US2925317A - Shrinkproofing of protein fibers with polyalkyleneimines - Google Patents

Shrinkproofing of protein fibers with polyalkyleneimines Download PDF

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Publication number
US2925317A
US2925317A US610690A US61069056A US2925317A US 2925317 A US2925317 A US 2925317A US 610690 A US610690 A US 610690A US 61069056 A US61069056 A US 61069056A US 2925317 A US2925317 A US 2925317A
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imine
shrinkproofing
solution
fiber
wool
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US610690A
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Joseph E Moore
Jr Clay E Pardo
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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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines

Definitions

  • This invention relates to processes for shrinkproofing and felt-proofing proteinaceous fibers, especially wool.
  • the invention is concerned with procedures wherein the fiber is treated with a preformed polyalkyleneimine and then cured withthe application of heat whereby to produce a fiber which exhibits a marked resistance to shrinkage as compared with the original fiber. Further objects and advantages of the invention will be obvious from the description herein.
  • These compounds can be prepared, for .example, by polymerizing the alkylene imine in the pres.- ence of a catalyst such as sodium bisulphate, hydrochloric acid, sulphuric acid, acetic acid, hydrogen peroxide, and so forth.
  • a catalyst such as sodium bisulphate, hydrochloric acid, sulphuric acid, acetic acid, hydrogen peroxide, and so forth.
  • the solution applied to the protein fibers inaccordance with this invention contains as its principal ingredient the preformed polyalkylene imine.
  • concentration of this agent in the solution is not critical and may be, for
  • the solution may contain both water and a watersoluble organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl a1cohol,'any of the isomeric butyl alcohols, acetone, etc.
  • a mixed solvent of water and alcohol or ketone is particularly useful where the particular imine chosen is not completely water-soluble.
  • the treating solution should be preferably alkaline,
  • agents such as sulphuric acid, hydrochloric acid, phosphoric acid,
  • the wool After the wool has been impregnated with the imine .solution, it is subjected to a heat curing operation. This simply involves subjecting the textile material to a temperature from about 75 to about 150C. to promote reaction between the imine and the wool whereby the imine becomes bonded to the protein molecule and can tific basis.
  • the polyalkylene imine actually reacts with the wool, forming part of the formed by immersing the wool in an excess of the solu- 7 tion or by applying the solution by spraying, brushing or other conventional application techniques. To assist in wetting the wool with the solution, it may be run through padding rolls or the like.
  • polyethylene imine is the preferred shrinkproofing agent of this invention
  • any other polyalkylene imine Typical examples are the polymers of: propylene imine; 1,2-butylene imine; 2,3-buty1ene no longer be removed by washing.
  • the time of cure will vary depending on the temperature selected, the chemical nature of the fiber being treated, the degree of shrinkproofing desired, and so on. In general, a cure time of about 15 min. to about 2 hours may be used.
  • a preferred curing operation involves heating for about 30 minutes to one hour at C.
  • the textile material After the textile material has been cured it may be Washed with water or laundered to remove excess imine which'is not actually bonded to the protein molecules. The textile material is then dried in the usual manner and is ready for use.
  • the proportion of polyalkylene imine bonded to the protein fiber may be varied widely by varying the concentration of polyalkylenimine in the treatment solution taken up by the fibrous material. Usually these conditions are so chosen that the fiber takes up about from 0.1% to 10% of its weight of polyalkylene imine. In general the larger the proportion of imine taken up by the fiber, the greater will be the shrinkage protection afiorded. It is also obvious that the degree of shrinkproofing attained will vary depending on such factors as the original characteristics of the fiber, the type of polyalkylene imine chosen and so forth. In any particular situation the fiber may be subjected to pilot experiments, applying different proportions of the chosen polyalkylene imine and selecting the conditions which give the desired degree of shrinkproofing.
  • the process. of. this invention is particularly adapted for the treatment of wool but may also be applied to other proteinaceous fiberssuch as mohair, fibers from fleece-bearing animals other than sheep and goats, animal hair, silk, fibers made from proteins such as zein,.casein, peanut protein, keratin, etc.
  • the proteinaceous fiber may be in the form of actual fibers or may be in the form of threads, yarns, woven or knitted materials, garments, etc.
  • EXAMPLE An aqueous solution was prepared containing of polyethylene imine (molecular weight about 20,000 to 30,000). The solution had a pH of 11.3.
  • the cloth samples were then placed in an oven where they were subjected to a temperature of 120 C. One lot of the samples was subjected to this heat for 30 minutes, another lot for 60 minutes.
  • the cured cloth samples were weighed to determine the uptake of polyethylene imine.
  • the shrinkage characteristics of the cloth samples were determined 'by subjecting them to a laundering operation in which the cloth was violently agitated in a 0.5% solution of sodium oieate at 40 C. with a cloth to solution ratio of 1:50, the area of the cloth being measuredbefore and after laundering. With this method of laundering, untreated cloth samples gave an area shrinkage of 36%.
  • samples of the cloth which had been subjected to the above polyethylene imine treatment and curing were washed for 2 hours in running hot (55 C.) water. After'this washing treatment the samples were dried and the residual polyethylene imine content was determined as well as shrinkage by the above laundering treatment.
  • a process for shrinkproofing protein fibers which comprises impregnating the protein fiber with an aqueous alkaline solution, having a pH about from 9-to 11, containing a preformed polyethylene imine having-a molecular weight of about from 20,000 to 30,000, and curing the impregnated protein fiber at a temperature from about C. to about 150 C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Description

