CA1086750A - Process for making imidazolinium salts, fabric conditioning compositions and methods - Google Patents
Process for making imidazolinium salts, fabric conditioning compositions and methodsInfo
- Publication number
- CA1086750A CA1086750A CA277,088A CA277088A CA1086750A CA 1086750 A CA1086750 A CA 1086750A CA 277088 A CA277088 A CA 277088A CA 1086750 A CA1086750 A CA 1086750A
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- Canada
- Prior art keywords
- carbon atoms
- group
- composition
- agent
- imidazoline
- Prior art date
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
-
- 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
- D06M13/322—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 nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/47—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds
- D06M13/473—Compounds containing quaternary nitrogen atoms derived from heterocyclic compounds having five-membered heterocyclic rings
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract of the Disclosure The invention described herein is, in one aspect, a process for making quaternary imidazolinium salts, essentially free of amines, amine salts and alkoxylated forms of the imidazolinium salts, having the following structure:
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from l to about 4 carbon atoms; D is optional and, where present, is selected from the group con-sisting of wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps:
A. Forming a mixture of an actuating or esterifying agent having an aliphatic or cycloaliphatic hydrocarbon group i containing from about 10 to about 22 carbon atoms associat-ed with each acyl group and an alkylene or polyalkylene polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 to about 1.5:1;
B. Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100°C
to about 250°C and then drawing a vacuum of from about 0.4 mm mercury to about 10 mm mercury for from about 1 to about 8 hours to form an imidazoline product in a mix-ture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B with an alkoxylating agent in an amount equal to from about 1%
to about 5% by weight of the imidazoline product mixture while maintaining the temperature at from about 80°C to about 140°C for a period of from about 0.5 to about 8 hours; and D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least 1:1.
Also disclosed are fabric conditioning compositions containing the above-defined quaternary imidazolinium conditioning agents.
Aqueous liquid fabric conditioning compositions according to this invention possess desirable stability and conditioning properties.
ii
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from l to about 4 carbon atoms; D is optional and, where present, is selected from the group con-sisting of wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps:
A. Forming a mixture of an actuating or esterifying agent having an aliphatic or cycloaliphatic hydrocarbon group i containing from about 10 to about 22 carbon atoms associat-ed with each acyl group and an alkylene or polyalkylene polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 to about 1.5:1;
B. Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100°C
to about 250°C and then drawing a vacuum of from about 0.4 mm mercury to about 10 mm mercury for from about 1 to about 8 hours to form an imidazoline product in a mix-ture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B with an alkoxylating agent in an amount equal to from about 1%
to about 5% by weight of the imidazoline product mixture while maintaining the temperature at from about 80°C to about 140°C for a period of from about 0.5 to about 8 hours; and D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least 1:1.
Also disclosed are fabric conditioning compositions containing the above-defined quaternary imidazolinium conditioning agents.
Aqueous liquid fabric conditioning compositions according to this invention possess desirable stability and conditioning properties.
ii
Description
51) BACKGROUND OF THE IN~ENTION
This invention relates to the production of quater-nary imidazolinium fabric conditioning agents essentially free of amines, amine salts and alkoxylated forms of the quaternary imidazolinium salts. The present invention additionally relates to a fabric conditioning composition containing an imidazolinium agent essentially free of amines and amine salts and a method for conditioning fabrics.
In the conventional home laundering process, soiled fabrics are subjected to cleaning with a detergent composition in the main wash cycle and rinsing with water in the final cycle. Optionally, during the rinsing cycle a fabric con-ditioning composition is added. Such compositions contain a fabric softener or fabric antistat material for imparting to the rinsed fabrics softening and antistat properties. The rinsed fabrics are oftentimes, thereafter, dried in an automatic clothes dryer.
Many different types of fabric conditioning agents ;
have been used in rinse cycle added fabric conditioning com-positions. The most favored type of agent has been the quat-ernary ammonium compounds. These compounds may take the form of noncyclic quaternary ammonium salts having preferably two lon~ chain alkyl groups attached to the nitrogen atom. Addi-tionally, imidazolinium salts have been used by themselves or in combination with other agents in the treatment of fabrics.
U~S. Patent 2,874,074, February 17, 1959, to Johnson discloses using imidazolinium salts to condition fabrics. U.S. Patent 3,681,241, August 1, 1972, to Rudy, and U.S. Patent 3,033,704, -May 8, 1962, to Sherrill et al, disclose fabric conditioning -compositions containing mixtures of imidazolinium salts and other fabric conditioning agents.
This invention relates to the production of quater-nary imidazolinium fabric conditioning agents essentially free of amines, amine salts and alkoxylated forms of the quaternary imidazolinium salts. The present invention additionally relates to a fabric conditioning composition containing an imidazolinium agent essentially free of amines and amine salts and a method for conditioning fabrics.
In the conventional home laundering process, soiled fabrics are subjected to cleaning with a detergent composition in the main wash cycle and rinsing with water in the final cycle. Optionally, during the rinsing cycle a fabric con-ditioning composition is added. Such compositions contain a fabric softener or fabric antistat material for imparting to the rinsed fabrics softening and antistat properties. The rinsed fabrics are oftentimes, thereafter, dried in an automatic clothes dryer.
Many different types of fabric conditioning agents ;
have been used in rinse cycle added fabric conditioning com-positions. The most favored type of agent has been the quat-ernary ammonium compounds. These compounds may take the form of noncyclic quaternary ammonium salts having preferably two lon~ chain alkyl groups attached to the nitrogen atom. Addi-tionally, imidazolinium salts have been used by themselves or in combination with other agents in the treatment of fabrics.
U~S. Patent 2,874,074, February 17, 1959, to Johnson discloses using imidazolinium salts to condition fabrics. U.S. Patent 3,681,241, August 1, 1972, to Rudy, and U.S. Patent 3,033,704, -May 8, 1962, to Sherrill et al, disclose fabric conditioning -compositions containing mixtures of imidazolinium salts and other fabric conditioning agents.
-2 75~
While the prior art shows the use of quaternary imidazolinium salts as fabric conditioning agents, it is silent about the problems encountered in making stable fabric conditioning compositions containing such agents and aldehydes.
The manufacture of imidazolinium salts generally involves ~-the reaction of a polyamine with an acyl containing material such as an acid or ester to form an imidazoline and then a quaternizing of the imidazoline. U.S. Patents 2,355,837, August 15, 1944, and 2,267,965, December 30, 1941, to Wilson;
and U.S. Patent 2,520,102, August 22, 1950, to Tryon, all disclose methods for making imidazolines used in making imidazolinium salts. It has been found in the present inven-tion that in addition to the imidazoline compound formed in the described reaction, primary and secondary amines are also present. During the subsequent quaternization step, these amines cause some of the imidazoline compound to form the imidazoline amine salt rather than the quaternary imida-zolinium salt. The imidazoline amine salt, when present in ; an aqueous medium having a near neutral or higher pH, is cap-able of undergoing ring opening to form free amines which will then react with aldehydic compounds in the composition much the same as free amines which have not been converted to the salt form. The result is that the odor of the composition degrades (perfumes generally contain aldehydes), the color and the pH change and aldehyde preservatives degrade. The aforementioned Johnson patent describes making quaternary imidazolinium salts, but is silent about how to overcome the problems descrlbed while still achieving an end praduct which is sufficiently high in imidazolinium salt to be commercially attractive. In the process aspect of the present invention the undesirable amines are "capped" using an alkoxylating ':
While the prior art shows the use of quaternary imidazolinium salts as fabric conditioning agents, it is silent about the problems encountered in making stable fabric conditioning compositions containing such agents and aldehydes.
