A US 3335060 A US3335060 A US 3335060A US 3087775 A US3087775 A US 3087775A
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nitric acid
cotton
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Robert M Reinhardt
Terrence W Fenner
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/13—Cyanoethylation of fibers

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  • an alkali-soluble cellulosic textile material must possess enough strength to withstand the rigorous stresses and strains of processing on normal textile machinery. Along with these substantial strength requirements, because of the transient uses for which these textile materials are employed, their solubility must be suflicient to allow essentially complete removal of these textile members without undue complications to normal plant practices.
  • This objective is accomplished by a two step treatment: first, cotton textile materials are partially etherified to a low degree of substitution (D.S., the average number of substituent ether groups per anhydroglucose unit), in the range of from about 0.01 to about 0.6, and secondly, treatment of the partially etherified cotton with aqueous solutions of nitric acid.
  • the process may be carried out on fabric, thread, yarn, or fiber.
  • nitric acid treatments of cellulose have been used to prepare alkalisoluble materials.
  • the products have been either highly nitrated materials (nitrocellulose) prepared under rigorous, usually anhydrous, reaction conditions with nitric acid and strong dehydrating agents, or materials nitrated to a lower degree but under conditions requiring mixed reagent techniques such as the use of nitric acid-phosphoric acid or nitric acid-sulfuric acid solutions, or materials which are not textile fibers but are produced in solution or are cast as films.
  • the nitric acid treatment is carried out on partially etherified cottons. It is not necessary to use anhydrous conditions, dehydrating compounds 3,087,775 Patented Apr. 30, 1963 or mixed acid techniques. A fibrous product is produced which has good strength and is soluble in alkaline solutions. Further, by using partially etherified cottons instead of native or mercerized cotton as a starting material, less drastic conditions may be employed in nitric acid treatment step. With partially etherified cottons, products with higher solubility are obtained with more dilute concentrations of nitric acid, shorter treatment times, and lower temperatures than if the nitric acidtreatment was carried out on native or mercerized cotton.
  • the two step treatment accomplishes the objectives through multiple efiects.
  • a small amount of ether groups are introduced. These ether groups are alkali-solubilizing and would result in a alkali-soluble material if the etherification was carried out to greater extent. Further, these other groups exert a swelling effect which makes the partially etherified cotton highly accessible for reaction in the nitric acid treatment step.
  • the preferred partially etherified cottons which may be employed in the process of this invention include partially aminoethylated, carbamoylethylated, carboxyethylated, carboxymethylated, cyanoethylated, hydroxyethylrated, and phosphonomethylated cotton.
  • nitration of the cellulosic hydroxyls proceeds only to a low degree as evidenced by a modified Kjeldahl nitrogen analysis of the products.
  • the nitrogen introduced is usually 1.2% or less.
  • the low extent of oxidation during this step may be estimated by carboxyl and carbonyl analysis.
  • some hydrolytic cleavage of glucosidic linkages takes place, this cleavage is not extensive as evidenced by the considerable strength retained by the product. Drastic loss of strength is a consequence of a relatively small amount of cleavage of glucosidic linkages. The extent of this cleavage may be more accurately estimated by DR (degree of polymerization) determinations.
  • the partial etherification step may be carried out by any of the known methods which will be apparent to those skilled in the art.
  • Partial aminoethylation of cotton may be carried out, for example, as described by Guthrie in Textile Research Journal 17, 625-9 (1957).
  • the aminoethyl ether of cellulose may be represented by the formula in which R represents the anhydroglucose unit.
  • Partial carbamoylethylation of cotton may be carried out, for example, as described by Frick, Reeves, and Guthrie in Textile Research Journal 27, 2949 (1957).
  • the carbamoylethyl ether of cellulose may be represented by the formula ROCH CH C(O)NH in which R represents the anhydroglucose unit.
  • Partial car-boxyethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 25, 246-53 (1955).
  • the carboxyethyl ether of cellulose may be represented by the fiormula ROCH CH COOH in which R represents the anhydroglucose unit.
  • Partial carboxymethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 22, 787-92 (1952).
  • carboxymethyl ether of cellulose may be represented by the formula ROCH COOH in which R represents the anhydroglucose unit.
