US3294780A - Process for making crosslinked cellulose derivatives utilizing halo-acrylic acids - Google Patents

Process for making crosslinked cellulose derivatives utilizing halo-acrylic acids Download PDF

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US3294780A
US3294780A US338533A US33853364A US3294780A US 3294780 A US3294780 A US 3294780A US 338533 A US338533 A US 338533A US 33853364 A US33853364 A US 33853364A US 3294780 A US3294780 A US 3294780A
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cellulose
acid
salt
halo
sodium hydroxide
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Austin L Bullock
Charles H Mack
John D Guthrie
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof

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  • This invention relates to crosslinked fibrous cellulose derivatives containing free reactive carboxyl groups, and to a process for producing same.
  • crosslinking is closely related to the set that is imparted to cotton cellulose either in the attainment of resiliency and permanent creases in washwear fabrics or in the development of a fiber or yarn crimp needed to produce stretch yarns and fabrics.
  • the presence of hydrophylic groups also have a pronounced effect on the properties.
  • cellulose can be crosslinked by means of halo-acrylic acids, such as chloroacrylic acid.
  • halo-acrylic acids such as chloroacrylic acid.
  • These cellulose derivatives which contain both crosslinks between cellulose chains and free, reactive carboxyl groups may be highly substituted, and at the same time may be insoluble and highly resistant to swelling. in addition these derivatives possess improved wrinkle resistant properties, and increased water of imbibition, which is an indication of increased moisture absorptivity.
  • These derivatives can be prepared from either granular or fibrous cellulose; from yarns or from fabrics.
  • the cellulose may be obtained from wood pulp, cotton, hemp, ramie, or it may be a regenerated cellulose, such as rayon.
  • the cellulose derivatives provide an improved absorbent material, as well as an ion exchange material of value in biochemical separations and other chemical processes.
  • the derivatives when produced in the yarn form or in the fabric form provide useful textile materials which have an enhanced afiinity for basic dyes.
  • the tabrics also possess improved wrinkle resistant properties.
  • the said cellulosic derivatives, object of this invention may be prepared by reacting cellulose with a halo-acrylic acid such as alpha-chloroacrylic acid, beta-chloroacrylic acid, alpha-beta-dichloroacrylic acid, and the alkali metal salts of these acids, in the presence of sodium hydroxide.
  • a halo-acrylic acid such as alpha-chloroacrylic acid, beta-chloroacrylic acid, alpha-beta-dichloroacrylic acid, and the alkali metal salts of these acids, in the presence of sodium hydroxide.
  • the pure acid, if liquid, can be used, or it can be diluted with a suitable solvent, such as water or acetone.
  • the preferred concentration of the sodium hydroxide is an aqueous 20% to 40%; however, the concentration of the sodium hydroxide may vary widely so long as it is present in excess of the amount necessary to neutralize 3,294,780 Patented Dec. '27, 1966 "ice any acidic materials developed during the reaction.
  • the sodium hydroxide may be applied to the cellulosic material either prior to the acid, or simultaneously with the salt of the acid, or after the cellulosic material has been impregnated with the acid. When the cellulosic material is being impregnated in either the yarn or the fabric form the process is carried out in standard padding equipment. The reaction in such cases is completed by curing the textile material at temperatures about from to -120 C.
  • the extent of the reaction is limited at temperatures lower than about 80 C., and excessive yellowing occurs at temperatures higher than about 1 20" C.
  • the alkali metal salts of the haloacrylic acids we prefer to cure at temperatures of from C. to 120 C. for periods of from 10 to 30 minutes, the lower temperatures being used with the longer time intervals.
  • the free haloacrylic acids we prefer to cure at temperatures of from C. to C. for periods of from 15 to 30 minutes, the lower temperatures being used with the 10m er time intervals.
  • the heat of neutralization and/ or reaction may be sufiicient to complete the reaction.
