CA1172652A

CA1172652A - Fabric softening compounds and method

Info

Publication number: CA1172652A
Application number: CA000354551A
Authority: CA
Inventors: James M. Richmond
Original assignee: Akzona Inc
Current assignee: Akzona Inc
Priority date: 1979-07-02
Filing date: 1980-06-23
Publication date: 1984-08-14
Also published as: EP0021546A2; ES492977A0; ES8105808A1; AU5978880A; BR8004059A; EP0021546A3

Abstract

ABSTRACT OF THE DISCLOSURE

Novel fabric softening compounds of the formulae , and

Description

! ~ 1 7 2 6 5 2 BACKGROUND OF THE INVENTION
This invention relates to fabric softening compounds and to a method for softening textiles~ More particularly this inven-tion relates to certain quaternary ammonium compourlds and their use in softening textiles.
~ uaternary ammonium compounds arld their use in softening textiles or conditioning other substrates such as hair have been long recognized in the prior art. Such quaternary ammonium compounds which have alkoxy groups, such as ethoxy, attached to the quaternary nitrogen atom have also been known in the art. In this respect, reference may be made to U.S. Patent Nos. 2,189,397,

2~775,604, 2,824,861, 3,026,169, 3,352,709, 3,456~013, 3,872,138, 4,118,324, 4,129,506, 4,134,970, 4,136,039, and 4,139,477.
One of the properties of concern to users of such quaternary ammonium compounds is the liquidity of the product.
Thus, it is desirable that fabric softening compounds be as liquid as possible to reduce the necessity, for example, of utilizing heated railroad cars for transportation of the bulk compound, or the use of heated holding tanks and transfer lines to assure that the compound is malntained in a liquid state. Th~s is especially true in view of the recent desirability to minimize the energy which Is needed for any type of processing. Therefore, if d more liquid product is produced, the amount of energy required to transport and store the product is minimized. Also, liquid products are generally cold water dispersible, negating the need to heat water to make diluted solutions or dispersions of the !~
;concentrated softener.
j, It is, therefore, an object of the invention to provide quaternary ammonium compounds which exhiblt increased liquidity over other prior art compounds.

,! ~

~ 1 72B52 Also, as many of the quaternary ammonium com-pounds which are known in the art are chloride salts which are known to have corrosive properties, an object of this in-vention is to provide quaternary ammonium compounds which are less corrosive.
A further object is to produce compounds free of volatile and flammable solvents that serve only as a reaction media and have no value for providing softening.
SUMMARY OF THE INVENTION
It has now been surprisingly discovered that if a quaternary ammonium compound is produced having attached to the quaternary nitrogen an alkoxy group which has been esterified to form an acetate ester, the acetate salt thereof will be more li~uid than the corresponding acetate in which the alkoxy group has not been esterified. The acetate salts of this invention are less corrosive than their chloride salt analogs. Thus the present invention provides novel com-pounds of the following formulae:

R~~ 2CHO)x CCHOCCH3 ~

, and Rl(C~2CHO)x CCH3 L R5\ (CH2CHO)y(CCH2)z'l L OCCH3

-3-~ 172~
wherein R1 and R2 are independ,~ntly selected from the yroup consisting of aliphatic radicals containing from abollt 8 to about 22 carbon atoms, R3 and R4 are independently selected from the ; ~roup consisting of hydrogen and methyl, R5 is selected from the group consistiny of hydrogen and aliphatic radicals containing from about 8 to al~out 22 carbon atoms, x and y are independently integers from 1 to about 20, and z is O or 1.
Also, provided is a method for soft,~ning textiles com-prising contacting said textiles with an effective amount of a compound of one of the foregoing formulae. Typically the textiles are contacted with the compound which is in the form of a solu-tion.
DE-SCRIPTION OF THF PREFERRED EMBODIMENTS
In the compounds of the present invention which are described hereinabove it is generally desirable that the alkoxy group in the cationic moiety be an ethoxy, propoxy, or mixed ethoxy/propoxy group. Of course, if a mixed group is utilized, the chain may be either random or block. As indicated, such an alkoxy chain may contain from 1 to about 20 alkoxy units, typical-I ly from about 1 to about 5~ and preferably about 1 alkoxy unit.
I¦ The long chain aliphatic groups present in the cationic ¦Imoiety as indicated contain from about 8 to about 22 carbon atoms.
Preferably, the aliphatic groups contain from about 12 to about 18 lcarbon atoms. The aliphatic groups may be either saturated groups, and thus alkyl9 or may be unsaturated groups, and thus alkenyl~ Typically, such groups are derived from, for example, ~animal fatty acids such as tallow fatty acids or grease acids ,(Flomkoy fat), hydrogenated tallow fatty acids, and coconut fatty !
acids.