  • Partial cyanoethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 25, 24653 (1955)
  • the cyanoethyl etherof cellulose may be represented by the formula ROCH CH CN in which R represents the anhydroglucose unit.
  • Partial hydroxyethylation of cotton- may be carried out, for example, as described by Lawrie, Reynolds, and Ward in Journal of the Society of Dyers and Colourists 56, 6-17 (1940)
  • the hydroxyethyl ether of cellulose may be represented by the formula ROCH CH OI-I in which R represents the anhydroglucose unit.
  • Partial phosphonomethylation of cotton may be carried out, for example, as described by Drake, Reeves, and Guthrie in Textile Research Journal 29, 270- 1959).
  • the phosphonomethyl ether of cellulose may be represented' by the formula ROCH P(O) (OH) in which R represents the anhydroglucose unit.
  • Partially etherified cottons with a degree of substitution of from about 0.04 to about 0.55 are preferred for the process of this invention.
  • the degree of substitution and the severity of conditions required in the nitric acid treatment for good alkali-solubility are inversely related.
  • the nitric acid treatment step may be carried out within widely varying limits.
  • the treatment may be effected at temperatures ranging from about room temperature to boiling and at nitric acid concentrations varying from about 10% to about 70%. With higher temperatures, the treatment time is reduced'and may be as little as a few seconds.
  • the treatment temperature is correspondingly adjusted in inverse relation to treatment time. With the lower concentrations of nitric acid the time of treatment required is extended and may range to periods of 24 hours or longer. For the lower con centrations of nitric acid, the time of treatment necessary may thus be reduced by an adjustment towards higher temperatures.
  • the preferred range of conditions for the nitric acid treatment'step thus encompasses treatment times of from about 0.5 minute to about 75 'minutes, at temperatures of from about room temperature to the boiling temperature of the nitric acid solution, using concentrations'of nitric acid of about 10% to about 70%, the time and temperature of the nitric acid treatment being inversely related to thenitric acid concentration.
  • alkali-soluble textile material Uses for alkali-soluble textile material are well known in the art. Among such uses are the preparation of open work fabrics by weavingsoluble yarns and ordinary yarns in such a manner that upon dissolution of the soluble yarns the open-work pattern eifect is produced in the fabric. Other uses may include utilization of alkali-soluble threads for basting or for connecting threads in the string-sock knitting process. The soluble members are readily removed by a subsequent alkali treatment. Alkalisoluble fabric is used as a backing cloth in a process for the manufacture of lace,
  • Percent alkali-solubility l00[W EXAMPLE 1
  • Samples of cotton cloth were: (a) mercerized by treatment with 20% sodium hydroxide; (b) aminoethylated to a D.S. of 0.08 by treatment with Z-aminoethyl sulfuric acid and 40% sodium hydroxide; (c) carbamoylethylated to a D.S. of 0.25 by impregnation with an aqueous solution containing 50% acrylamide and 4% sodium hydroxide followed by heating at C. for five minutes; (d) carboxyethylated to a D.S.
  • EXAMPLE 2 A sample of cotton was hydroxyethyl-ated to a D.S. of 0.5'0-by treatment similar to that of sample (g) of Example 1. It was treated with nitric acid as in Example 1. The alkali-solubility was 89.5%.
  • EXAMPLE 3 Samples of partially carboxymcthylated cotton, D.S. 0.10, were treated with aqueous solutions containing 70% nitric acid, by weight, at 26 C. for various periods of time of from minutes to 75 minutes. For comparison, a sample of mercerized cotton was treated for 75 minutes. The properties of the treated samples are shown in the EXAMPLE 5 Samples of partially carboxymethylated cotton (D.S. 0.08) and of mercerized cotton cloth were treated with an aqueous solution containing 70% nitric acid, by weight, at 40 C. for 5 minutes. The nitric acid treatedcarboxymethylated tabric was 88.4% alkali soluble and retained 73.5% of its original strength. The nitric acid treated mercerized fabric was only 53.0% alkali-soluble and retained 89.4% of its original strength.