The manufacture of imidazolinium salts generally involves ~-the reaction of a polyamine with an acyl containing material such as an acid or ester to form an imidazoline and then a quaternizing of the imidazoline. U.S. Patents 2,355,837, August 15, 1944, and 2,267,965, December 30, 1941, to Wilson;
and U.S. Patent 2,520,102, August 22, 1950, to Tryon, all disclose methods for making imidazolines used in making imidazolinium salts. It has been found in the present inven-tion that in addition to the imidazoline compound formed in the described reaction, primary and secondary amines are also present. During the subsequent quaternization step, these amines cause some of the imidazoline compound to form the imidazoline amine salt rather than the quaternary imida-zolinium salt. The imidazoline amine salt, when present in ; an aqueous medium having a near neutral or higher pH, is cap-able of undergoing ring opening to form free amines which will then react with aldehydic compounds in the composition much the same as free amines which have not been converted to the salt form. The result is that the odor of the composition degrades (perfumes generally contain aldehydes), the color and the pH change and aldehyde preservatives degrade. The aforementioned Johnson patent describes making quaternary imidazolinium salts, but is silent about how to overcome the problems descrlbed while still achieving an end praduct which is sufficiently high in imidazolinium salt to be commercially attractive. In the process aspect of the present invention the undesirable amines are "capped" using an alkoxylating ':
- 3 -.... ~
~0~;7S;~
agent in an amount sufficient to cap the primary and secondary amines but not cap to any apprecia~le degree the cyclic tertiary amine wh.ich forms the imidazolinium salt.
It is therefore, an object of this invention to provide a process for making quaternary imidazolinium salts which are essentially free of amines, amine salts and alkoxy-lated forms of the imidazolinium salts.
It is another object of this invention to provide a fabric conditioning composition comprising a quaternary imidazolinium salt and being essentially free of amines and amine salts.
It is still another object of this invention to provide a method for conditioning fabrics by treating them ..
with the desired imidazolinium salts.
These and other objects will become apparent from the description which follows.
As used herein all percentages and ratios are by weight unless otherwise specified.
SUMMARY OF THE INVENTION
; ', The present invention encompasses in one aspect a : :
process for making quaternary imidazolinium salts, essentially : -.
free of amines, amine salts and alkoxylated forms of the imidazolinium salts r having the following structure:
¦ 12 ~
- CH - R X
7 CH - R4 .
D - Rl :
wherein R and Rl are aliphatic or cycloaliphatic hydrocarbon ~-~: .
~ .
7~
groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from l to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms; D is optional and, where pre~ent, is selected from the group con-sisting of ~ n 2n~ ~ tCnH2nt NH-C- and ~CH2~ ~O-C-wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps: :~
. Forming a mixture of an acylating or esterifying agent having an aliphatic or cycloaliphatic hydrocarbon group containing from about lO to about 22 carbon atoms associat-ed with each acyl group and an alkylene or polyalkylene -polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 ~.
to about 1.5:1;
: , . Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100C
to about 250C and then drawing a vacuum of from about 0.~ mm mercury to about 10 mm mercury for from about l to about 8 hours to form an imidazoline product in a mixture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B with .:
an alkoxylating agent in an amount equal to from about . ~ ~ _ 5 _ ù ~
s~
1% to about 5~ by weight of the imidazoline product mix-ture wh.ile maintaining the temperature at from about 80C
to about 140C for a period of from about 0.5 to about 8 hours; and :~
D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least l:l.
N - CH - R X
N - CH - R4 ~
D - Rl :.
In an optional form D may be absent and Rl attached directly to the number l nitrogen in the ring. In another .
option, Rl and D may be absent and in their place a group from the imidazoline forming amine may be present. It is to be appreciated that while the R2 group is shown as being on -:
the number 3 nitrogen, it may also be present on the number 1 nitrogen.
The invention also encompasses a fabric condition-ing composition comprising the above defined quaternary imidazolinium salt which is essentially free of amines and ~ :
amine salts. Methods of conditioning fabrics with the imidazolinium salts are also provided. `: ~
DET~ILED DESCRIPTION OF T~E INVENTION -In accordance with this invention, quaternary imi- ~ :
dazolinium salts essentially free of amines, amine salts and alkoxylated forms of the imidazolinium salts are produced.
. - . - . . ~
...... ~ . . .... .. .. ... ... . . . . . ....... . .... ...... ........ ;.i ~.
The reaction to form the desired imidazolinium salt involves the ~ollowing steps:
Formation of Im~dazoline The imidazoline precursor for the desired imidazolin-ium salt is formed by reacting acylating or esterifying agents with alkylene or polyalkylene polyamines having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group. The reac-tion is conducted at`a temperature of about 100C to about 250C for a period of about 3 to about 24 hours, at a molar ratio of acyl groups to primary amine and hydroxyl groups ranging from about 0.33:1 to about 1.5:1, preferably from -about 1:1 to about 1.5:1, and under reflux or at atmospheric pressure or slightly greater. To facilltate the formation ~;
of the imidazoline rlng structure the reaction mlxture may subsequently be~subjected~ to a vacUum of-~ from about 0.4 to about 10 mm of mercury for a period of from about l to about 8 hours.~ The resulting mixture contains in addition -to the desixed imidazoline some of~the original acylatlng material, some of the origlnal polyamine, some of the non-cyclized intermediate amlde produots and other mixed reaction products;. The acylating or esterifylng agent~ may be~any acid or other acyl containing compound having~an aliphatic .
or cycloaliphatic hydrocarbon group of about 10-22 carbon - .
atoms. Examples of such materials lnclude the fatty acids lauric, decanoic, undecanoic, dodecancic, tridecanoic, myristio, pentadecanolc~,~hexadecanoic, palmitic and the like.
~referred`fatty acids are the mixtures thereof derived from tallow, soybean~ or coconut oils. Particularly preferred are the~sort or-hardened~ta~llow fatty acids. Other acylating or esterifying agents include~the alkyl esters of~the fatty ~ 7 _ o~
acids and the naturall~ occurring glyceride esters. The latter are preferred for use herein.
The polyamine ma-terial, as indicated abo~e, has either two or three amino groups wherein one is a primary or secondary amino group in the 2 position to a primary amine group. These preferably take the following form:
where X may be, for example, hydrogen, ~CH2-CH2)n-NH2 , tCH -C~I2t -OH or ~CH2 CH2~n 3 wherein n is from 1 to :
about 6. Examples of such polyamines include diethylenetri-amine, ethylenediamine, hydroxyethyl ethylenediamine, etc.
Addition of Second Long Chain Alkyl or Substituted Alkyl Group As described above, the formation of the imidazoline ;
is accomplished by reacting a polyamine with an acylating or esterifying agent. If the amount of acylating or esterifying agent used is not sufficient to form an amide or ester with at least two of the amine or hydroxyl groups present in the poly-amine (the molar ratio of acyl groups to primary amine or hydroxyl groups being from about 0.33 to about 0.66), the imidazoline formed will only have a long chain group of the i type desired positioned at the 2 position rather than at both the 1 and 2 positions of the imidazoline ring. The mono substituted material then has to be reacted further with an ~
acylating or esterifying agent. The reaction temperature is ~-... . .
generally the same as the generalized reaction given above while the molar ratio of acylating agent or esterifying agent .. . . .
to mono substituted imidazoline ranges from about 1:1 to about 1.5:1 and the reaction time ranges from about 1 to about 24 -hours. Optionally, a vacuum of from about 004 to about 10 mm . ~ . - . .. . ..... .
of mercury is drawn. This reaction can be exemplified as follows using diethylenetriamine as the polyalkylene poly-amine:
R - C - OH + NH2-CH2-CH2-NH-cH2-cH2 N~I2 ~ : , 1l H20 removed R - C - NH-CH2-CH2 - NH CH2 C 2 2 2 ;
.: `' ~ N - ICH2 R - C \ ¦ + H20 (removed) N - CH2 :
where R is an aliphatic or cycloaliphatic hydrocarbon group containing from about 10 to about 22 carbon atoms. ~ .