, 2,925,317 Patented Feb. 16, 96Q
SHRINKPROOFING OF PROTEIN FIBERS WITH 7 POLYALKYLENEIMINES Joseph E. Moore, Pinole, and Clay E. Pardo, Jr.', Albany,
Califl, assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Application September 18,1956 Serial N- 610,690
. 4 Claims. c1. ti-127.6) I (Granted under Title 35, US. Code (1952), sec. 266) A non-exclusive,irrevocable, royalty-free license in theinvention herein described, throughout the world for all purposes of the United States Government, with the powerto grant sublicenses for such purposes, is hereby granted to the Government of the United States of America.
This invention relates to processes for shrinkproofing and felt-proofing proteinaceous fibers, especially wool. In particular, the invention is concerned with procedures wherein the fiber is treated with a preformed polyalkyleneimine and then cured withthe application of heat whereby to produce a fiber which exhibits a marked resistance to shrinkage as compared with the original fiber. Further objects and advantages of the invention will be obvious from the description herein.
It is well known that laundering causessevere shrinkage to woolen textiles. This technical disadvantage seriously restricts the applications of wool in the textile industry and much research has been undertaken to modify the natural fiber to improve its shrinkage properties'. In general, known methods of treating wool to imine; 2,2-dimethy1-ethylene imine; 2,2,3-trimethylethylene imine; 2,2-dimethyl-3-propyl-ethylene imine; cyclohexyl fethylene imine; phenyl ethylenimine, etc.
These compounds, as well known in the art, can be prepared, for .example, by polymerizing the alkylene imine in the pres.- ence of a catalyst such as sodium bisulphate, hydrochloric acid, sulphuric acid, acetic acid, hydrogen peroxide, and so forth. Generally, it is preferred to use the polyalkylene imines which are at least partially soluble in water.
The solution applied to the protein fibers inaccordance with this invention contains as its principal ingredient the preformed polyalkylene imine. The concentration of this agent in the solution is not critical and may be, for
example, as low as 0.1% or 'as high as 10%. Usually water is used as the sole solvent for the imine. However, the solution may contain both water and a watersoluble organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl a1cohol,'any of the isomeric butyl alcohols, acetone, etc. The use of a mixed solvent of water and alcohol or ketone is particularly useful where the particular imine chosen is not completely water-soluble.
' In order to achieve a maximum shrinkproofing effect, it is necessary to control the pH of the polyalkylene imine solution which is applied to the protein fiber. "Acid conditions are not suitable as they prevent production of a shrink-resistant product. To achieve best results, the treating solution should be preferably alkaline,
improve its shrinkage characteristics have the disadjust the pH to the above-cited range,'one may add to the treatment solution an acid or alkaline substance as needed. To decrease the pH, one may add agents such as sulphuric acid, hydrochloric acid, phosphoric acid,
-sodium bisulphite, monosodium phosphate, etc. To inpreformed polyalkyleneimine, the shrinkage characteris almost completely shrinkproof under usual launderingprocedures. The reason for the effectiveness of the process'of this invention cannot be explained on a scienlcrease the pH one may add such agents as sodium carbonate, trisodium phosphate, borax, potassium carbonate, tetrasodium pyrophosphate, andso forth.
After the wool has been impregnated with the imine .solution, it is subjected to a heat curing operation. This simply involves subjecting the textile material to a temperature from about 75 to about 150C. to promote reaction between the imine and the wool whereby the imine becomes bonded to the protein molecule and can tific basis. However, it is believed that the polyalkylene imine actually reacts with the wool, forming part of the formed by immersing the wool in an excess of the solu- 7 tion or by applying the solution by spraying, brushing or other conventional application techniques. To assist in wetting the wool with the solution, it may be run through padding rolls or the like.
Although polyethylene imine is the preferred shrinkproofing agent of this invention, one can use any other polyalkylene imine. Typical examples are the polymers of: propylene imine; 1,2-butylene imine; 2,3-buty1ene no longer be removed by washing. The time of cure will vary depending on the temperature selected, the chemical nature of the fiber being treated, the degree of shrinkproofing desired, and so on. In general, a cure time of about 15 min. to about 2 hours may be used. A preferred curing operation involves heating for about 30 minutes to one hour at C.
After the textile material has been cured it may be Washed with water or laundered to remove excess imine which'is not actually bonded to the protein molecules. The textile material is then dried in the usual manner and is ready for use.