  • EXAMPLE 6 Samples of partially carboxymethylated cotton (D.S. 0.08) and ot mercerized cotton were treated with an aqueous solution containing 35% nitric acid, by weight, at the boil for 0.5 minute. Alkali-solubilities were 96.3% and 27.9%, respectively.
  • EXAMPLE 7 Samples of partially carboxymethylated cotton (D.S. 0.08) and of mercerized cotton were treated with an aqueous solution containing 10% nitric acid, by weight, at the boil for 4 minutes. Alkalisolubilitics were 96.7% and 53.2%, respectively.
  • a process for producing an aqueous alkali soluble cotton cellulosic textile material which comprises etherit'ying the cotton cellulosic textile material to a degree of substitution of from about 0.01 to about 0.6 and oxidizing the cellulose chain of the partially etherified textile material by treating the partially etherified cotton cellulosic textile material with an aqueous solution of nitric acid in a concentration of from about 10% to about by weight, at a temperature of from about room temperature to that of the boiling point of the aqueous nitric acid solution, tor a period of time of trout about 0.5 minute to about minutes, the time and temperature of the nitric acid treatment being inversely related to the nitric acid concentration.

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Description

United States Patent 3,087,775 PRODUCTION OF ALKALI-SOLUBLE CELLULOSIC TEXTILE MATERIALS BY THE NITRIC ACID gllzgTMENT 0F PARTIALLY ETHERIFIED COT- Robert M. Reinhardt and Terrence W. Feuner, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture N0 Drawing. Filed June 1, 1960, Ser. No. 33,350 8 Claims. (Cl. 8-116) (Granted under Title 35, U.S. Code (1952), sec. 266) A non-exclusive, irrevocable royalty-free license in the invention herein described, throughout the world for all purposes of the United States Government, with the ,7 power to grant sublicenses for such purposes, is hereby granted to the Government of the United States of Amer- This invention relates to alkali-soluble cellulosic textile materials and methods of their production.
It is known that certain chemical modifications of cotton can be employed to prepare cellulosic derivatives which are alkali-soluble. However, many of those chemical modifications involve the use of the uneconomical reagents and/ or uneconomical conditions of reaction. Further, many of these chemical modifications results in nonfibrous products or products which are so weakened and degraded that their value as textile materials is lost.
To be a useful article of commerce for textile usage, an alkali-soluble cellulosic textile material must possess enough strength to withstand the rigorous stresses and strains of processing on normal textile machinery. Along with these substantial strength requirements, because of the transient uses for which these textile materials are employed, their solubility must be suflicient to allow essentially complete removal of these textile members without undue complications to normal plant practices.
It is an object of this invention to provide a process for the production of alkali-soluble cellulosic textile materials which possess the strength and solubility characterics necessary for industrial utilization. This objective is accomplished by a two step treatment: first, cotton textile materials are partially etherified to a low degree of substitution (D.S., the average number of substituent ether groups per anhydroglucose unit), in the range of from about 0.01 to about 0.6, and secondly, treatment of the partially etherified cotton with aqueous solutions of nitric acid. The process may be carried out on fabric, thread, yarn, or fiber.
It is a further objective of this invention to provide a process which is more economical than convention-a1 processes in that only inexpensive reagents are used and in that more economical reaction conditions, notably shorter reaction times, lower reaction temperatures, and more dilute concentrations of reagent may be employed in the nitricacid treatment step than would be operative without the unique complementary efiect of the combined steps of the two step process.
As is known to those skilled in the art, nitric acid treatments of cellulose have been used to prepare alkalisoluble materials. In the prior art, however, the products have been either highly nitrated materials (nitrocellulose) prepared under rigorous, usually anhydrous, reaction conditions with nitric acid and strong dehydrating agents, or materials nitrated to a lower degree but under conditions requiring mixed reagent techniques such as the use of nitric acid-phosphoric acid or nitric acid-sulfuric acid solutions, or materials which are not textile fibers but are produced in solution or are cast as films.