The primary amine present in the imidazoline formed -above than has to be converted to an amide to attach the second long chain R group in the following manner:
N - 7E2 -~ Rl - C - OE >
IN C 2 ;~:
~ 7 ~ :
R - C \ ¦ + H20 CH2--C~2--NE-C~Rl ~ ~ ~ g-7~i~
where Rl is an aliphatic or cycloaliphatlc hydrocarbon group containing from about 10 to about 22 carbon atoms. The group in the above formula corresponds to D in the formula given above in the Summary of the Invention section. It should be appreciated that D may be another divalent radical or - absent depending on the choice and concentration of polyamineand acylating or esterifying agent. See, for example, U.S.
Patent 2,267,965 to Wilson, mentioned previously, where an hydroxy group is attached to the 1 position of the imidazoline ~
ring. Also the o-ther U.S. Patent to Wilson mentioned pre- ~-viously, U.S. Patent 2,355,837, for other polyamines.
Of course, if the amount of acylating or esterifying agent used contains a number of acylating groups sufficient to form an amide or ester with at least two of the amine or hydroxyl groups (ratio of acyl to primary amine or hydroxyl groups is from about 0.67 to about 1.5:1, preferably 1:1 to about 1.1:1), the long chain group in the 1 position would be present as a result of the initial imidazoline forming reaction. The following represents such a reaction:
.. .. .
O ..
Il , .
. .,.. , j.. ..
: li ( lH - O - C - R ~ NH2-CH2-CH2-NH CH2 CH2 2 >
11 .
CH2 - O - C - R ~
.
1 ~ C-R
(I) ,~' - 10 -i ~t.
75(~
(II~
N - CH
R - C ~
IH -CH -N~ - 11 - R
Some of the intermediate amides shown above~ as well as some of the starting materials, other intermediates, water and other complexes are present as diluents along wi-th the desired --~
substituted imidazoline. Some of the diluents are removed during the vacuum stage of the reaction.
Alkoxylation of Imidazoline The formation of the 1,2-substituted imidazoline product will have as components~in~addition to the desired imidazoline product the materials notèd as diluents in the glyceride reaction above. If the imidazoline reaction forma-tion is the fatty acid reaction given above wherein the 2 substituted imidazoline is formed first and then the second long chain aliphatlc or cycloaliphatic hydrocarbon group is `
added~in~the l position by means of a reactlon with a fatty acid, or other agent, the desired imidazoline is going to be present in a mixture containing some of the imldazoline substituted only at the 2 position and ratty acid or other agent. Similarly, regardless of which reaction route is used, there will be ~rimary~and/or secondary amines present in the final ml~l~e due to~ either unreacted initial amine or the amide in,ermediate products. The materials which have pri-:: :
mary and secondary amine groups present are undesirable since in the quaternizing step, to be discussed subsequently, the amines cause the~dlsubstituted imidazoline to be trans~~ormed .. . . . : . ~ , - . - . .~ .
.- ... . . . . .. . -~o~ o to an amine salt rather than a quaternary salt which, in turn, is capable of reverting to free amines when present in an aqueous compositîon having a pH of about 5 or greater. The patent issued to Johnson, U.S. Patent 2,874,074, February 17, -1959, mentioned earlier in this specification, disclosed making the 1,2-substituted imidazoline by the two step fatty acid process. Johnson utilizes the 2 substituted imidazoline as made by Wilson, U.S. Patent 2,355,837, August 15, 1944, or U.S. Patent 2,267,965, December 30, 1941. The imidazoline product as made by Johnson would contain a mixture of the 1,2 substituted material, the 2 substituted material, other amine containing materials and fatty acid. The 2 substituted material and the other amines are undesirable, as indicated above, due to their ability to cause the imidazoline salt to be formed.
The present applicants have found that the undesir-able amine products present in the 1,2 substituted imidazoline : ,. .. .
reaction mixture can be effectively capped by treating the mixture with an alkylene oxide, preferably propylene oxide.
The alkylene oxide serves to "cap" the amines by attaching an alkylene oxide moiety to the free amine. It is important that all of the primary and secondary amines are capped, but only a minimum of the tertiary amine in the imidazoline.
To achieve these goals the mixture containing the desired 1,2 substituted imidazoline is treated with an amount of an alkylene oxide amounting to ~rom about 1 to 5% by weight of the mixture to be treated, while the temperature is kept at from about ~0C to about 140C and a vacuum is optionally drawn amounting to from about 2 to about 15 mm mercury. The vacuum helps to rid the system of excess alkylene oxide, polyamine and other low boiling diluents. The imidazoline .~, . . .
..
... - .. - . . . . . . , - . . . . ... ~ . . . .
751[D
containing mixture can also be diluted with an organic sol-vent such as isopropyl alcohol or glymes to facilitate the alkylene oxide treatmen-t. Such solvents are used in an amount of from a~out 1 to about 25% ~y weight of the imidazoline mixture. The time of the reaction ranges from about 0.5 to about 8 hours. U.SO Patent 2,713,582, July 19, 1955, to Smith, discloses making fully alkoxylated imidazolines as a precursor for carboxylate detergent products. Examples of alkoxylating agents other than propylene oxide include butyl-ene oxide, glycide, ethylene oxide, cyclohexame oxide, etc.
Quaternization The alkylene oxide treated mixture from above is treated with an alkylating agent to form the desired quaternary imidazolinium material essentially free of amines, amine salts and alk~xylated forms of the imidazolinium salts. The imidazolinium product preferably contains a total less than about 4~, preferably less than about 2%, of primary amines, secondary amines and cyclic tertiary amine salts and less than about 25%, preferably 4%, of the alkoxylated form of the imidazolinium salt. The limit on the alkoxylated form is the result of wanting to make the nonalkoxylated imidazolinium - :
salt as pure as~possible and is not related to the amine/amine salt stability problem. The alkylating agent can be any of the known agents such as methylchloride, ethylbromide, di-ethylsulfate, dlmethylsul~ate, hexadecylchloride, among many others. The reaction can be exemplified in -the following manner:
, ' ~ '-' ' '' `-.
.: .
:
.
.
, ~
;7~0 DN -- fH-R
R -- C~ ¦ + ~CH3~ 2~04 N -- CH -- R
~0~;7S;~
agent in an amount sufficient to cap the primary and secondary amines but not cap to any apprecia~le degree the cyclic tertiary amine wh.ich forms the imidazolinium salt.
It is therefore, an object of this invention to provide a process for making quaternary imidazolinium salts which are essentially free of amines, amine salts and alkoxy-lated forms of the imidazolinium salts.
It is another object of this invention to provide a fabric conditioning composition comprising a quaternary imidazolinium salt and being essentially free of amines and amine salts.
It is still another object of this invention to provide a method for conditioning fabrics by treating them ..
with the desired imidazolinium salts.
These and other objects will become apparent from the description which follows.
As used herein all percentages and ratios are by weight unless otherwise specified.
SUMMARY OF THE INVENTION
; ', The present invention encompasses in one aspect a : :
process for making quaternary imidazolinium salts, essentially : -.
free of amines, amine salts and alkoxylated forms of the imidazolinium salts r having the following structure:
¦ 12 ~
- CH - R X
7 CH - R4 .
D - Rl :
wherein R and Rl are aliphatic or cycloaliphatic hydrocarbon ~-~: .
~ .
7~
groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from l to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms; D is optional and, where pre~ent, is selected from the group con-sisting of ~ n 2n~ ~ tCnH2nt NH-C- and ~CH2~ ~O-C-wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps: :~
. Forming a mixture of an acylating or esterifying agent having an aliphatic or cycloaliphatic hydrocarbon group containing from about lO to about 22 carbon atoms associat-ed with each acyl group and an alkylene or polyalkylene -polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 ~.
to about 1.5:1;
: , . Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100C
to about 250C and then drawing a vacuum of from about 0.~ mm mercury to about 10 mm mercury for from about l to about 8 hours to form an imidazoline product in a mixture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B with .:
an alkoxylating agent in an amount equal to from about . ~ ~ _ 5 _ ù ~
s~
1% to about 5~ by weight of the imidazoline product mix-ture wh.ile maintaining the temperature at from about 80C
to about 140C for a period of from about 0.5 to about 8 hours; and :~
D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least l:l.