The proportion of polyalkylene imine bonded to the protein fiber may be varied widely by varying the concentration of polyalkylenimine in the treatment solution taken up by the fibrous material. Usually these conditions are so chosen that the fiber takes up about from 0.1% to 10% of its weight of polyalkylene imine. In general the larger the proportion of imine taken up by the fiber, the greater will be the shrinkage protection afiorded. It is also obvious that the degree of shrinkproofing attained will vary depending on such factors as the original characteristics of the fiber, the type of polyalkylene imine chosen and so forth. In any particular situation the fiber may be subjected to pilot experiments, applying different proportions of the chosen polyalkylene imine and selecting the conditions which give the desired degree of shrinkproofing.
The process. of. this invention is particularly adapted for the treatment of wool but may also be applied to other proteinaceous fiberssuch as mohair, fibers from fleece-bearing animals other than sheep and goats, animal hair, silk, fibers made from proteins such as zein,.casein, peanut protein, keratin, etc. The proteinaceous fiber may be in the form of actual fibers or may be in the form of threads, yarns, woven or knitted materials, garments, etc.
The invention is further demonstrated by the following example which is given onlyby way of illustration but not limitation.
EXAMPLE An aqueous solution was prepared containing of polyethylene imine (molecular weight about 20,000 to 30,000). The solution had a pH of 11.3.
Samples of woolen cloth were immersed in the solution and the cloth was run through padding rolls to assist in wetting it with the treatment solution. The cloth samples picked up about 120% of their weight of the solution.
The cloth samples were then placed in an oven where they were subjected to a temperature of 120 C. One lot of the samples was subjected to this heat for 30 minutes, another lot for 60 minutes.
The cured cloth samples were weighed to determine the uptake of polyethylene imine. The shrinkage characteristics of the cloth samples were determined 'by subjecting them to a laundering operation in which the cloth was violently agitated in a 0.5% solution of sodium oieate at 40 C. with a cloth to solution ratio of 1:50, the area of the cloth being measuredbefore and after laundering. With this method of laundering, untreated cloth samples gave an area shrinkage of 36%.
Also, samples of the cloth which had been subjected to the above polyethylene imine treatment and curing were washed for 2 hours in running hot (55 C.) water. After'this washing treatment the samples were dried and the residual polyethylene imine content was determined as well as shrinkage by the above laundering treatment.
The results obtained are set forth in the following table:
Properties of woolen cloth impregnated with 5% solution of polyethyleneimine and cured at 120 C.
Sample A B Curing time at 120 0., minutes l 30 PROPERTIES BEFORE HOT WATER EXTRACTIQN Uptake of polyethyleneimine, Percent 3. 62 4. 25 Area Shrinkage, Percent zero zero PROPERTIES AFTER WATER EXTRACTION Uptake of polyethyleneimine, Percent 3. 49 2. 25 Area.Shrinkage, Percent 1. 88 vzero take of polyethylene imine was 0.95% and the area shrinkage after laundering was 19.9%.
Having thusdescribed the invention, what-is claimed 1. A process for shrinkproofing protein fibers-which comprises impregnating the protein fiber with an aqueous alkaline solution, having a pH about from 9-to 11, containing a preformed polyethylene imine having-a molecular weight of about from 20,000 to 30,000, and curing the impregnated protein fiber at a temperature from about C. to about 150 C.
2. A process for shrinkproofing wool which comprises impregnating wool with an aqueous alkaline solution, having a pH about from 9 toll, containing a preformed polyethylene imine having a molecular weight ;of about from 20,000 to 30,000, and curing the impregnated =wool at a temperature-from about 75 C. to about 150 :C.
3. The process of :claim 2 wherein the solution of preformed polyethylene imine has a pH of about ll.
4. The. process of claim'2 wherein :the impregnated wool is cured at about C. for about onehour.
References .Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A PROCESS FOR SHRINKPROOFING PROTEIN FIBERS WHICH COMPRISES IMPREGNATING THE PROTEIN FIBERS WITH AN AQUEOUS ALKALINE SOLUTION, HAVING A PH ABOUT FROM 9 TO 11, CONTAINING A PREFORMED POLYETHYLENE IMINE HAVING A MOLECULAR WEIGHT OF ABOUT FROM 20,000 TO 30,000, AND CURING THE IMPREGNATED PROTEIN FIBER AT A TEMPERATURE FROM ABOUT 75*C. TO ABOUT 150*C.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168510A (en) * 1961-02-02 1965-02-02 Swift & Co Fatty amine derivatives of proteins
US3279882A (en) * 1964-07-07 1966-10-18 Stevens & Co Inc J P Process of stabilizing proteinaceous materials through treatment with a polyethyleneimine and a polyaziridine
DE1265114B (en) * 1961-04-25 1968-04-04 Stevens & Co Inc J P Process for reducing the shrinkage and matting of fibers, threads, yarns and fabrics made of wool or silk
US3388964A (en) * 1965-08-19 1968-06-18 Agriculture Usa Shrinkproofing wool with dhsocyanates and ethylenimine
US3393968A (en) * 1964-06-08 1968-07-23 Agriculture Usa Cellulose reacted with ethyleneimine in the presence of glacial acetic acid
US20100122918A1 (en) * 1999-11-04 2010-05-20 Smith Francis X Ophthalmic and contact lens solution