In the present invention the nitric acid treatment is carried out on partially etherified cottons. It is not necessary to use anhydrous conditions, dehydrating compounds 3,087,775 Patented Apr. 30, 1963 or mixed acid techniques. A fibrous product is produced which has good strength and is soluble in alkaline solutions. Further, by using partially etherified cottons instead of native or mercerized cotton as a starting material, less drastic conditions may be employed in nitric acid treatment step. With partially etherified cottons, products with higher solubility are obtained with more dilute concentrations of nitric acid, shorter treatment times, and lower temperatures than if the nitric acidtreatment was carried out on native or mercerized cotton.
The two step treatment accomplishes the objectives through multiple efiects. In the first or partial etherification step, a small amount of ether groups are introduced. These ether groups are alkali-solubilizing and would result in a alkali-soluble material if the etherification was carried out to greater extent. Further, these other groups exert a swelling effect which makes the partially etherified cotton highly accessible for reaction in the nitric acid treatment step.
The preferred partially etherified cottons which may be employed in the process of this invention include partially aminoethylated, carbamoylethylated, carboxyethylated, carboxymethylated, cyanoethylated, hydroxyethylrated, and phosphonomethylated cotton.
In the second or nitric acid treatment step, three chemical reactions may take place: nitration of cellulosic bydroxyls, oxidation along the cellulosic chain, and hydrolysis of glucosidic linkages of the cellulosic chain. All three reactions are efficacious in producing alkalisolubility. v
In the nitric acide treatment step, nitration of the cellulosic hydroxyls proceeds only to a low degree as evidenced by a modified Kjeldahl nitrogen analysis of the products. The nitrogen introduced is usually 1.2% or less. The low extent of oxidation during this step may be estimated by carboxyl and carbonyl analysis. Although some hydrolytic cleavage of glucosidic linkages takes place, this cleavage is not extensive as evidenced by the considerable strength retained by the product. Drastic loss of strength is a consequence of a relatively small amount of cleavage of glucosidic linkages. The extent of this cleavage may be more accurately estimated by DR (degree of polymerization) determinations.
No claim is made singly for the partial etherification or for the nitric acid treatment step. The process of this invention utilizes the unique complementary or synergistic effect of the combination of the two treatments.
The partial etherification step may be carried out by any of the known methods which will be apparent to those skilled in the art.
Partial aminoethylation of cotton may be carried out, for example, as described by Guthrie in Textile Research Journal 17, 625-9 (1957). The aminoethyl ether of cellulose may be represented by the formula in which R represents the anhydroglucose unit.
Partial carbamoylethylation of cotton may be carried out, for example, as described by Frick, Reeves, and Guthrie in Textile Research Journal 27, 2949 (1957). The carbamoylethyl ether of cellulose may be represented by the formula ROCH CH C(O)NH in which R represents the anhydroglucose unit.
Partial car-boxyethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 25, 246-53 (1955). The carboxyethyl ether of cellulose may be represented by the fiormula ROCH CH COOH in which R represents the anhydroglucose unit.
Partial carboxymethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 22, 787-92 (1952). The
3 carboxymethyl ether of cellulose may be represented by the formula ROCH COOH in which R represents the anhydroglucose unit.
Partial cyanoethylation of cotton may be carried out, for example, as described by Daul, Reinhardt, and Reid in Textile Research Journal 25, 24653 (1955) The cyanoethyl etherof cellulose may be represented by the formula ROCH CH CN in which R represents the anhydroglucose unit.
Partial hydroxyethylation of cotton-may be carried out, for example, as described by Lawrie, Reynolds, and Ward in Journal of the Society of Dyers and Colourists 56, 6-17 (1940) The hydroxyethyl ether of cellulose may be represented by the formula ROCH CH OI-I in which R represents the anhydroglucose unit.
Partial phosphonomethylation of cotton may be carried out, for example, as described by Drake, Reeves, and Guthrie in Textile Research Journal 29, 270- 1959). The phosphonomethyl ether of cellulose may be represented' by the formula ROCH P(O) (OH) in which R represents the anhydroglucose unit.
Partially etherified cottons with a degree of substitution of from about 0.04 to about 0.55 are preferred for the process of this invention. The degree of substitution and the severity of conditions required in the nitric acid treatment for good alkali-solubility are inversely related.
