Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.

Patents

  1. Advanced Patent Search
Publication numberUS3535073 A
Publication typeGrant
Publication dateOct 20, 1970
Filing dateOct 25, 1967
Priority dateOct 25, 1967
Publication numberUS 3535073 A, US 3535073A, US-A-3535073, US3535073 A, US3535073A
InventorsChance Leon H, Daigle Donald J, Drake George L Jr
Original AssigneeUs Agriculture
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Crosslinking cotton with haloalkyl phosphine oxides
US 3535073 A
Abstract  available in
Images(4)
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

- phosphine oxide,

United States Patent Int. Cl. D06m 13/28 US. Cl. 8120 26 Claims ABSTRACT OF THE DISCLOSURE Improved wet wrinkle recovery is obtained by crosslinking cotton in the presence of a base with certain bisand tris(ha1oalky1)phosphine oxides.

A nonexclusive, 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 certain organophosphorus compounds useful as textile finishing agents. Specifically, this invention relates to haloalkyl phosphine oxides. More specifically, this invention relates to a process for crosslinking cellulosic textiles with bisand tris(haloalkyl) phosphine oxides to impart to the finished products Wet wrinkle resistance.

Inventors know of no prior art which would teach the treatment of textiles by any similar process. Details of the work which led to the unexpected discovery of the instant invention have been disclosed by these inventors in their crosslinking Cotton with Halomethylphosphine Oxides, which paper appears in the American Dyestufi Reporter 56(17), page 614 (1967).

The principal object of the instant invention is to provide a process for crosslinking fibrous cellulosic textiles.

A further object of the instant invention is to provide a process for producing fibrous cellulosic textiles with an improved wet wrinkle recovery quality.

In the inventigative work which led to the instant invention it has been found that phosphine oxides of the graphic formula where X is a halogen, will react with cellulosic hydroxyl groups in the presence of alkaline catalysts to crosslink cellulose. It has also been found that phosphine oxides of the graphic formula where X is a halogen, will react with cellulosic hydroxyl groups in the presence of alkaline catalysts to crosslink cellulose.

Compounds which are useful reagents in practicing the invention include tris(chloromethyDphosphine oxide, tris(bromomethyl)phosphine oxide, tris(iodomethyl) methyl bis(chloromethyl)phosphine oxide, methyl bis(bromomethyl)phosphine oxide, methyl bis(iodomethyl)phosphine oxide, and the like.

The reaction of the reagents of the invention, above, with cellulosic materials takes place between the cellulosic hydroxyl groups and the halogen atoms of the phosphine 3,535,073 Patented Oct. 20, 1970 oxides, thereby crosslinking the cellulose through stable ether linkages. Cellulose crosslinking is proven by insolubility of the products of the reaction, which are cellulosic derivatives, in a standard 0.5 molar cupriethylenediamine hydroxide aqueous solutiona common cellulose solvent.

Cotton fibers, regenerated cellulose, and other natural cellulosic fibers can be employed in reducing the invention to practice; nevertheless, the preferred application would be on cotton fabrics.

The tris(chloromethyl)phosphine oxide and methyl bis(chloromethyl)phosphine oxide were unexpectedly found to be soluble in water and in aqueous alkali, and for this reason could be applied to cellulosic materials from a single bath. The bromoand iodo-phosphine oxides are insoluble in water or in aqueous alkali. They can be conveniently applied from miscible organic solvent in which the phosphine oxides are soluble. Dimethylformamide is a particularly suitable solvent for the compounds of this invention. It is preferable that water be present in the solutions of the phosphine oxides so that penetration into cellulosic fibers can be achieved. When a combination of water and an organic solvent is used it is necessary to carry out the application to cellulose in two steps. The aqueous alkali may be applied to the cellulose first, followed by the solution of the phosphine oxide, or the phosphine oxide may be applied first followed by the aqueous alkali.

The application of the water soluble phosphine oxides to cotton fabric may be carried out as follows: The cotton fabric is then impregnated with the solution, the fabric dried and cured at temperatures ranging about from to C. for about from 5 to 30 minutes of time.