N - CH - R X
N - CH - R4 ~
D - Rl :.
In an optional form D may be absent and Rl attached directly to the number l nitrogen in the ring. In another .
option, Rl and D may be absent and in their place a group from the imidazoline forming amine may be present. It is to be appreciated that while the R2 group is shown as being on -:
the number 3 nitrogen, it may also be present on the number 1 nitrogen.
The invention also encompasses a fabric condition-ing composition comprising the above defined quaternary imidazolinium salt which is essentially free of amines and ~ :
amine salts. Methods of conditioning fabrics with the imidazolinium salts are also provided. `: ~
DET~ILED DESCRIPTION OF T~E INVENTION -In accordance with this invention, quaternary imi- ~ :
dazolinium salts essentially free of amines, amine salts and alkoxylated forms of the imidazolinium salts are produced.
. - . - . . ~
...... ~ . . .... .. .. ... ... . . . . . ....... . .... ...... ........ ;.i ~.
The reaction to form the desired imidazolinium salt involves the ~ollowing steps:
Formation of Im~dazoline The imidazoline precursor for the desired imidazolin-ium salt is formed by reacting acylating or esterifying agents with alkylene or polyalkylene polyamines having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group. The reac-tion is conducted at`a temperature of about 100C to about 250C for a period of about 3 to about 24 hours, at a molar ratio of acyl groups to primary amine and hydroxyl groups ranging from about 0.33:1 to about 1.5:1, preferably from -about 1:1 to about 1.5:1, and under reflux or at atmospheric pressure or slightly greater. To facilltate the formation ~;
of the imidazoline rlng structure the reaction mlxture may subsequently be~subjected~ to a vacUum of-~ from about 0.4 to about 10 mm of mercury for a period of from about l to about 8 hours.~ The resulting mixture contains in addition -to the desixed imidazoline some of~the original acylatlng material, some of the origlnal polyamine, some of the non-cyclized intermediate amlde produots and other mixed reaction products;. The acylating or esterifylng agent~ may be~any acid or other acyl containing compound having~an aliphatic .
or cycloaliphatic hydrocarbon group of about 10-22 carbon - .
atoms. Examples of such materials lnclude the fatty acids lauric, decanoic, undecanoic, dodecancic, tridecanoic, myristio, pentadecanolc~,~hexadecanoic, palmitic and the like.
~referred`fatty acids are the mixtures thereof derived from tallow, soybean~ or coconut oils. Particularly preferred are the~sort or-hardened~ta~llow fatty acids. Other acylating or esterifying agents include~the alkyl esters of~the fatty ~ 7 _ o~
acids and the naturall~ occurring glyceride esters. The latter are preferred for use herein.
The polyamine ma-terial, as indicated abo~e, has either two or three amino groups wherein one is a primary or secondary amino group in the 2 position to a primary amine group. These preferably take the following form:
where X may be, for example, hydrogen, ~CH2-CH2)n-NH2 , tCH -C~I2t -OH or ~CH2 CH2~n 3 wherein n is from 1 to :
about 6. Examples of such polyamines include diethylenetri-amine, ethylenediamine, hydroxyethyl ethylenediamine, etc.
Addition of Second Long Chain Alkyl or Substituted Alkyl Group As described above, the formation of the imidazoline ;
is accomplished by reacting a polyamine with an acylating or esterifying agent. If the amount of acylating or esterifying agent used is not sufficient to form an amide or ester with at least two of the amine or hydroxyl groups present in the poly-amine (the molar ratio of acyl groups to primary amine or hydroxyl groups being from about 0.33 to about 0.66), the imidazoline formed will only have a long chain group of the i type desired positioned at the 2 position rather than at both the 1 and 2 positions of the imidazoline ring. The mono substituted material then has to be reacted further with an ~
acylating or esterifying agent. The reaction temperature is ~-... . .
generally the same as the generalized reaction given above while the molar ratio of acylating agent or esterifying agent .. . . .
to mono substituted imidazoline ranges from about 1:1 to about 1.5:1 and the reaction time ranges from about 1 to about 24 -hours. Optionally, a vacuum of from about 004 to about 10 mm . ~ . - . .. . ..... .
of mercury is drawn. This reaction can be exemplified as follows using diethylenetriamine as the polyalkylene poly-amine:
R - C - OH + NH2-CH2-CH2-NH-cH2-cH2 N~I2 ~ : , 1l H20 removed R - C - NH-CH2-CH2 - NH CH2 C 2 2 2 ;
.: `' ~ N - ICH2 R - C \ ¦ + H20 (removed) N - CH2 :
where R is an aliphatic or cycloaliphatic hydrocarbon group containing from about 10 to about 22 carbon atoms. ~ .
The primary amine present in the imidazoline formed -above than has to be converted to an amide to attach the second long chain R group in the following manner:
N - 7E2 -~ Rl - C - OE >
IN C 2 ;~:
~ 7 ~ :
R - C \ ¦ + H20 CH2--C~2--NE-C~Rl ~ ~ ~ g-7~i~
where Rl is an aliphatic or cycloaliphatlc hydrocarbon group containing from about 10 to about 22 carbon atoms. The group in the above formula corresponds to D in the formula given above in the Summary of the Invention section. It should be appreciated that D may be another divalent radical or - absent depending on the choice and concentration of polyamineand acylating or esterifying agent. See, for example, U.S.
Patent 2,267,965 to Wilson, mentioned previously, where an hydroxy group is attached to the 1 position of the imidazoline ~
ring. Also the o-ther U.S. Patent to Wilson mentioned pre- ~-viously, U.S. Patent 2,355,837, for other polyamines.
Of course, if the amount of acylating or esterifying agent used contains a number of acylating groups sufficient to form an amide or ester with at least two of the amine or hydroxyl groups (ratio of acyl to primary amine or hydroxyl groups is from about 0.67 to about 1.5:1, preferably 1:1 to about 1.1:1), the long chain group in the 1 position would be present as a result of the initial imidazoline forming reaction. The following represents such a reaction:
.. .. .
O ..
Il , .
. .,.. , j.. ..
: li ( lH - O - C - R ~ NH2-CH2-CH2-NH CH2 CH2 2 >
11 .
CH2 - O - C - R ~
.
1 ~ C-R
(I) ,~' - 10 -i ~t.
75(~
(II~
N - CH
R - C ~
IH -CH -N~ - 11 - R
Some of the intermediate amides shown above~ as well as some of the starting materials, other intermediates, water and other complexes are present as diluents along wi-th the desired --~
substituted imidazoline. Some of the diluents are removed during the vacuum stage of the reaction.
Alkoxylation of Imidazoline The formation of the 1,2-substituted imidazoline product will have as components~in~addition to the desired imidazoline product the materials notèd as diluents in the glyceride reaction above. If the imidazoline reaction forma-tion is the fatty acid reaction given above wherein the 2 substituted imidazoline is formed first and then the second long chain aliphatlc or cycloaliphatic hydrocarbon group is `
added~in~the l position by means of a reactlon with a fatty acid, or other agent, the desired imidazoline is going to be present in a mixture containing some of the imldazoline substituted only at the 2 position and ratty acid or other agent. Similarly, regardless of which reaction route is used, there will be ~rimary~and/or secondary amines present in the final ml~l~e due to~ either unreacted initial amine or the amide in,ermediate products. The materials which have pri-:: :
mary and secondary amine groups present are undesirable since in the quaternizing step, to be discussed subsequently, the amines cause the~dlsubstituted imidazoline to be trans~~ormed .. . . . : . ~ , - . - . .~ .