In the present invention, the nitric acid treatment step may be carried out within widely varying limits. The treatment may be effected at temperatures ranging from about room temperature to boiling and at nitric acid concentrations varying from about 10% to about 70%. With higher temperatures, the treatment time is reduced'and may be as little as a few seconds. The treatment temperature is correspondingly adjusted in inverse relation to treatment time. With the lower concentrations of nitric acid the time of treatment required is extended and may range to periods of 24 hours or longer. For the lower con centrations of nitric acid, the time of treatment necessary may thus be reduced by an adjustment towards higher temperatures.
The preferred range of conditions for the nitric acid treatment'step thus encompasses treatment times of from about 0.5 minute to about 75 'minutes, at temperatures of from about room temperature to the boiling temperature of the nitric acid solution, using concentrations'of nitric acid of about 10% to about 70%, the time and temperature of the nitric acid treatment being inversely related to thenitric acid concentration.
Uses for alkali-soluble textile material are well known in the art. Among such uses are the preparation of open work fabrics by weavingsoluble yarns and ordinary yarns in such a manner that upon dissolution of the soluble yarns the open-work pattern eifect is produced in the fabric. Other uses may include utilization of alkali-soluble threads for basting or for connecting threads in the string-sock knitting process. The soluble members are readily removed by a subsequent alkali treatment. Alkalisoluble fabric is used as a backing cloth in a process for the manufacture of lace,
Having thus described in a general way the operation of the process of this invention, details of the process are listed below in specific examples which illustrate the application of' the process to cotton textile materials.
The following laboratory techniques were used for determination of strength and alkali-solubility of the products.
Determination of strength-The strength of the cellulosic textile materialswas determined on one-inch strips by the standard test method of the American Society for Testing Materials as specified by A.S.T.M. Committee D-13 in Standard General Methods of Testing Woven Textile Fabrics, Philadelphia, Pennsylvania, 1951, test method D39-49. The results are-expressed as the percentage of the original strength of the fabric which is retained after the treatment.
Determination of alkali-solubility.-Approximately one gram of air-equilibrated cellulose textile material was accurately weighed on an analytical balance. The sample was transferred to a flask containing a boiling 10% aqueous solution of sodium hydroxide in an amount sufficient to give a :1 liquor to sample ratio, by weight. The solution containing the sample was maintained at boiling for 10 minutes. At the end of this period, the solution and residue were quantitatively transferred to a previously weighed centrifuge tube. The tube was then centrifuged for 8 minutes at 1700 r.p.m. to affect separation of the residue and clear supernatant solution. The solution was decanted and the residue washed twice with distilled water, twice with dilute acetic acid solution, and then four times with distilled water. The residue was then dried, equilibrated, and weighed in the analytical balance. From the weight of the residue, the alkali-solubility of the sample was calculated:
Percent alkali-solubility=l00[W EXAMPLE 1 Samples of cotton cloth were: (a) mercerized by treatment with 20% sodium hydroxide; (b) aminoethylated to a D.S. of 0.08 by treatment with Z-aminoethyl sulfuric acid and 40% sodium hydroxide; (c) carbamoylethylated to a D.S. of 0.25 by impregnation with an aqueous solution containing 50% acrylamide and 4% sodium hydroxide followed by heating at C. for five minutes; (d) carboxyethylated to a D.S. of 0.12 by hydrolysis of partially cyanoethylated cotton with 20% sodium hydroxide solution for 16 hours at 25 C.; (e) carboxymethylated to a D.S. of 0.10 by treatment with 17% aqueous chloro- -acetic acid and 50% sodium. hydroxide solution; (f) cyanoethylated to a D.S. of 0.55 by impregnation with 2% sodium hydroxide solution followed by treatment with acrylonitrile at 55 Q; (g) hydroxyethylated to a D.S. of 0.25 byimpregnation with 7% sodium hydroxide solution-followed. by treatment with 10% ethylene oxide in perchloroethylene at 25 C.; (h) phosphonomethylated to a D.S. of 0.04 by treatment with 6.8% disodium salt of chloromethylphosphonic acid in the presence of 25% sodium hydroxide. The fabrics were washed and dried. They were then treated with an aqueous solution containing 70% nitric acid, by weight, for 30 minutes at 26 C. (room temperature), and thoroughly washed with distilled water and dried. The alkali-solubilities of the treated samples are shown in the following table.
