US2351581A - Stabilization of cellulosic fabrics with oxymethyl quaternary salts - Google Patents

Description

Patented June 20, 1944 2,351,581 STABILIZATION OF CELLULOSIC FABRICS WITH OXYMETHYL QUATERNARY SALTS Louis B. Bock, Huntingdon Valley, and" Alva L. Houk, Philadelphia, Pa., assignors to Riihm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing. Application April 5, 1941,

Serial No. 387,066

- 8 Claims.

This invention deals with a method for the stabilization of cellulosic fabrics against marked changes in dimensionsby treating and heating venting distortion and changes in dimensions.

Such resin treatment, however,- imparts other properties to fabrics which are not always desired.

It is an object of this invention to render fabrics composed of cotton, linen, rayon, or other cellulosic fibers resistant to shrinking or stretching. It is also an object to stabilize fabrics against changes in dimensions with preservation of appearance and handle. It is a further object to stabilize cellulosic fabrics without incorporating therewith resins, particularly resins which contain nitrogen.

These objects are accomplished by impregnating a cellulosic fabric with a solution containing about 5% or more of a quaternary ammonium compound having an oxymethyl or methyl ether substituent and heating the impregnated fabric until reaction between fabric and compound takes place. In the reaction a methyl ether group from the salt combines with celluloseto form a new compound and to yield an amine or amine salt which may be removed by volatilization, washing or other suitable procedure if desired. For the optimum condition for stabilization the impregnated fabric should be at the desired finished dimensions when the reaction takes place. These dimensions are preferably attained during the stage at which the fabric impregnated with solution is being dried. Drying may be performed at low or high temperatures and may be performed as a separate step or as one incidental to and as part of the heating of the impregnated fabric to effect the reaction described.

The quaternary ammonium compounds which have been found useful in this invention are of the general formula R1\ /R: ROOH:-N\

wherein R is an aliphatic or cycloaliphatic hydrocarbon group or an aralkyl group of not over 13 carbon atoms. X is an anion, and R1, R2 and Rs are selected to satisfy three valences of the nitrogen from at least one member of the class consisting of trivalent unsaturated hydrocarbon chains which jointly with the nitrogen form a heterocycle, divalent saturated aliphatic chains which Jointly with the nitrogen form a heterocycle, and monovalent alicyclic, araliphatic, and

octyl, hexyl, butyl, ethyl, undecenyl, methallyl,

allyl, capryl, isobutyl, isopropyl, cyclohexyl, methyl cyclohexyl, benzyl, methyl benzyl, butyl benzyl, etc. Typical of X are hydroxyl, chloride, bromide, iodide, ethyl sulfate, sulfate, formate, acetate, and the like.

The nature of R1, R2, and Rs may be widely varied. When the three groups are taken together, they constitute a trivalent unsaturated hydrocarbon group which together with the nitrogen forms a heterocycle such as occurs in pyridine, quinoline, picoline, or the like. When two of the groups together form a divalent saturated aliphatic group, there is present a group such as is found in piperidine, morpholine, pyrrolidlne, etc. in' which the divalent group together with the nitrogen forms a heterocycle. Along with such a divalent group. a monovalent group is present to satisfy the remaining valence of the nitrogen. When R1, R2, or Rs represent monovalent groups, they may represent any open chain groupssuch' as aliphatic hydrocarbon groups or aliphatic groups containing a. functional group such as hydroxyl, halogen, nitrile, amide, ester, ether, aldehyde, ketone, amine, etc. Similarly, the monovalent groups may be obtained from araliphatic groups such as benzyl, phenoxyethyl, butylphenoxyethyl, methylphenoxyethoxyethyl, ethoxyphenoxyethyl, phenylthioethyl, etc. or from alicyclic groups, such as cyclohexyl, methyl cyclohexyl, cyclohexylcyclohexyl, etc. 7

Typical of the quaternary ammonium salts which have been found useful in this invention are the following:

CH; CHQCQH;

CaHnOCHg-N C GHzCgH HC CH:

C CH

can can CeHICHIOCH N C CHlCHaCl CH: CHI

O H|0 CHr- Br CHzCHaOCHrCHaOQH;