.- ... . . . . .. . -~o~ o to an amine salt rather than a quaternary salt which, in turn, is capable of reverting to free amines when present in an aqueous compositîon having a pH of about 5 or greater. The patent issued to Johnson, U.S. Patent 2,874,074, February 17, -1959, mentioned earlier in this specification, disclosed making the 1,2-substituted imidazoline by the two step fatty acid process. Johnson utilizes the 2 substituted imidazoline as made by Wilson, U.S. Patent 2,355,837, August 15, 1944, or U.S. Patent 2,267,965, December 30, 1941. The imidazoline product as made by Johnson would contain a mixture of the 1,2 substituted material, the 2 substituted material, other amine containing materials and fatty acid. The 2 substituted material and the other amines are undesirable, as indicated above, due to their ability to cause the imidazoline salt to be formed.
The present applicants have found that the undesir-able amine products present in the 1,2 substituted imidazoline : ,. .. .
reaction mixture can be effectively capped by treating the mixture with an alkylene oxide, preferably propylene oxide.
The alkylene oxide serves to "cap" the amines by attaching an alkylene oxide moiety to the free amine. It is important that all of the primary and secondary amines are capped, but only a minimum of the tertiary amine in the imidazoline.
To achieve these goals the mixture containing the desired 1,2 substituted imidazoline is treated with an amount of an alkylene oxide amounting to ~rom about 1 to 5% by weight of the mixture to be treated, while the temperature is kept at from about ~0C to about 140C and a vacuum is optionally drawn amounting to from about 2 to about 15 mm mercury. The vacuum helps to rid the system of excess alkylene oxide, polyamine and other low boiling diluents. The imidazoline .~, . . .
..
... - .. - . . . . . . , - . . . . ... ~ . . . .
751[D
containing mixture can also be diluted with an organic sol-vent such as isopropyl alcohol or glymes to facilitate the alkylene oxide treatmen-t. Such solvents are used in an amount of from a~out 1 to about 25% ~y weight of the imidazoline mixture. The time of the reaction ranges from about 0.5 to about 8 hours. U.SO Patent 2,713,582, July 19, 1955, to Smith, discloses making fully alkoxylated imidazolines as a precursor for carboxylate detergent products. Examples of alkoxylating agents other than propylene oxide include butyl-ene oxide, glycide, ethylene oxide, cyclohexame oxide, etc.
Quaternization The alkylene oxide treated mixture from above is treated with an alkylating agent to form the desired quaternary imidazolinium material essentially free of amines, amine salts and alk~xylated forms of the imidazolinium salts. The imidazolinium product preferably contains a total less than about 4~, preferably less than about 2%, of primary amines, secondary amines and cyclic tertiary amine salts and less than about 25%, preferably 4%, of the alkoxylated form of the imidazolinium salt. The limit on the alkoxylated form is the result of wanting to make the nonalkoxylated imidazolinium - :
salt as pure as~possible and is not related to the amine/amine salt stability problem. The alkylating agent can be any of the known agents such as methylchloride, ethylbromide, di-ethylsulfate, dlmethylsul~ate, hexadecylchloride, among many others. The reaction can be exemplified in -the following manner:
, ' ~ '-' ' '' `-.
.: .
:
.
.
, ~
;7~0 DN -- fH-R
R -- C~ ¦ + ~CH3~ 2~04 N -- CH -- R
4 ~ :
l ~
1 3 ¦ ~3 ;
~ f R -- C l C 3 04 . .
D--R
~.. ...... .. ..
wherein D, R, Rl, R3 and R4 are as described previously.
The amount of alkylating agent used should be equiva- , lent to the amount of the imidazoline treated on a molar basis.
However, an excess of the alkylating agent is generally used to~assure maximum quaternization. The amount of excess em- , ployed should be sufficient so that the pH of the reaction medium is in the range of from about 5 to about 7. The reac-tion time generally ranges from about 1 to about 12 hours and the temperature from about 40 to about 80C. If desired, a base may be added during the alkylation to aid quaterniza-tion. ' ,, The imidazolinium salt as formed above has out- ; ' standing fabric conditioning properties, softening and anti- '' static,~while additionally allowing fabric conditioning compo- ,~', ' , altions to be made which have improved aldehyde stability.
~ A preferred imidazolinium salt contains Rl and R groups ' 0 ¦ ~having~ 20 carbon atoms such as the following wherein the R groups are tallow outs~
.-::
.
.
- 14 - '; ' 7~i~
CH 2 ~) CT 11 - C ~ f CH3SO4 L CH2-CH ~-NH - C - CTallOJ
wherein CT 11 w is an aliphatic hydrocarbon chain derived from tallow fatty acid. ~-Other quaternary imidazolinium salts have desirable properties can be formed by substituting a different R group for tallow in the acylating or esterifying agent, a different alkylene or polyalkylene polyamine for diethylenetriamine, and a different anion, in the alkylating agent.
Fabric Conditioning Compositions The present invention is also directed to composi-tions comprising 1,2 substituted quaternary imidazolinium salts, said compositions containing a total less than about 4%, preferably less than about 2%, of primary amines, second~
ary amines and cyclic tertiary amine salts based on the weight of the imidazolinium salt. Additionally, the compositions preferably contàin less than about 25%, more preferably less than about 4%,~ of the alkoxylated form of the imidazolinium salt based on the weight of the nonalkoxylated form of the imidazolinium salt. The desired imidazolinium salt can be prepared using the process previously described, or another process which will yield the imidazolinium salt and will not have more than the above indicated levels of the various undesirable compounds. As indicated earlier, the imidazolinium compounds of interest herein have the formula:
~ ',`',' .
7~C~
R2 (~) N - CR
l ' DRl _ ~. .
wherein D is optional and, where present is selected from the group consisting of ~ n 2n~ ' ~Cn~2n~ N~ - C- and -~CH2tn-o-c-whereln n is a number from 1 to about 6. R and R1 arealiphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R3 and R4 are hydrogen, hydroxyl, short chain alkyl having from 1 to 4 carbon atoms or hydroxy forms of the short chain alkyl. Examples of D
are ( l n 2n ~ t n 2n) N~ C-, tCH2tn-o-lcl- , among manyothers.
O .. , where n is a number from about 1 to about 6. R2 is an alkyl group having from about 1 to 8 carbon atoms or an aralkyl group which was associated with the alkylating agent used ~
to quaternize the imidazoline compound. Examples of such -cations are methyl, ethyl, benzyl, etc. X is an anion ;associated with the alkylating agent and may be, for example, chloride, bromide, methylsulfate, ethylsulfate, among others.
: . :
It is to be recognized that while the quaternization is indi- ~
~ ': ` ' ~ );
-: ; ; : . . ~ .
~67S~
cated as having taken place at 3-nitrogen, quaternization at the l-nitrogen atom is not excluded. A pxeferred quaternary imidazolinium salt is the methylsulfate salt shown about.
The compositions of the present invention are pre-ferably aqueous and may contain any desired level of the quaternary imidazolinium salt. ~lowever, the compositions preferably contain from about 1 to about 15% of the salt and most preferably from about 2 to about 8~.
In addition to the preferred quaternary imidazolinium salt, the compositions of the present invention may also contain other fabric conditioning (sof-tening~antistatic) agents. Such other agents may be described as cationic or nonionic organic materials which are free of primary amines, secondary amines and cyclic tertiary amine saLts and are generally employed as fabric conditioning agents during the rinsing cycle of the household laundering process. They are organic, waxy materials having a melting tor softening) point between 25C and 115C. Such materials possess both fabric softening and fabric antistat properties.
Generally the cationic nitrogen-containing compounds such as quaternary ammonium compounds have one or two straight-chain organic groups of at least eight carbon atoms.
Preferably, they have one or two such groups of from 12 to 22 carbon atoms. Preferred cation-active softener compounds include the quaternary ammonium antistat/softener compounds corresponding to the formula:
Rl R3 +
/ X ' ~: -- ~ . . - ~
7Si~
wherein Rl is hydrogen or an aliphatic group o~ from 1 to 22 carbon atoms; R2 is an aliphatic group having from 12 to 22 carbon atoms; R3 and R4 are each alkyl groups of from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate radicals.