  • the salt alone, or the acid and the sodium hydroxide mixedprior to impregnation are used for impregnation, curing at the higher temperatures is necessary.
  • the material is, treated with dilute hydrochloric acid to convert the carboxylic acid groups from the basic to the acidic form.
  • the cellulosic derivative is then washed with water, to eliminate the ionic chlorine.
  • Resiliency of these derivatives is established by employing the Wrinkle Recovery Test (ASTM Dl295-60T) values obtained upon testing the fabrics as the criteria. Absorbency of these derivatives is established by using the water of imbibition values as the, criterion. An increase in the value of the imbibitioncom-pa-red with the untreated cellulosic materialindicates increased absorbency in the treated cellulosic derivative.
  • Example 1 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of the potassium salt of aIpha-chlo-roacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by Weight of water. The wet sample was placed on a pinframe, and dried and cured 10 minutes at 100 C.
  • the sample was then Washed, while still on the pinframe, with running tap water until free of caustic, and dried on the pinframe.
  • the product was insoluble in a 0.5 molar aqueous cupriethylenediamine hydroxide solution, and had a carboxyl content of 49.7 millimoles per 100 grams.
  • the Wrinkle Recovery Tests (ASTM D1295- 60T) yielded respectively wet and dry values of 230 and 203, warp and filling, (W and F), as compared to the 10% sodium hydroxide treated fabric values, which were respectively 171 and 187 (W and F).
  • the fabric treated by process of this invention had a water of imbibit-ion value of 50%, while the 20% sodium hydroxide treated fabric had a value of 37%, and the untreated printcloth a value of 31%.
  • the water of imbibition. value is here used as the criterion for evaluation of the absorbency of the fabrics, and is substantially different from moisture regain at 65% relative humidity. (Ref. Textile Research 1., vol. 30, No. 3, March 1960.)
  • Example 2 A sample of cotton printcloth was padded with a solution containing parts by Weight of the sodium salt of beta-chloroacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by weight of water. The wet sample was framed, dried and cured, washed, and dried as was the sample processed in Example 1.
  • the product was insoluble in the 0.5 molar cupriethylenediamine hydroxide solution, and had a carboxyl content of 38.7 millimoles per 100 grams.
  • the wet and dry wrinkle recovery angle values were respectively 216 and 181 (W and F) compared with the corresponding values of 171 and 187 [for the 20% sodium hydroxide treated fabric values.
  • the fabric treated by the process of our invention had a water of irnbibition value of 44%, while the 20% sodium hydroxide treated fabric had a value of 37%, and the untreated cotton printcloth a value of 31%.
  • Example 3 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of the sodium salt of alpha-beta-dichloroacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by weight of water. The wet sample was framed, dried and cured, washed, and dried as was the sample processed in Example 1.
  • the product was insoluble in the 0.5 mole cupriethylenediamine hydroxide solution, and had a carboxyl content of 32.5 millimoles per 100 grams.
  • the wet and dry wrinkle recovery angle values were respectively 227 and 198 (W and F) compared with the corresponding 171 and 187 values of the 20% sodium hydroxide treated fabric.
  • Example 4 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of alpha-beta-dichloroacrylic acid, and 90 parts by weight of water, and dried in a vented oven for minutes at 65 C. The dry fabric sample was then padded with a sodium hydroxide solution, placed on a pinframe, and cured 15 minutes at 120 C. The chemically modified fabric was then washed with water until free of caustic, and dried.
  • Example 5 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of alpha-beta-dichloroacrylic acid, and parts by weight of water, and dried in a vented oven for 15 minutes at 65 C. The dry fabric sample was then padded with a 40% sodium hydroxide solution, placed on a pinframe, and cured 30 minutes at 105 C. The chemically modified fabric was removed from the frame, washed free of caustic, refrained, and dried. It was insoluble in the 0.5 molar cupriethylenediamine hydroxide solution, and had a carboxyl content of 23 millimoles per grams.
  • a process for crosslinking cellulose which comprises:
  • a process for crosslinking cellulose which comprises:

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

United States Patent PROCESS FOR MAKING CROSSLINKED CELLU- LOSE DERIVATIVES UTILIZING HALO-ACRYL- IC ACIDS Austin L. Bullock, Charles H. Mack, and John D. Guthrie, New Orleans, La., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed Jan. 17, 1964, Ser. No. 338,533
5 Claims. (Cl. 260-212) 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 power to grant sublicenses (for such purposes, is hereby granted to the Government of the United States of America.
This invention relates to crosslinked fibrous cellulose derivatives containing free reactive carboxyl groups, and to a process for producing same.
-It is Well known that highly substituted cellulose derivatives containing su'bstituents having hydrophilic groups such as carboxymethylcellulose tend to swell, gelatinize, or even dissolve in either dilute acids, dilute alkalies, or water. This tendency to swell, gelatinize, or dissolve when highly substituted prevents the use of such derivatives in many cases where insolubility and a low degree of swelling are important.
:It is also well known that crosslinking is closely related to the set that is imparted to cotton cellulose either in the attainment of resiliency and permanent creases in washwear fabrics or in the development of a fiber or yarn crimp needed to produce stretch yarns and fabrics. The presence of hydrophylic groups also have a pronounced effect on the properties.
While crosslinking is accomplished by reacting cellulose with di-halo and di-vinyl derivatives there have been no reports of the reaction of vinyl halides with cellulose to form either a chemically modified cellulose or a crosslinked cellulose.
We have discovered that cellulose can be crosslinked by means of halo-acrylic acids, such as chloroacrylic acid. These cellulose derivatives, which contain both crosslinks between cellulose chains and free, reactive carboxyl groups may be highly substituted, and at the same time may be insoluble and highly resistant to swelling. in addition these derivatives possess improved wrinkle resistant properties, and increased water of imbibition, which is an indication of increased moisture absorptivity.
These derivatives can be prepared from either granular or fibrous cellulose; from yarns or from fabrics. The cellulose may be obtained from wood pulp, cotton, hemp, ramie, or it may be a regenerated cellulose, such as rayon. The cellulose derivatives provide an improved absorbent material, as well as an ion exchange material of value in biochemical separations and other chemical processes. The derivatives when produced in the yarn form or in the fabric form provide useful textile materials which have an enhanced afiinity for basic dyes. The tabrics also possess improved wrinkle resistant properties.
The said cellulosic derivatives, object of this invention, may be prepared by reacting cellulose with a halo-acrylic acid such as alpha-chloroacrylic acid, beta-chloroacrylic acid, alpha-beta-dichloroacrylic acid, and the alkali metal salts of these acids, in the presence of sodium hydroxide. The best results are obtained when an excess of the alkali is used. The pure acid, if liquid, can be used, or it can be diluted with a suitable solvent, such as water or acetone.
The preferred concentration of the sodium hydroxide is an aqueous 20% to 40%; however, the concentration of the sodium hydroxide may vary widely so long as it is present in excess of the amount necessary to neutralize 3,294,780 Patented Dec. '27, 1966 "ice any acidic materials developed during the reaction. The sodium hydroxide may be applied to the cellulosic material either prior to the acid, or simultaneously with the salt of the acid, or after the cellulosic material has been impregnated with the acid. When the cellulosic material is being impregnated in either the yarn or the fabric form the process is carried out in standard padding equipment. The reaction in such cases is completed by curing the textile material at temperatures about from to -120 C. The extent of the reaction is limited at temperatures lower than about 80 C., and excessive yellowing occurs at temperatures higher than about 1 20" C. In those instances where the alkali metal salts of the haloacrylic acids are employed, we prefer to cure at temperatures of from C. to 120 C. for periods of from 10 to 30 minutes, the lower temperatures being used with the longer time intervals. In those instances where the free haloacrylic acids are employed, we prefer to cure at temperatures of from C. to C. for periods of from 15 to 30 minutes, the lower temperatures being used with the 10m er time intervals.
If the pure acid in a concentrated solution of the acid is used for impregnation the heat of neutralization and/ or reaction may be sufiicient to complete the reaction. However, if either the salt alone, or the acid and the sodium hydroxide mixedprior to impregnation, are used for impregnation, curing at the higher temperatures is necessary. Once the reaction is complete the cellulosic material is washed until free of alkali, and dried in any feasible manner.
Proof of crosslinkage is established by submitting the cellulosic derivative to wetting with cupriethylenediamine hydroxide solution. The latter swells and dissolves cellulose, but does not afiect crosslinked celluloses. The presence of available carboxylic acid sites is indicated by the affinity of the cellulosic materials for dyes such as methylene blue. This is confirmed by titration of the cellulosic derivative with a standardized base solution.
-Prior to titration the material is, treated with dilute hydrochloric acid to convert the carboxylic acid groups from the basic to the acidic form. The cellulosic derivative is then washed with water, to eliminate the ionic chlorine.