Br CHgCHjC O 0 04B:

Hi H:

CllHuOCHg-N Br CHaCEC CeHl HI Ha CSHIC ONHOH:

cmc 5 011mm CH; CH:

HO B CgHeOCH! C E:

CgHuCH(CHe)-O CHI {l CHo a CH: f

CIHI

nHuOCHr-N ClHuOCHr-N CHaC O 0 \CIHI CH CH1 CHIOCH HC'OO 05111 0 CHI-N (mm CH3 When the R radical of the methyl ether group contains four to eight carbon atoms, the stabilization eflect is most marked without causing changes in appearance or handle. The stabilization eflect, however, clearly persists through ether groups containing radicals of twelve carbon atoms. Very long ether chains, which are useful in water-proofing, may have an opposite effect from that desired, probably because of the lubricating action of these groups.

The fabrics which are improved in stability as to dimensions by the process herein described include those woven from cotton, linen, regenerated cellulose or the several types, etc. and those woven from mixtures 01' the cellulocic materials.

Further details of stabilizing fabrics are presented in the following illustrative examples.

EXAMPLE 1 A piece of a '78 x 72, 4 yd. 36 in. cotton sheeting was impregnated with a 10% aqueous solution of butoxymethyl pyridinlum chloride. The

CIHI

CHI

sheeting was then dried at room temperature while it was held in a frame. The dried fabric was heated in an oven at 130 C. for 30 minutes. The fabric was removed from the frame and a piece of this fabric was carefully measured, laundered in a hot solution of soap and soda ash, rinsed, dried and ironed. The dimensions of the washed piece were determined and the shrinkage found to be 1% in the warp.

A piece of the original cloth, not treated with butoxymethyl pyridinium chloride, but laundered in an identical manner, shrank 4% along the warp.

EXAMPLE 2 A piece of 80x 80; 4 yd. 36 in. cotton sheeting was. held at desired dimensions by being clamped in a frame, and, while so held, was impregnated with a 10% aqueous solution of isoamyloxymethyl isopropyloxymethyl dimethyl ammonium chloride. It was thereafter freed of excess solution, dried at 30 C., heated in an oven at 130C. for one-half hour, and removed from the frame. Pieces of this treated cloth were marked, carefully measured, washed in a hot (70 C.) solution of soap and soda ash, rinsed, .dried. and pressed. Shrinkage along the warp was found to be 1.9% while the shrinkage of the original, untreated, but laundered fabric was found to be 5.25%.

. EXAMPLE 3 A piece of dyed as in., as x ca, 3.4 yds. per

inch staple was clamped ina frame impregnated with an aqueous solution containing 12% of dibutoxymethyl dimethyl ammonium chloride and 2% ammonium chloride. The impregnated fabric was air-dried, and placed in an oven at 130 C. for 30 minutes. The cloth was removed from the frame and carefully measured. It was then laundered in a hot solution of soap and soda ash, rinsed, dried and ironed. The shrinkage was now found to be 3.1% in the warp whereas the original fabric shrank 7.5%. In this case shrinkage in the filling was also determined as 0.6% in the treated P ece and 359% in the original fabric.

Similar tests were made with a variety of quaternary ammonium salts containing a methyl ether group, using the same cotton sheeting throughout the tests. The conditions of these tests and the reduction in shrinkage obtained as a result of the processing are summarized in the following table. The column headed Percent soln. shows the concentration of the quaternary salt used for impregnating the fabric. After the impregnated fabrics had been dried in a frame, they were heated for the period of time at the temperatures indicated. The cloth was then measured, laundered, as in the above examples, and again measured. The shrinkage found for each piece is recorded and also the decrease in shrinkage based on controls with untreated cloth laundered with the treated cloth.