Because of their excellent softening efficacy and ready availability, preferred cationic antistat/softener compounds of the invention are the dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow. As employed herein, alkyl is intended as including unsaturated compounds such as are present in -alkyl groups derived from naturally occurring fatty oils.
The term "tallow" refers to fatty alkyl groups derived from tallow fatty acids. Such fatty acids give rise to quaternary softener compounds wherein Rl and R2 have predominantly from 16 to 18 carbon atoms. The term "coconut" refers to fatty acid groups from coconut oil fatty acids. The coconut-alkyl , Rl and R2 groups have from about 8 to about 18 carbon atoms and predominate in C12 to Cl~ alkyl groups. Representative ;
examples o~ quaternary softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate;
dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ::
ammonium chloride; dieicosyl dimethyl ammonium chloride;
didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chlor~ide; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate; di(coconut-alkyl) dimethyl ammonium chloride.
,~ ' - ~ -~67S~
~n especially preEerred class of quaternary ammonium antistat/softeners of the invention correspond to the formula:
~l3 - ~ - C~l~ X~
wherein Rl and R2 are each straight chain aliphatic groups of from 12 to 22 carbon atoms and X is halogen, e.g., chloride or methyl sulfate. Especially preferred are ditallow di-methyl ammonium chloride and di(hydrogenated tallow-alkyl) dimethyl ammonium chloride and di(coconut-alkyl) dimethyl ammonium chloride, these compounds being preferred from the standpoint of excellent softening properties and ready availability.
Nonionic fabric antistat/softener materials include -a wide varlety of materials including sor~itan esters, fatty alcohols and their derivatives and the like. One preferred type of nonionic fabric antistat/softener material comprises the esterified cyclic dehydration products of sorbitol, i.e., .
sorbitan ester. Sorbitol, itself prepared by catalytic hydro-genation of glucose, can be dehydrated in well-known fashion to form mixtures of cyclic 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See Brown; U.S. Patent 2,322,821; issued June 29, 1943.) The resulting complex mixtures of cyclic anhydrides of sorbital are collectively :
referred to herein as "sorbitan". It will be recognized that this "sorbitan" mixture will also contain some free .
uncyclized sorbital.
Sorbitan ester fabric antistak/softener materials useful herein are prepared by esterifying the "sorbitan"
mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty (C10-C24~ acid or fatty acid halide. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, complex mixtures of mono-, di-, tri-, and tetra-esters almost always result from such reactions, and the stoichiometric ratios of the reactants can simply be adjusted to favor the desired reaction product.
The foregoing complex mixtures of esterified cyclic dehydration products of sorbitol (and small amounts of esterified sorbitol) are collectively referred to herein as "sorbitan esters". Sorbitan mono- and di-esters of lauric, myristic, palmitic, stearic and behenic acids-are particularly useful herein for conditioning the fabrics being treated. Mixed sorbitan esters, e.g., mixtures of -the foregoing esters, and mixtures prepared by esterifying sorbitan with fatty acid mixtures such as the mixed tallow and hydrogenated pa~m oil fatty acids, are useful herein and are economically attractive. Unsat- i urated C10-Cl8 sorbitan esters, e.g., sorbitan mono-oleate, usually are present in such mixtures. It is to be recog-nized that all sorbitan esters, and mix-tures thereof, which are essentially water-insoluble and which have fatty hydrocarbyl "tails", are useful fabric antistat/softener materials in the context of the present invention.
The preferred alkyl sorbitan ester fabric anti-stat/softener materials herein comprise sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan di-stearate, sorbitan dibehenate, and mixtures thereof, the ` C,~
- . " ~ - - - : , , ~
mixed coconutalkyl sorbitan mono- and di-esters and the mixed tallowalkyl sorbitan mono- and di-esters. The tri- and tetra-esters o~ sorbitan with lauric, myristic, palmitic, stearic and behenic acids, and mixtures thereof, are also useful herein.
Another useful type of nonionic fabric antistat/
softener material encompasses the substantially water-insoluble compounds chemically classified as fatty alcohols. Mono-ols, di-ols, and poly-ols having the requisite melting points and water-insolubility properties set forth above are useful herein. Such alcohol-type fabric conditioning materials also include the mono- and di-fatty glycerides which contain at least one "free" OH group.
All manner of water-insoluble, high melting alcohols (including mono- and di-glycerides), are useful herein, inas-much as all such materials are fabric sustantive. Of course, it is desirable to use those materials which are colorless, so as not to alter the color of the fabrics being treated.
Toxicologically acceptable materials which are safe for use in contact with skin should be chasen.
A preferred type of unesterified alcohol useful herein includes the higher melting members of the so-called fatty alcohol class. Although once limited to alcohols ob-tained from natural fats and oils, the term "fatty alcohols"
has come to mean those alcohols which correspond to the alcohols obtainable from fats and oils, and all such alcohols can be made by synthetic processes. Fatty alcohols prepared -by the mild oxidation of petroleum products are useful herein.
Another type of material which can be classified as an alcohol and which can be employed as a fabric antistat/
softener material in the instant invention encompasses various ~ ~
:' :':
, ~ ,~
i7S;~
esters of polyhydric alcohols. Such "ester-alcohol" materials which have a ~elting point within the range recited herein and which are substantially water-insoluble can be employed herein when they contain at least one free hydroxyl group, i.e., when they can be classified chemically as alcohols.
The alcoholic di-esters o~ glycerol useful herein include both the 1,3-di-glycerides and the 1,2-di-glycerides.
In particular, di-glycerides containing two C8-C20, prefer-ably C10-C18, alkyl groups in the molecule are useful fabric conditioning agents.
Non-limiting examples of ester-alcohols useful herein include: glycerol-1,2-dilaurate; glycerol-1,3-dilaurate;
glycerol-1,2-myristate; glycerol-1,3-dimyristate; glycerol-l, 2-dipalmitate; glycerol-1,3-dipalmitate; glycerol-1j2-di-stearate and glycerol-1,3-distearate. Mixed glycerides avail-:
able from mixed tallowalkyl fatty acids, i.e., 1,2-ditallow-alkyl glycerol and 1,3-ditallowalkyl glycerol, are economically attractive for use herein. The foregoing ester-alcohols are preferred for use herein due to their ready availability from natural fats and oils. ~ ~
Mono- and dl-ether alcohols, ~especially the C10-C18 di-ether~alcohols having at least one free~-OH graup,~ also fall within the definition of alcohols useful as fabric anti-stat/softener materials herein. The ether-alcohols can be -prepared by the classic Williamson ether synthesis. As with the ester-alcohols, the reaction conditions are chosen such :
that at least one ree, unetherified -OH group remains in the molecule.;~
~ Ether-alcohols useful herein include glycerol-1,2-3`0 ~ ~ dllauryI ether; glycerol-1,3-distearyl ether; and butane :
t~etra-ol-1,2,3-trioctanyl ether.
~ ~ ~ ` ' . .
~36~
The fabric antistat/softeners rnentioned above can be used alone or as mix-tures in combination with the imidazol-inium compound in the practice of the present invention.
The ayents when present ;n the co~positions of the present invention are normally present in amount ranging from about 1 to 12~ by weight of the composition, preferably from about 1 to about 8%. Preferred mixtures are mixtures of the quat-ernary imidazolinium salt with a sorbitan ester, a fatty -alcohol, or a quaternary ammonium compound. A most preferred mixture is the quaternary imidazolinium salt with ditallow dimethyl ammonium chloride (DTDMAC). These two compounds are pre-ferably used in a weight ratio of ~rom about 80/20 to about 20/80 and most preferably in a weight ratio of from 30/70 to 70/30 imidazolinium/DTDMAC.
Conventional liquid fabric conditioning composition components may be dissolved or dispersed in the composition.