Table I Alkali-solubility,
Fabric treated with nitric acid: Percent Mercerized cotton 65.6 Aminoethylated cotton 97.1 Carbamoylethyla-ted cotton 80.5
Carboxyethylated cotton 100.0
Carboxymethyla-ted cotton 98.3 cyanoethylated cotton 96.3 Hydroxyethylated cotton 82.7 Phosphonomethylated cotton 82.8
EXAMPLE 2 A sample of cotton was hydroxyethyl-ated to a D.S. of 0.5'0-by treatment similar to that of sample (g) of Example 1. It was treated with nitric acid as in Example 1. The alkali-solubility was 89.5%.
EXAMPLE 3 Samples of partially carboxymcthylated cotton, D.S. 0.10, were treated with aqueous solutions containing 70% nitric acid, by weight, at 26 C. for various periods of time of from minutes to 75 minutes. For comparison, a sample of mercerized cotton was treated for 75 minutes. The properties of the treated samples are shown in the EXAMPLE 5 Samples of partially carboxymethylated cotton (D.S. 0.08) and of mercerized cotton cloth were treated with an aqueous solution containing 70% nitric acid, by weight, at 40 C. for 5 minutes. The nitric acid treatedcarboxymethylated tabric was 88.4% alkali soluble and retained 73.5% of its original strength. The nitric acid treated mercerized fabric was only 53.0% alkali-soluble and retained 89.4% of its original strength.
EXAMPLE 6 Samples of partially carboxymethylated cotton (D.S. 0.08) and ot mercerized cotton were treated with an aqueous solution containing 35% nitric acid, by weight, at the boil for 0.5 minute. Alkali-solubilities were 96.3% and 27.9%, respectively.
EXAMPLE 7 Samples of partially carboxymethylated cotton (D.S. 0.08) and of mercerized cotton were treated with an aqueous solution containing 10% nitric acid, by weight, at the boil for 4 minutes. Alkalisolubilitics were 96.7% and 53.2%, respectively.
We claim:
1. A process for producing an aqueous alkali soluble cotton cellulosic textile material which comprises etherit'ying the cotton cellulosic textile material to a degree of substitution of from about 0.01 to about 0.6 and oxidizing the cellulose chain of the partially etherified textile material by treating the partially etherified cotton cellulosic textile material with an aqueous solution of nitric acid in a concentration of from about 10% to about by weight, at a temperature of from about room temperature to that of the boiling point of the aqueous nitric acid solution, tor a period of time of trout about 0.5 minute to about minutes, the time and temperature of the nitric acid treatment being inversely related to the nitric acid concentration.
2. The process of claim 1 in which the partial etherification employed is aminoethylation.
3. The process of claim 1 in which the partial etherification employed is carbamoylethylat-ion.
4. The process of claim 1 in which the partial etherification employed is icarboxyet-hylation.
5. The process of claim 1 in which the partial etherification employed is carboxymethyl-ation.
6. The process of claim 1 in which the partial etherification employed is cyanoethyl-ation.
7. The process of claim 1 in which the partial etherification employed is hydroxyethylation.
8. The process of claim 1 in which the partial etherification employed is phosphonomethylation.
References Cited in the file of this patent UNITED STATES PATENTS Datlow Feb. 15, 1949 OTHER REFERENCES Lawrie et al.: J. of the Soc. of 'Dyers and Colourists, 56 pp. 6-17, 1940.
Guthrie: Textile Research J ournal 17, pp. 625-629, 1947.
Erick et al.: Textile Research J. 27, pp. 294-299, 1957.
-D-aul et al.: Textile Research J. 25, pp. 246-253, 1955.
Daul et al. Textile Research J. 22, pp. 787-792, 1952.
Daul et a1; Textile Research J. 25, pp. 246-253, 1955.
Drake et al.: Textile Research J. 29, pp. 270-275, 1959'.
Reinhardt et a1.: Industrial and Engineering Chemistry, vol. 50, No. 1, January 1958, pp. 83-86.