The application of the water insoluble phosphine oxides to cotton fabric may be carried out as follows: The phosphine oxide is dissolved in a suitable water-miscible organic solvent, and water added in a quantity such that precipitation of the phosphine oxide does not occur. The fabric is then impregnated with the solution, dried, and cured at temperatures about from 110 to 150 C. for about from 5 to 30 minutes of time, the longer times are required for the lower temperatures.

Any alkali hydroxide or alkali carbonate is a suitable catalyst for the reaction of the bisand tris(haloalkyl) phosphine oxides of the instant invention with cellulosic textiles. Sodium carbonate or sodium hydroxide are preferred catalysts. Catalyst concentrations may be varied about from 0.5% to 10%.

The cellulosic textile can be impregnated and heated by any apparatus conventionally used for processing such materials.

Restating the invention, it can be described in general as a process for imparting wet wrinkle resistance to cotton and other cellulosic textiles comprising:

(a) impregnating a cotton or other cellulosic textile with a solution containing about from 0.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate, and about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris(chloromethyDphosphine oxide, tris(bromomethyl)phosphine oxide, tris- (iodomethyl)phosphine oxide, methyl bis(chloromethyl) phosphine oxide, methyl bis(bromomethyl)phosphine oxide, and methyl bis(iodomethyDphosphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C., and

(c) curing the dried impregnated textile for about from to 30 minutes of time at about from 110 to 150 C., using the longer periods of time with the lower temperatures.

The following examples illustrate the methods of carrying out the invention, and are included for purposes of illustration, not as a limitation thereof. Wrinkle recovery tests were carried out by the Monsanto method, ASTM designation D142459. All percentages and parts in the examples are by weight.

EXAMPLE 1 Eight solutions were prepared by dissolving tris(chloromethyl)phosphine oxide in aqueous sodium hydroxide of the concentrations indicated in Table I. External cooling was employed when necessary to prevent the solution from heating up spontaneously. Each solution contained of the phosphine oxide. Fabric samples were impregnated with the solutions, dried for 5 minutes at 85 C., and cured in an oven for 5 minutes at 150 C. or minutes at 110 C. The samples were then washed free of alkali, and submitted to wet wrinkle recovery tests, and phosphorus and chlorine analyses. The results obtained are shown in Table I. Highest phosphorus and chlorine content, and wet wrinkle recovery values were obtained at 10% NaOH concentration. Fibers from all of the samples were found insoluble in 0.5 molar cupriethylenediamine hydroxide (Cuene).

TABLE 1 NaOII Curing Phos- Wet wrinkle concn., temp., phorus, Chlorine, recovery angle, percent percent percent degrees 110 0. 17 0. 34 185 Control. 1G4

EXAMPLE 2 Fabric samples were treated in exactly the same way as in Example 1 except that methyl bis(chloromethyl) phosphine oxide was used. Fabric and other data are shown in Table II.

All fabric samples were insolubles in Cuene, contained phosphorus and chlorine, and had improved wet wrinkle recovery over the control.

EXAMPLE 3 Tris(bromomethyl)phosphine oxide (5.0 grams) was dissolved in 22.5 grams of dimethyl formamide. Water (22.5 grams) was added. Five samples of cotton printcloth were impregnated with the solution and dried for 5 minutes at 85 C. Each sample was then impregnated with a dilferent concentration of aqueous sodium hydroxide, again dried for 5 minutes at 85 C., and cured for 5 minutes at 150 C. Fabric and other data are shown in Table III.

TABLE III Wet wrinkle Phosphorus, Bromine, recovery angle, NaOH percent percent egrees 0. 15 0. 09 106 0. l4 0. 04 195 0. 11 0.03 180 0. 0!) 0. 02 204 0. 18 0.26 221 Control 164 All of the samples were insoluble in Cuene.