These conventional components include clay materials, aldehyde -preservatives, emulsifiers, thickeners, opacifiers, coloring agents, brightenersj fluorescers~ pH adjustment agents and perfume materials. Such optional materials generally comprise about 0.01~ to 10~ by weight of the composition.
~ Proc e s s lng The aqueous fabric conditioning compositions herein can be prepared by adding the~fabric softening and static :-control agents to water using conventional techniques. For examplel the agent or agents can be heated to form a liquid oily phase and can be added wlth mixing to water maintained at elevated temperatures. Optional ingredients can be added according to methods known in the art. The composition is then adjusted to a pH of from about 3 to about 9, preferably, from about 4.5 to 7.
- - ~
~ 23 -s~
composition Usage The compositions o~ the pre~ent invention are pre-ferably used in the rinse cycle of the conventional automatic laundry operations. Generally, rinse water has a temperature of from about 15C to about 60C.
When compositions of the present invention are added to the rinse cycle, the fabric conditioning agents are generally present at levels of from about 2 ppm to about 500 ppm, preferably from about 10 ppm to about 100 ppm. These concentration levels achieve superior fabric softening and static control.
In general, the invention herein in its fabric conditioning method aspect comprises: (a) washing fabrics in a conventional automatic washing machine with a deter-gent composition (normally containing a detersive surfactant or mixture of surfactants selected from the group consisting of anionic, nonionic, amphoteric or ampholytic surfactants), (b) rinsing the fabrics, and (c3 adding during the rinse stage of the operation the above-described levels of the fabric conditioning agents. Preferably, a final step (dl includes drying the fabrics in an automatic dryer at a tem-perature of at least about 38C. This drying stage facili-tates spreading of the fabric conditioning materials herein across the fabric surfaces and is especially useful when the particulate sorbitan ester material is utilized.
The following exemplifies the fabric conditioning -~
compositions and methods of this invention and the benefits -achleved by the utilization of such compositions and methods.
These examples are illustrative of the invention herein and ~30~ are not necessarily considered as limiting thereof.
.: :
`il f ~ .
EXA~PLE I
~ n imidazolinium salt essentially free of amines, amine salts and propoxylated imidazolinium salts is prepared in the following manner:
A. Diethylenetriamine and hardened tallow triglyceride in a molar ratio of amine/triglyceride of approximately 1.4/1 are added to a reaction vessel.
B. The amine and triglyceride are reacted for a period of three hours at a temperature of approximately 185C and a-tmospheric pressure.
C. The pressure in the reaction vessel is reduced to approxi-mately 10 mm mercury and kept at that condition for a period of two hours. The product at this point is the imidazoline intermediate for the desired imidazolinium salt plus unreactants and primary and secondary amines from intermediate amide products. The reaction mixture - -is analyzed using conventional analytical techniques for the amount of imidazoline and primary and secondary amines. -D. The reaction vessel is cooled to 80C and isopropyl alcohol is added to the vessel in an amount equal to ,~
:::
approximately 20% of the vessel's contents. The solvent aids in keeping the reaction medium fluid.
E. Propylene oxide is added to the reaction vessel in an amount equal to approximately 2% o~ the imidazoline and unreactants. This amount is sufficient to convert the unreacted primary and secondary amines to propoxylated tertiary amine. ~ -. The reaction vessel is subjec-ted to a vacuum of approxi- -mately 10 mm mercury for a period of 1 hour. ~-.: ~: ' :, f~ '' ' ,.
~' ~ . ' , ~ . - ~ - . . . : . . - . - . .; - . . .. .
~ 7SiO
G. The propoxylated reaction mixture is finally charged with an alkylating a~ent in the form of dimethylsul- .
fate. The amount of alkylating agent originally used is slightly less than the number of moles of imidazoline formed after step C above. As the alkylation proceeds the pH of the reaction medium is monitored and additional dimethylsulfate is added until the pH is in the 5-7 range.
The product formed in the above reaction is l-methyl-l-tallow-amidoethyl-2-tallow imidazolinium methylsulfate which is essentially free of amines and amine salts.
EXAMPLE II
The following compositions are prepared:
A B
Imidazolinium salt of 26.25 grams --Example 1 Imidazolinium salt of -- 26.25 grams Example I made without employing the propylene oxide step Aldehyde source 0.55 grams0.55 grams Water g.s. to 1000 grams-~.s. to 1000 grams '~. .
The pH of both samples are adjusted to 5.8 with sodium hydroxide.
Compositions A and B are analyzed for remaining aldehyde after one week at the temperatures shown below. The amount of aldehyde o~iginally in the compositions is 550 ppm.
:' -.
26 - ~
i7SI~
Temperature A B
70F 510 ppm 470 ppm The above figures demonstrate the improved aldehyde stability with the imidazolinium essentially free of amines and amine salts. Similar results are obtained with other imidazolinium salts made using polyamines and acylating or ~
esterifying agents other than the diethylenetriamine and ~. .
tal1ow triglyceride of Example I.
. ~
"
"
:
' ,, ~..
:.
.. .
:` ~: :, , ~ ~: ' :. .
...
:- ... .
l ~
1 3 ¦ ~3 ;
~ f R -- C l C 3 04 . .
D--R
~.. ...... .. ..
wherein D, R, Rl, R3 and R4 are as described previously.
The amount of alkylating agent used should be equiva- , lent to the amount of the imidazoline treated on a molar basis.
However, an excess of the alkylating agent is generally used to~assure maximum quaternization. The amount of excess em- , ployed should be sufficient so that the pH of the reaction medium is in the range of from about 5 to about 7. The reac-tion time generally ranges from about 1 to about 12 hours and the temperature from about 40 to about 80C. If desired, a base may be added during the alkylation to aid quaterniza-tion. ' ,, The imidazolinium salt as formed above has out- ; ' standing fabric conditioning properties, softening and anti- '' static,~while additionally allowing fabric conditioning compo- ,~', ' , altions to be made which have improved aldehyde stability.
~ A preferred imidazolinium salt contains Rl and R groups ' 0 ¦ ~having~ 20 carbon atoms such as the following wherein the R groups are tallow outs~
.-::
.
.
- 14 - '; ' 7~i~
CH 2 ~) CT 11 - C ~ f CH3SO4 L CH2-CH ~-NH - C - CTallOJ
wherein CT 11 w is an aliphatic hydrocarbon chain derived from tallow fatty acid. ~-Other quaternary imidazolinium salts have desirable properties can be formed by substituting a different R group for tallow in the acylating or esterifying agent, a different alkylene or polyalkylene polyamine for diethylenetriamine, and a different anion, in the alkylating agent.
Fabric Conditioning Compositions The present invention is also directed to composi-tions comprising 1,2 substituted quaternary imidazolinium salts, said compositions containing a total less than about 4%, preferably less than about 2%, of primary amines, second~
ary amines and cyclic tertiary amine salts based on the weight of the imidazolinium salt. Additionally, the compositions preferably contàin less than about 25%, more preferably less than about 4%,~ of the alkoxylated form of the imidazolinium salt based on the weight of the nonalkoxylated form of the imidazolinium salt. The desired imidazolinium salt can be prepared using the process previously described, or another process which will yield the imidazolinium salt and will not have more than the above indicated levels of the various undesirable compounds. As indicated earlier, the imidazolinium compounds of interest herein have the formula:
~ ',`',' .
7~C~
R2 (~) N - CR
l ' DRl _ ~. .
wherein D is optional and, where present is selected from the group consisting of ~ n 2n~ ' ~Cn~2n~ N~ - C- and -~CH2tn-o-c-whereln n is a number from 1 to about 6. R and R1 arealiphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R3 and R4 are hydrogen, hydroxyl, short chain alkyl having from 1 to 4 carbon atoms or hydroxy forms of the short chain alkyl. Examples of D
are ( l n 2n ~ t n 2n) N~ C-, tCH2tn-o-lcl- , among manyothers.