Resiliency of these derivatives is established by employing the Wrinkle Recovery Test (ASTM Dl295-60T) values obtained upon testing the fabrics as the criteria. Absorbency of these derivatives is established by using the water of imbibition values as the, criterion. An increase in the value of the imbibitioncom-pa-red with the untreated cellulosic materialindicates increased absorbency in the treated cellulosic derivative.
The following examples are illustrative of the invention, and show parts and percentages by weight, unless otherwise stated.
Example 1 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of the potassium salt of aIpha-chlo-roacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by Weight of water. The wet sample was placed on a pinframe, and dried and cured 10 minutes at 100 C.
The sample was then Washed, while still on the pinframe, with running tap water until free of caustic, and dried on the pinframe. The product was insoluble in a 0.5 molar aqueous cupriethylenediamine hydroxide solution, and had a carboxyl content of 49.7 millimoles per 100 grams. The Wrinkle Recovery Tests (ASTM D1295- 60T) yielded respectively wet and dry values of 230 and 203, warp and filling, (W and F), as compared to the 10% sodium hydroxide treated fabric values, which were respectively 171 and 187 (W and F).
The fabric treated by process of this invention had a water of imbibit-ion value of 50%, while the 20% sodium hydroxide treated fabric had a value of 37%, and the untreated printcloth a value of 31%.
Note: The water of imbibition. value is here used as the criterion for evaluation of the absorbency of the fabrics, and is substantially different from moisture regain at 65% relative humidity. (Ref. Textile Research 1., vol. 30, No. 3, March 1960.)
Example 2 A sample of cotton printcloth was padded with a solution containing parts by Weight of the sodium salt of beta-chloroacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by weight of water. The wet sample was framed, dried and cured, washed, and dried as was the sample processed in Example 1.
The product was insoluble in the 0.5 molar cupriethylenediamine hydroxide solution, and had a carboxyl content of 38.7 millimoles per 100 grams. The wet and dry wrinkle recovery angle values were respectively 216 and 181 (W and F) compared with the corresponding values of 171 and 187 [for the 20% sodium hydroxide treated fabric values.
The fabric treated by the process of our invention had a water of irnbibition value of 44%, while the 20% sodium hydroxide treated fabric had a value of 37%, and the untreated cotton printcloth a value of 31%.
Example 3 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of the sodium salt of alpha-beta-dichloroacrylic acid, 20 parts by weight of sodium hydroxide, and 70 parts by weight of water. The wet sample was framed, dried and cured, washed, and dried as was the sample processed in Example 1.
.The product was insoluble in the 0.5 mole cupriethylenediamine hydroxide solution, and had a carboxyl content of 32.5 millimoles per 100 grams. The wet and dry wrinkle recovery angle values were respectively 227 and 198 (W and F) compared with the corresponding 171 and 187 values of the 20% sodium hydroxide treated fabric.
Example 4 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of alpha-beta-dichloroacrylic acid, and 90 parts by weight of water, and dried in a vented oven for minutes at 65 C. The dry fabric sample was then padded with a sodium hydroxide solution, placed on a pinframe, and cured 15 minutes at 120 C. The chemically modified fabric was then washed with water until free of caustic, and dried. It was insoluble in the 0.5 molar cupriethylenediamine hydroxide solution, and had a carboxyl content of 19 millimq s P 100 m 4 Example 5 A sample of cotton printcloth was padded with a solution containing 10 parts by weight of alpha-beta-dichloroacrylic acid, and parts by weight of water, and dried in a vented oven for 15 minutes at 65 C. The dry fabric sample was then padded with a 40% sodium hydroxide solution, placed on a pinframe, and cured 30 minutes at 105 C. The chemically modified fabric was removed from the frame, washed free of caustic, refrained, and dried. It was insoluble in the 0.5 molar cupriethylenediamine hydroxide solution, and had a carboxyl content of 23 millimoles per grams.
We claim:
1. A process for crosslinking cellulose which comprises:
(a) impregnating the said cellulose with an aqueous mixture containing an alkali salt of a halo-acrylic acid selected from the group consisting of the potassium salt of alpha-chloroacrylic acid, the sodium salt of beta-chloroacrylic acid, and the sodium salt of alpha beta-dichloroacrylic acid in combination with sodium hydroxide, the ratio of salt to sodium hydroxide to water being 1:2:7, respectively, and
(b) drying and curing the said impregnated cellulose for about from 10 to 30 minutes, at about from 100 to 120 C., the shorter periods of time used with the higher temperatures.
2. The process of claim 1 wherein the said alkali salt is the potassium salt of alpha-chloroacrylic acid.
3. The process of claim 1 wherein the said alkali salt is the sodium salt of beta-chloroacrylic acid.
4. The process of claim 1 wherein the said alkali salt is the sodium salt of alpha-beta-dichloroacrylic acid.
5. A process for crosslinking cellulose which comprises:
(a) impregnating the said cellulose with an aqueous alpha-beta-dichloroacrylic acid solution,
( b) drying the wet cellulose for about 15 minutes at about 65 C.,
(c) impregnating the dried cellulose with an aqueous sodium hydroxide solution about from 20% to 40% by Weight, and
(d) drying and curing the Wet cellulose for about from 15 to 30 minutes, at about from to C., the shorter periods of time used with the higher temperatures.
References Cited by the Examiner UNITED STATES PATENTS 2,524,399 10/ 1950 Schoene et al. 8-116 3,208,994 9/1965 Flodin 260-209 DONALD E. CZAJA, Primary Examiner.
R- W. MULCAHY, Assistant Examiner.