EXAMPLE 4 Methyl bis(iodomethyl)phosphine oxide (5.0 grams) was dissolved in 22.5 grams of dimethyl formamide at 70 C. Water (22.5 grams) was added while holding the temperature at about 70 C. Six samples of cotton printcloth were impregnated with the hot solution and dried for 5 minutes at C. Each sample was then impregnated with a different concentration of aqueous sodium hydroxide, again dried for 5 minutes at 85 C., and cured for 5 minutes at 150 C. Fabric and other data are shown in Table IV.

A number of samples of cotton printcloth were treated with methyl bis(chloromethyl)phosphine oxide as in Example 2 except that sodium carbonate solutions were used instead of the sodium hydroxide solutions. Crosslinking was observed as present in the treated samples when determined by their insolubility in the Cuene.

EXAMPLE 6 A sample of printcloth was treated with tris(bromomethyl)phosphine oxide as in Example 3 except that a 10% sodium carbonate solution was used instead of 10% sodium hydroxide solution. The fibers were insoluble in the Cuene. The fabric contained 0.12% phosphorus and 0.23% bromine.

We claim:

1. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with a solution containing about from 0.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate, and about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris(chloromethyl)phosphine oxide, tris(bromornethyl)phosphine oxide, tris (iodomethyl)phosphine oxide, methyl bis(chloromethyl)phosphine oxide, methyl bis(bromomethyl) phosphine oxide, and methyl bis(iodomethyl)ph0sphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C., and

(c) curing the dried, impregnated textile for about from 5 to 30 minutes of time at about from 110 to C., using the longer periods of time with the lower temperatures.

2. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with an aqueous solution containing about from 2.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate, and about from to of a haloalkylphosphine oxide selected from the group consisting of tris(chloromethyl)phosphine oxide, and methyl bis(chloromethyl)phosphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C., and

(c) curing the dried, impregnated textile for about from 5 to 30 minutes of time at about from 110 to 150 C., using the longer periods of time with the lower temperatures.

3. The process of claim 2 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is tris(chloromethyl)phosphine oxide.

4. The process of claim 2 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is methyl bis(chloromethyl)phosphine oxide.

5. The process of claim 2 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is tris (chloromethyl) phosphine oxide.

6. The process of claim 2 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is methyl bis(chloromethyl)phosphine oxide.

7. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with an aqueous solution containing about from 1.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C.,

(c) impregnating the dried textile from step (b) with a 50% aqueous dimethylformamide solution containing about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris(bromomethyl)phosphine oxide, and methyl his (bromomethyl)phosphine oxide,

(d) drying the reimpregnated textile from step (c) for about 5 minutes of time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5 to 30 minutes of time at about from 110 to 150 C., using the longer periods of time with the lower temperatures.

8. The process of claim 7 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is tris(bromomethyl) phosphine oxide.

9. The process of claim 7 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is methyl bis(bromomethyl)phosphine oxide.

10. The process of claimv 7 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is tris(bromomethyl)phosphine oxide.

11. The process of claim 7 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is methyl bis(bromomethyl)phosphine oxide.

12. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with an aqueous solution containing about from 0.5 to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C.,

(c) impregnating the dried textile from step (b) with a 50% aqueous dimethylformamide solution at 70 C. containing about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris(iodomethyl)phosphine oxide, and methyl bis (iodomethyl)phosphine oxide,

(d) drying the reimpregnated textile from step (c) for about 5 minutes of time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5 to 30 minutes of time at about from 110 to 150 C., using the longer periods of time with the lower temperatures.

13. The process of claim 12 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is tris(iodomethyl)phosphine oxide.

14. The process of claim 12 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is methyl bis (iodomethyl)phosphine oxide.

15. The process of claim 12 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is tris(iodomethyl)phosphine oxide.

16. The process of claim 12 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is methyl bis(iodomethyl)phosphine oxide.

17. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with a 50% aqueous dimethylformamide solution containing about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris (bromomethyl)phosphine oxide, and methyl bis (bromomethyl) phosphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time at about C.,

(c) impregnating the dried textile from step (b) with an aqueous solution containing about from 1.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate,

(d) drying the reimpregnated textile from step (c) for about 5 minutes of time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5 to 30 minutes of time at about from to C., using the longer periods of time with the lower temperatures.