Tsar: I

Reduction of shrinkage by impregnating and heating with certain quaternary salts Percent Min. Temp. Shrink- Percent aoln Quwmm heated heated age reduction 1 l Percent Control-30 alone 30 130 4.0 5 Butoxyma'thyipyridlnlum chloride 30 130 1. 0 75.0 do 110 1. 3 57. 5 10 Butoxymethyl trimethyl ammonium chloride 30 130 1.3 67.5 10 Dodecylorymethyl trlmethyl ammonium chloride. 30 130 l. 07 50. 8 10 Z-ethylhexyloxymethyl cyclohexyl dimethyl ammonium chloride. 30 130 1. 57 63. 2 10 Butox ethyl dibenzyl methyl ammonium chloride... 30 130 1.54 59. 1 10 Benzy or ethyl dimethyl benzyl ammonium chloride 5 150 1. 97 50. 8 10 Methally oxymethyl dimethyl benzyl ammonium chloride..." '30 130 1. 54 59. 1 10 Butox methyl triethanol ammonium chloride 80 130 2. 95 25. 3 t0 Z-ethy haxyloxymethyl triethyl ammonium chloride 15 130 0. 08 75. 5 Bntoxymethyl dimothyl benzyl ammonium chloride 15 100 2.6 35.0

10 Isoamyloxymethyl 2-hydroxy-propoyl dimethyl ammonium ch 0. 130 1.64 59.1 10 Decyloxymethyl 3-dimethylamino z-hydroxypropyl dimethyl ammonium chloride 30 130 l. 64 59. 1 l0 Methallyloxymethyl 2-formylpropyl dimethyl ammonium 1o 'n 'en 12-: 1a 11 1 ldim a. 1 i 30 m u oxyme y ormyp eny propy e y ammonum chlotidm--. 30 130 i. 64 50. 1 20 Benzyloxymethyl 2-formglpropgll dlmethyl ammonium chloride. 30 130 1. 3 67. 5 10 Butoxymethyl 8dimet ylam o-2-formylisobutyl dimethyl ammonium chloride 30 130 1. 97 50.8 10 Butoxymethyl Z-earbo-octyloxyethyl dlmethyl ammonium 1o p i "rife-"15' "'1""'i1li"&ii1i'iil"i 30 130 m7 ecy oxyme y p any prop y e y ammo um chloride 30 130 1.64 50.1 10v Dodecyioxymethyl 2-cyanoethyl dimethyi ammonium chloride. 30 130 2. 6 35. 0 10 -2-chloroethyl.dimethyl benzyl ammonium chloride 30 130 1.64 59. 1

l0 Bntoxymethyl dimethyl butyramidomethyl ammonium chloride 30 130 1.97 50.8

lb. spunrayon slub was clamped in a rigid frame EXAMPLE 5 and impregnated with a 10% aqueous solution of dibutoxymethyl dimethyl ammonium chloride. It was dried at room temperature and then placed A piece of 38in 88 x 62, 3.5 yds. per 11)., allspun bright viscose rayon challis, 1.5 denier, 11';

An all-spun rayon fabric was pinned under slight tension to a rigid frame and the cloth was marked at measured distances. It was impregnated with a 5% aqueous solution 'of bis(butoxymethyl) dimethyl ammonium hydroxide, airdried, and heated in a drier at C. for 30 minutes. At this point the distances between marks were recorded. The cloth was then washed at 70 C. in a bath containing soap and soda ash, rinsed, andironed without stretching. The dimensions were again measured. The difference in measurements showed that about 5% shrinkage had occurred in the warp. Pieces of unsalts may act as buifers or as catalysts.

treated fabric washed in the same soap solution shrank 8.8%.

The above procedure was repeated with this spun rayon fabric but a 10% solution of bis(butoxymethyl) dimethyl ammonium hydroxide was used. The results obtained were identical with those for the 5% solution.

The procedure was again repeated, but a solution of the corresponding chloride was used. A shrinkage of 5.9% was obtained. Like all of these fabrics this cloth was also more resistant to stretching than the usual washed spun rayon fabric. While the stabilization from the salt was appreciable, it will be noted that the improvement was even greater in the case of the hydroxide. From these tests and from others it is evident that the oxymethyl quaternary ammonium hydroxides are more effective on regenerated cellulose than the salts. There may also be used mixtures of hydroxide and salt forms. on cotton the salt forms appear somewhat more effective than the hydroxide. I

In general. solutions containing about 5% to about 20% of a quaternary ammonium compound having a methyl ether group are satisfactory for impregnating cellulosic fabrics and producing the desired stabilization. There may be used in conjunction with these solutions salts of weak acids and strong bases, such as sodium acetate, sodium phosphate, or the like or salts of strong acids and weak bases, such as ammonium chloride. These They are, however, not essential for the successful application of the quaternary salts. There may also be used organic solvents to improve solubility and to lessen the viscosity of solutions.