Claims (1)

1. A PROCESS FOR CROSSLINKING CELLULOSE WHICH COMPRISES: (A) IMPREGNATING THE SAID CELLULOSE WITH AN AQUEOUS MIXTURE CONTAINING AN ALKALI SALT OF A HALO-ACRYLIC ACID SELECTED FROM THE GROUP CONSISTING OF THE POTASSIUM SALT OF ALPHA-CHLOROACRYLIC ACID, THE SODIUM SALT OF BETA-CHLOROCACRYLIC ACID, AND THE SODIUM SALT OF ALPHA-BETA-DICLOROACRYLIC ACID IN COMBINATION WITH SODIUM HYDROXIDE, THE RATIO OF SALT TO SODIUM HYDROXIDE TO WATER BEING 1:2:7. RESPECTIVELY, AND (B) DRYING AND CURING THE SAID IMPREGNATED CELLULOSE FOR ABOUT FROM 10 TO 30 MINUTES, AT ABOUT FROM 100* TO 120*C., THE SHORTER PERIODS OF TIME USED WITH THE HIGHER TEMPERATURES.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328971A2 (en) * 1988-02-16 1989-08-23 BASF Corporation Method of preparing cellulosic fibers having increased absorbency
WO2016156930A1 (en) * 2015-03-31 2016-10-06 Indian Institute Of Technology - Kanpur A process for preparation of bioplastics

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524399A (en) * 1948-07-07 1950-10-03 Us Rubber Co Cellulose treated with di-vinyl sulfone to shrinkproof
US3208994A (en) * 1961-10-25 1965-09-28 Pharmacia Ab Process for preparing hydrophilic copolymerization and product obtained thereby

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2524399A (en) * 1948-07-07 1950-10-03 Us Rubber Co Cellulose treated with di-vinyl sulfone to shrinkproof
US3208994A (en) * 1961-10-25 1965-09-28 Pharmacia Ab Process for preparing hydrophilic copolymerization and product obtained thereby

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0328971A2 (en) * 1988-02-16 1989-08-23 BASF Corporation Method of preparing cellulosic fibers having increased absorbency
EP0328971A3 (en) * 1988-02-16 1991-11-27 BASF Corporation Method of preparing cellulosic fibers having increased absorbency
WO2016156930A1 (en) * 2015-03-31 2016-10-06 Indian Institute Of Technology - Kanpur A process for preparation of bioplastics

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