Reinhardt et al.: Textile Research Journal, vol. XXIX, No. 10, October 1959, pp. 802-810, particularly p. 810. l

Claims (1)

1. A PROCESS FOR PRODUCING AN AQUEOUS ALKALI SOLUBLE COTTON CELLULOSIC TEXTILE MATERIAL WHICH COMPRISES PARTIALLY ETHERIFYING THE COTTON CELLULOSE TEXTILE MATERIL TO A DEGREE OF SUBSTITUTION OF FROM ABOUT 0.01 TO ABOUT 0.6 AND OXIDIZING THE CELLULOSE CHAIN OF THE PARTIALLY ETHERIFIED TEXTILE MATERIAL BY TREATING THE PARTIALLY ETHERIFIED COTTON CELLULOSIC TEXTILE MATERIAL WITH AN AQUEOUS SOLUTION OF NITRIC ACID IN A CONCENTRATION OF FROM ABOUT 10% TO ABOUT 70% BY WEIGHT, AT A TEMPERATURE OF FROM ABOUT ROOM TEMPERATURE TO THAT THE BOILING POINT OF THE AQUEOUS NITRIC ACID SOLUTION, FOR A PERIOD OF TIME OF FROM ABOUT 0.5 MINUTE TO ABOUT 75 MINUTES, THE TIME AND TEMPERATURE OF THE NITRIC ACID TREATMENT BEING INVERSELY RELATED TO THE NITRIC ACID CONCENTRATION
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372979A (en) * 1965-02-17 1968-03-12 Agriculture Usa Production of alkali-soluble cellulosic textile materials by the aluminum nitrate treatment of partially etherified cottons and the oxidation of cellulose with aluminum nitrate
US4076933A (en) * 1976-02-27 1978-02-28 International Telephone And Telegraph Corporation Process for producing a regenerated shaped cellulosic fiber
US4076932A (en) * 1976-02-27 1978-02-28 International Telephone And Telegraph Corporation Process for producing regenerated cellulosic articles
US4086418A (en) * 1976-02-27 1978-04-25 International Telephone And Telegraph Corporation Process for producing a regenerated hollow cellulosic fiber
US6051034A (en) * 1998-09-30 2000-04-18 Springs Industries, Inc. Methods for reducing pilling of towels
WO2022002999A1 (en) 2020-07-03 2022-01-06 Agfa-Gevaert Nv A separator for water electrolysis
EP3974559A1 (en) 2020-09-24 2022-03-30 Agfa-Gevaert Nv A manufacturing method for a reinforced separator

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US2461632A (en) * 1947-01-24 1949-02-15 Datlow Joseph Method of nitrating cellulose lacebacking fabrics

Patent Citations (1)

* Cited by examiner, † Cited by third party
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US2461632A (en) * 1947-01-24 1949-02-15 Datlow Joseph Method of nitrating cellulose lacebacking fabrics

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3372979A (en) * 1965-02-17 1968-03-12 Agriculture Usa Production of alkali-soluble cellulosic textile materials by the aluminum nitrate treatment of partially etherified cottons and the oxidation of cellulose with aluminum nitrate
US4076933A (en) * 1976-02-27 1978-02-28 International Telephone And Telegraph Corporation Process for producing a regenerated shaped cellulosic fiber
US4076932A (en) * 1976-02-27 1978-02-28 International Telephone And Telegraph Corporation Process for producing regenerated cellulosic articles
US4086418A (en) * 1976-02-27 1978-04-25 International Telephone And Telegraph Corporation Process for producing a regenerated hollow cellulosic fiber
US6051034A (en) * 1998-09-30 2000-04-18 Springs Industries, Inc. Methods for reducing pilling of towels
WO2022002999A1 (en) 2020-07-03 2022-01-06 Agfa-Gevaert Nv A separator for water electrolysis
EP3974559A1 (en) 2020-09-24 2022-03-30 Agfa-Gevaert Nv A manufacturing method for a reinforced separator
WO2022063584A1 (en) 2020-09-24 2022-03-31 Agfa-Gevaert Nv A manufacturing method for a reinforced separator

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