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131145A (en) * 1934-09-15 1938-09-27 Ig Farbenindustrie Ag Process for increasing the reactivity of naturally or artificially shaped articles or materials and product obtained thereby
US2202169A (en) * 1935-01-25 1940-05-28 Ig Farbenindustrie Ag Method of protecting goods containing proteins against insects
US2269997A (en) * 1939-03-09 1942-01-13 Du Pont Nu-sulphonylalkylenimine polymers
US2526637A (en) * 1948-04-02 1950-10-24 Du Pont Shrinkproofed wool and method of producing same
US2553696A (en) * 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2677681A (en) * 1951-10-06 1954-05-04 Allied Colloids Mfg Company Lt Derivatives of ethylene imine
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2817602A (en) * 1956-09-18 1957-12-24 Jr Clay E Pardo Shrinkproofing of wool with epoxy resins and polyalkyleneimines

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2131145A (en) * 1934-09-15 1938-09-27 Ig Farbenindustrie Ag Process for increasing the reactivity of naturally or artificially shaped articles or materials and product obtained thereby
US2202169A (en) * 1935-01-25 1940-05-28 Ig Farbenindustrie Ag Method of protecting goods containing proteins against insects
US2269997A (en) * 1939-03-09 1942-01-13 Du Pont Nu-sulphonylalkylenimine polymers
US2553696A (en) * 1944-01-12 1951-05-22 Union Carbide & Carbon Corp Method for making water-soluble polymers of lower alkylene imines
US2526637A (en) * 1948-04-02 1950-10-24 Du Pont Shrinkproofed wool and method of producing same
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2677681A (en) * 1951-10-06 1954-05-04 Allied Colloids Mfg Company Lt Derivatives of ethylene imine
US2817602A (en) * 1956-09-18 1957-12-24 Jr Clay E Pardo Shrinkproofing of wool with epoxy resins and polyalkyleneimines

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3168510A (en) * 1961-02-02 1965-02-02 Swift & Co Fatty amine derivatives of proteins
DE1265114B (en) * 1961-04-25 1968-04-04 Stevens & Co Inc J P Process for reducing the shrinkage and matting of fibers, threads, yarns and fabrics made of wool or silk
US3393968A (en) * 1964-06-08 1968-07-23 Agriculture Usa Cellulose reacted with ethyleneimine in the presence of glacial acetic acid
US3279882A (en) * 1964-07-07 1966-10-18 Stevens & Co Inc J P Process of stabilizing proteinaceous materials through treatment with a polyethyleneimine and a polyaziridine
US3388964A (en) * 1965-08-19 1968-06-18 Agriculture Usa Shrinkproofing wool with dhsocyanates and ethylenimine
US20100122918A1 (en) * 1999-11-04 2010-05-20 Smith Francis X Ophthalmic and contact lens solution

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