18. The process of claim 17 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is tris bromomethyl phosphine oxide.

19. The process of claim 17 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is methyl bis(bromomethyl)phosphine oxide.

20. The process of claim 17 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is tris (bromomethyl) phosphine oxide.

21. The process of claim 17 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is methyl bis(bromomethyl)phosphine oxide.

22. A process for imparting wet wrinkle resistance to a cellulosic textile comprising (a) impregnating the cellulosic textile with a 50% aqueous dimethylformamide solution at 70 C. containing about from 5% to 10% of a haloalkylphosphine oxide selected from the group consisting of tris(iodomethyl)phosphine oxide, and methyl bis (iodomethyl) phosphine oxide,

(b) drying the wet, impregnated textile for about 5 minutes of time at about 85 C.,

(c) impregnating the dried textile from step (b) with an aqueous solution containing about from 0.5% to 10% of an alkali catalyst selected from the group consisting of sodium hydroxide and sodium carbonate,

(d) drying the reimpregnated textile from step (c) for about 5 minutes of time at about 85 C., and

(e) curing the twice-impregnated, twice-dried textile for about from 5 to 30 minutes of time at about from 110 to 150 C., using the longer periods of time with the lower temperatures.

23. The process of claim 22 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is tris(iodomethyl)phosphine oxide.

24. The process of claim 22 wherein the alkali catalyst is sodium hydroxide and the haloalkylphosphine oxide is methyl bis(iodomethyl)phosphine oxide.

25. The process of claim 22 wherein the alkali catalyst is sodium carbonate and the haloalkylphosphine oxide is tris (iodomethyl)phosphine oxide.

is sodium carbonate and the haloalkylphosphine oxide is methyl bis(iodomethyl)phosphine oxide.

References Cited UNITED STATES PATENTS Van Gorder et a1. 8-120 Dock Fon Toy et a1. 8-116 'Reeves et a1. 8116 Drake et a1. 8--120 1 Goldstein et a1. 8-116 7 26. The process of claim 22 wherein the alkali catalyst 8 FOREIGN PATENTS 893,283 4/1962 Great Britain.

OTHER REFERENCES 5 Drake et al., Textile Research Journal, vol. 29, pp.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2678330 *Feb 23, 1951May 11, 1954Celanese CorpBis-(2,3-dihalopropyl) chlorophosphonate
US2714100 *Aug 5, 1952Jul 26, 1955Victor Chemical WorksDiallyl monochloromethanephosphonate and polymers
US2814573 *Nov 9, 1954Nov 26, 1957Wilson A ReevesOrganic polymeric compositions containing nitrilo methylol-phosphorus polymers and bromine compounds
US2979374 *Oct 31, 1957Apr 11, 1961Drake Jr George LFibrous textile cellulosic phosphonomethyl ethers and process of preparation
US3160515 *Dec 18, 1961Dec 8, 1964Koppers Co IncMethod of treating wood with an improved fire retardant composition
GB893283A * Title not available
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US5300240 *Apr 2, 1993Apr 5, 1994Societe Francaise HoechstFinishing process for textiles, finishing bath for textiles using phosphinicosuccinic acid, phosphinicobissuccinic acid or their mixtures, finished textiles and use of said acids as finishes
US5385680 *Jan 24, 1994Jan 31, 1995Societe Francaise HoechstFinishing process for textiles, finishing bath for textiles using phosphinicosuccinic acid, phosphinicobissuccinic acid or their mixtures, finished textiles and use of said acids as finishes
EP0564346A1 *Mar 29, 1993Oct 6, 1993SOCIETE FRANCAISE HOECHST Société anonyme dite:Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof
Classifications
U.S. Classification8/120
International ClassificationD06M13/00, D06M13/285
Cooperative ClassificationD06M13/285
European ClassificationD06M13/285