In processing impregnated fabrics, heating between about 100 C. and about 160 C. is required to effect the desired reaction. In any case, however, the upper temperature limit should not ex ceed that at which scorching may occur during the period of heating. The permissible upper temperature limit varies somewhat with the time of heating and'also with the fabric.

We claim:

1. A process for stabilizing a cellulosic fabric against changes in dimensions, which comprises impregnating said fabric with a solution containing between about 5% and about 20% of a quaternary ammonium compound of the formula wherein R is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups of less than 13 carbon atoms, X is an anion, and R1, R2, and R3 are selected to satisfy three valences of the nitrogen from at least one member of the class consisting of trivalent unsaturated hydrocarbon groups which jointly with the nitrogen form a heterocycle, divalent saturated aliphatic groups which jointly with the nitrogen form a heterocycle, and monovalent alicyclic, araliphatic, and aliphatic groups, drying the impregnated fabric under conditions imparting the desired dimensions, *and heatin to cause reaction between fabric and salt.

2. A process for stabilizing a celiulosic fabric against changes in dimensions, which comprises impregnating said fabric with a solution containing between about 5% and about 20% of a quaternary ammonium compound of the formula Rocm -1 x a, wherein R is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups of less than 13 carbon atoms, X is an anion, and R1, R2, and Ra are selected to satisfy three valences of the nitrogen from at least one member of the class consisting of trivalent unsaturated hydrocarbon groups which jointly with the nitrogen form a wherein R is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups of less than 13 carbon atoms and R1, R2, and Rs are selected to satisfy three valences of the nitrogen from at least one member of the class consisting of trivalent unsaturated hydrocarbon groups which Jointly with the nitrogen form a heterocycle, divalent saturated aliphatic groups which jointly with the nitrogen form a. heterocycle, and monovalent alicyclic, araliphatic, and aliphatic groups, drying the impregnated fabric under conditions imparting the desired dimensions, and heating to cause reaction between fabric and quaternary compound.

4. A proces for stabilizing a cellulosic fabric against changes in dimensions which comprises impregnating said fabric with a solution containing between about 5% and about 20% of a quaternary ammonium salt of the formula wherein R. is selected from a member of the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and aralkyl groups of less than 13 carbon atoms and X is a salt forming anion, drying the impregnated fabric under conditions imparting the desired dimensions, and heating to cause reaction between fabric and salt at a termperature above about C. but below that at which scorching of the fabric would occur.

5. A process for stabilizing a cellulosic fabric 4 against changes in dimensions which comprises impregnating said fabric with a solution containing between about 5% and about 20% of a quaternary ammonium salt of the formula wherein R is an aliphatic hydrocarbon group having four to eight carbon atoms and I! is a halogen, drying the impregnated fabric under conditions imparting the desired dimensions, and

heating to cause reaction between fabric and salt at a temperature above about 100 C. but below that at which scorching oivthe fabric would occur. 6. A process for stabilizing a cellulosic fabric against changes in dimensions which comprises impregnating said fabric with a. solution containing between about 5% and about 20% of butoxymethyl pyridinium chloride, drying the impregnated fabric under conditions imparting the desired dimensions, and heating to cause reaction 7 between fabric and salt at a temperature above about 100 C. but below that at which scorching of the fabric would occur.

7. A process for stabilizing a cellulosic fabric against changes in. dimensionsfwhich comprises impregnating saidfabric with a solution containing between about 5% and about 20% of a quaternary ammonium compound of the formula R1 v/ 'aocnQr wherein R isselected from a'member-oi the class consisting of aliphatic and cycloaliphatic hydrocarbon groups and arallryl groups of less than 13 carbon atoms, 2: is an anion, R1 and Rs are 1 lower alkyl groups and R: is an aralkyl group, drying the impregnated fabric under conditions imparting the desired dimensions, and heating to cause reaction between fabric and salt at a temperature above about C. but below that