i 172652 The preparation of such quaternary ammoniuln compounds is relatively simply. First, one may star~ wlth the corresponding tertiary amine which may be reacted with acetic acid and the corresponding alkylene oxide such as ethy1ene or propylene oxide, in the presence of water. It has been found that some minimum amount of water is necessary to the reaction. Typically, the reaction would be performed in a closed reaction vessel at a temperature of about 80C and under a pressure of about 50 psig.
The reaction times will vary~ but typically will be on the order of about 6 hours. The product obtained from such a reaction will contain approximately 5% of the quaternary ammonium acetate salt having an acetate ester group in the cationic moiety.
To increase the yield o~ the acetate ester salt, one may further react the aforelnentioned reaction product, preferably after remov-al of the residual volatiles as through heating under reduced pressure, with acetic anhydride. Again, preferably, the product is heated under reduced pressure to remove remaining volatiles and the desired product recovered, As mentioned, the products of this invention are useful in softening textile materials. Because the products exhibit creased lîqu~d~ty, they are more desirable than their non-ester- !
ified counterparts. Also, as the quaternary ammonium compounds of the present invention are all acetate salts, rather than, for ex-ample, chloride salts, they are believed to exhibit reduced tendencies to corrode materials, such as metals9 with which they may come in contact. Typically, the compounds may exist as solutions, as in ethylene glycol containing about 50 to 75~ of quaternary ammonium compound, by weight~ As ethylene glycol is produced in the e~hoxyldtion react~on it is a convenlent solvent.

~ 1726~2 The solutions may also contain hexylene glycol as an additional ~solvent.
Another advantage of the products of the instant inven-tion is that although they soften textiles, they are capable of rendering them more hydrophobic than other quaternary ammonium compounds, thus making them especially desirable for softening textiles which are to be utilized in applicatlons such as rain-wear.
The compounds of this invention a1so may be useful asprecipitants and carriers for use in the manufacture of antibiot-ics. The compounds may also be used as combing aids and hair conditioners and in paper making as softeners, debonders, and antistatic agents. Furthermore, the compounds may be used as processing aids in foundries, in metal-working as emulsifiers and corrosion inhibitors and in surface modified clays, paints, oils, and lubricants.
This invention is described in more detail in the .
following non-limiting examples~
Exa~le 1 To a one-liter 316-stainless steel Parr pressure reactor was charged methyldi(hydrogenated tallow)amine (Armeen~ M2HT~ from Armak Company, Chicago, Illinois) (529 9, 1.0 gmol), glacial ace- i tic acid (60.0 9, 1.0 gmol), water (54.0 9, 3.0 gmol). This mixture was heated to 80C, the reactor vent closed and ethylene , oxide admitted (220 9, 5.0 gmol). This reaction mixture WdS heat-ed at 80C for about six hours as the reactor pressure decayed from 50 psig. Aliquots of this final mixture were analyzed and ll2.38g of unreacted amine, 86.63% of quaternary and no amine ace-i tate salt were found. This mixture had a pH of 8.67, while 3.9X
ethylene glycol, 4.2X diethylene glycol, 0.8% triethylene glycol, ~ 17~6~2 and 0.16% water was found. This final mlxture had a melting range~
of 34-37C, a pour point of 37C, and WdS a paste at room tempera-ture. Quaternary WdS isolated from this mixture and was shown to be a 95:5 mixture of the following structures IV and III, respec-tively, wherein RHT represents the aliphatic radicals obtained from hydrogenated tallow fatty acids:

IV. ~RHT)2N(CH3)cH2c~l20H] L

IiI. ~ H~ (CH3)c~l2c~20cc~ CCH
Examel_e 2 To 300 9 of.the final mixture prepared from Example 1 in a glass vessel was added acetic ~nhydride (58.8 9, 0.576 gmols) and the mixture placed on a steam bdth for about two hours. The volatiles were then removed from this reaction mixture with heat and reduced pressure provided by a vacuum pump. The product was analyzed and the quaternary present ~ound to be predominately that of Structure III as described in Example 1. This material had a melting range of 28-35C, a pour point of 35C and was a paste at room temperature.
Example 3 To a one-liter 316-stainless steel Parr pressure reactor was charged ditallowamine (Armeen~ 2T, froM Armak Company, Chicdgo, Illinois), (450 9; 0.88 gmol), glacial acetic acid (52.8 g; 0.88 gmol), water (54.0 g; 3~0 gmol)9 and (8.36 g, 0.044 gmol).
This mixture was heated to 80C, the reactor vent closed, and ethylène oxide added (155 g; 3.5 gmol~. This mixture was heated at 80C for about 8 hours as the reactor pressure decayed ~rom 50 ~ 1 7~5~ I

psig Analysis of this product showed 5.8% of unreac~ed amine, no amine acetdte salt, and 69.8% quaternary identified as that of Structure II, hereinbelow. This product was a very viscous liquid at room temperature and had a pour point oF 24C. Quaternary was isolated from an aliquot of this product and was shown to be a mixture of the following Structures IAJ IB and II in a ratio of IA
and IB to II o~ 7:100, respectively, wherein RT represents the aliphatic radicals obtained from tallow fatty c-cids:

IA- [ T)2NCH2CH20CC~ OCCH3]

IB. ~RT)2N(C~l2cH20ccH3)2 ] L

RT)2~(C~2cH201)2] ~ 3 Exam~ 4 A portion of the product of Example 3 was placed in a glass vessel and the volatiles remoYed with heat and reduced pressure provided by a vacuum pump. To 243.5 9 of this residue was added 61~2 9 of acetic anhydride and the mixture heated on the steam bath for about two hours. Volatiles were then removed from this mixture with heat and reduced pressure provided by a vacuum pump. This product was a thin liquid at room temperature, and had a pour point of 7C. Quaternary of this product was analyzed as predominately that of Structures IA and IB as described in Example 3.
The compositions of the foregoing examples were analyzed with respect to their viscosities, pour po~nts, me1ting ranges, and physical states at room temperature. Figure I ls a plot of il , .

Il .

.. . ,. .

the viscosity of the products identified dS having structures IA
and IB and plot of the viscosity of the product having the struc-ture identified as II. The Yiscosities were measured with a Brookfield (rvf) viscometer, utilizing spindle number 3 at 10 revolutions per minute. Similarly, Figure II is a plot of the viscosities for the compositions having structures II I and IV.
The data is compiled in Table I which shows that the quaternary ammonium acetate salts possessing acetate ester groups in the cationic moiety were consistently lower in viscosity than the corresponding dcetate salts which did not possess such acetate ester groups. Thus the compound of structure IA and IB were consistently lower in viscosity than the compound of structure Il and the compound of structure III was consistently lower in Yiscosity than the compound of structure IV. Table II summarizes the pour point, melt.ing ranges, and physical states ~or compounds possessing the 4 structuresO Again~ the compounds of structures I
and III consistently demonstrate.d d higher degree of liquidity than the compounds of structures II and IV, respecti~ely, ~' ;; , : I~` , .
: .
, , i:
1' 1 ` .
g- .
. .

~ 1 72~

TABIE I

VISCOSITY - CENTIPOISES
. TEMPERATURE STRUCTURE
( C) - - ~ ----~ = ~ = IV-410 3250* _ _ 230 . q~O 230 _

4~ 130 280 125 330 110 150 ~35 100 6~ 110 70 12~
7~ 50 ~~0 sa 80 _ ... ___ ___ ~ __ A ~y-intercept) -8.765 -9.114 ¦-7.390 -10.643 ; B (slope) .4381 4674 3916 5228 Correl ati on Coeffici ent 0.9909 O.9940 O.g858 1.000 ___ .~ ._ * EXCLUDED FROM CORRELATION OF ln n ~ A + B/T

.

., !i , I
1.
~ I ' ' ' .

!l ^lo-!l ~ 172~5~

TABLE I I

STRUCTURE
_ I ~ I I I IV
POUR POINTS, C 7 24 35 37 MELTING RANG~, C _ _ 28-35 34-37 PHYSICAL STATE Thi n Vi scous Paste Paste , AT R.T. Liquid Liquid ~ .

fH2CH2H
IA = T2NCH2CH20AC OAC ¦

IB = T2N(CH2C~120AC)2 OAC

; I I = T2N(CH2CH20H)2 OAC
(~) ;
. ~ '.
III = (HT)2NtCH3)CH2CH20AC OAC

IY = (HT)2N(CH3)CH2CH?OH OAC
i , I .

. : i .~ j, : ~ .

"

-Il-I' .

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A compound of the formula:

wherein R1 and R2 are independently selected from the group consisting of aliphatic radicals containing from about 8 to about 22 carbon atoms, R3 is selected from the group con-sisting of hydrogen and methyl, and x is an integer from 1 to about 20.

2. A compound of the formula:

wherein R1 is selected from the group consisting of ali-phatic radicals containing from about 8 to about 22 carbon atoms, R3 and R4 are independently selected from the group consisting of hydrogen and methyl, R5 is selected from the group consisting of hydrogen and aliphatic radicals containing from about 8 to about 22 carbon atoms, x and y are inde-pendently integers from 1 to about 20, and z is 0 or 1.

3. The compound of claim 1, wherein x is 1 and R3 is hydrogen.

4. The compound of claim 2, wherein x and y are 1 and R3 and R4 are hydrogen.

5. The compound of claims 1 or 3, wherein R1 and R2 are selected from the group consisting of aliphatic radicals containing from about 12 to about 18 carbon atoms.

6. The compound of claims 2 or 4, wherein R1 and R5 are selected from the group consisting of aliphatic radicals containing from about 12 to about 18 carbon atoms.

7. A method for softening textiles comprising contacting said textiles with an effective amount of the compound of claim 1.

8. A method for softening textiles comprising contacting said textileswith an effective amount of the compound of claim 2.

9. A method for softening textiles comprising contacting said textiles with an effective amount of the compound of claims 3 or 4.

10. The method of claims 7 or 8, wherein the textile is contacted with the compound in the form of a solution.