O .. , where n is a number from about 1 to about 6. R2 is an alkyl group having from about 1 to 8 carbon atoms or an aralkyl group which was associated with the alkylating agent used ~
to quaternize the imidazoline compound. Examples of such -cations are methyl, ethyl, benzyl, etc. X is an anion ;associated with the alkylating agent and may be, for example, chloride, bromide, methylsulfate, ethylsulfate, among others.
: . :
It is to be recognized that while the quaternization is indi- ~
~ ': ` ' ~ );
-: ; ; : . . ~ .
~67S~
cated as having taken place at 3-nitrogen, quaternization at the l-nitrogen atom is not excluded. A pxeferred quaternary imidazolinium salt is the methylsulfate salt shown about.
The compositions of the present invention are pre-ferably aqueous and may contain any desired level of the quaternary imidazolinium salt. ~lowever, the compositions preferably contain from about 1 to about 15% of the salt and most preferably from about 2 to about 8~.
In addition to the preferred quaternary imidazolinium salt, the compositions of the present invention may also contain other fabric conditioning (sof-tening~antistatic) agents. Such other agents may be described as cationic or nonionic organic materials which are free of primary amines, secondary amines and cyclic tertiary amine saLts and are generally employed as fabric conditioning agents during the rinsing cycle of the household laundering process. They are organic, waxy materials having a melting tor softening) point between 25C and 115C. Such materials possess both fabric softening and fabric antistat properties.
Generally the cationic nitrogen-containing compounds such as quaternary ammonium compounds have one or two straight-chain organic groups of at least eight carbon atoms.
Preferably, they have one or two such groups of from 12 to 22 carbon atoms. Preferred cation-active softener compounds include the quaternary ammonium antistat/softener compounds corresponding to the formula:
Rl R3 +
/ X ' ~: -- ~ . . - ~
7Si~
wherein Rl is hydrogen or an aliphatic group o~ from 1 to 22 carbon atoms; R2 is an aliphatic group having from 12 to 22 carbon atoms; R3 and R4 are each alkyl groups of from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate radicals.
Because of their excellent softening efficacy and ready availability, preferred cationic antistat/softener compounds of the invention are the dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow. As employed herein, alkyl is intended as including unsaturated compounds such as are present in -alkyl groups derived from naturally occurring fatty oils.
The term "tallow" refers to fatty alkyl groups derived from tallow fatty acids. Such fatty acids give rise to quaternary softener compounds wherein Rl and R2 have predominantly from 16 to 18 carbon atoms. The term "coconut" refers to fatty acid groups from coconut oil fatty acids. The coconut-alkyl , Rl and R2 groups have from about 8 to about 18 carbon atoms and predominate in C12 to Cl~ alkyl groups. Representative ;
examples o~ quaternary softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate;
dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ::
ammonium chloride; dieicosyl dimethyl ammonium chloride;
didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chlor~ide; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate; di(coconut-alkyl) dimethyl ammonium chloride.
,~ ' - ~ -~67S~
~n especially preEerred class of quaternary ammonium antistat/softeners of the invention correspond to the formula:
~l3 - ~ - C~l~ X~
wherein Rl and R2 are each straight chain aliphatic groups of from 12 to 22 carbon atoms and X is halogen, e.g., chloride or methyl sulfate. Especially preferred are ditallow di-methyl ammonium chloride and di(hydrogenated tallow-alkyl) dimethyl ammonium chloride and di(coconut-alkyl) dimethyl ammonium chloride, these compounds being preferred from the standpoint of excellent softening properties and ready availability.
Nonionic fabric antistat/softener materials include -a wide varlety of materials including sor~itan esters, fatty alcohols and their derivatives and the like. One preferred type of nonionic fabric antistat/softener material comprises the esterified cyclic dehydration products of sorbitol, i.e., .
sorbitan ester. Sorbitol, itself prepared by catalytic hydro-genation of glucose, can be dehydrated in well-known fashion to form mixtures of cyclic 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See Brown; U.S. Patent 2,322,821; issued June 29, 1943.) The resulting complex mixtures of cyclic anhydrides of sorbital are collectively :
referred to herein as "sorbitan". It will be recognized that this "sorbitan" mixture will also contain some free .
uncyclized sorbital.
Sorbitan ester fabric antistak/softener materials useful herein are prepared by esterifying the "sorbitan"
mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty (C10-C24~ acid or fatty acid halide. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, complex mixtures of mono-, di-, tri-, and tetra-esters almost always result from such reactions, and the stoichiometric ratios of the reactants can simply be adjusted to favor the desired reaction product.
The foregoing complex mixtures of esterified cyclic dehydration products of sorbitol (and small amounts of esterified sorbitol) are collectively referred to herein as "sorbitan esters". Sorbitan mono- and di-esters of lauric, myristic, palmitic, stearic and behenic acids-are particularly useful herein for conditioning the fabrics being treated. Mixed sorbitan esters, e.g., mixtures of -the foregoing esters, and mixtures prepared by esterifying sorbitan with fatty acid mixtures such as the mixed tallow and hydrogenated pa~m oil fatty acids, are useful herein and are economically attractive. Unsat- i urated C10-Cl8 sorbitan esters, e.g., sorbitan mono-oleate, usually are present in such mixtures. It is to be recog-nized that all sorbitan esters, and mix-tures thereof, which are essentially water-insoluble and which have fatty hydrocarbyl "tails", are useful fabric antistat/softener materials in the context of the present invention.
The preferred alkyl sorbitan ester fabric anti-stat/softener materials herein comprise sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan di-stearate, sorbitan dibehenate, and mixtures thereof, the ` C,~
- . " ~ - - - : , , ~
mixed coconutalkyl sorbitan mono- and di-esters and the mixed tallowalkyl sorbitan mono- and di-esters. The tri- and tetra-esters o~ sorbitan with lauric, myristic, palmitic, stearic and behenic acids, and mixtures thereof, are also useful herein.
Another useful type of nonionic fabric antistat/
softener material encompasses the substantially water-insoluble compounds chemically classified as fatty alcohols. Mono-ols, di-ols, and poly-ols having the requisite melting points and water-insolubility properties set forth above are useful herein. Such alcohol-type fabric conditioning materials also include the mono- and di-fatty glycerides which contain at least one "free" OH group.
All manner of water-insoluble, high melting alcohols (including mono- and di-glycerides), are useful herein, inas-much as all such materials are fabric sustantive. Of course, it is desirable to use those materials which are colorless, so as not to alter the color of the fabrics being treated.
Toxicologically acceptable materials which are safe for use in contact with skin should be chasen.
A preferred type of unesterified alcohol useful herein includes the higher melting members of the so-called fatty alcohol class. Although once limited to alcohols ob-tained from natural fats and oils, the term "fatty alcohols"
has come to mean those alcohols which correspond to the alcohols obtainable from fats and oils, and all such alcohols can be made by synthetic processes. Fatty alcohols prepared -by the mild oxidation of petroleum products are useful herein.
Another type of material which can be classified as an alcohol and which can be employed as a fabric antistat/
softener material in the instant invention encompasses various ~ ~
:' :':
, ~ ,~
i7S;~
esters of polyhydric alcohols. Such "ester-alcohol" materials which have a ~elting point within the range recited herein and which are substantially water-insoluble can be employed herein when they contain at least one free hydroxyl group, i.e., when they can be classified chemically as alcohols.
The alcoholic di-esters o~ glycerol useful herein include both the 1,3-di-glycerides and the 1,2-di-glycerides.
In particular, di-glycerides containing two C8-C20, prefer-ably C10-C18, alkyl groups in the molecule are useful fabric conditioning agents.
Non-limiting examples of ester-alcohols useful herein include: glycerol-1,2-dilaurate; glycerol-1,3-dilaurate;
glycerol-1,2-myristate; glycerol-1,3-dimyristate; glycerol-l, 2-dipalmitate; glycerol-1,3-dipalmitate; glycerol-1j2-di-stearate and glycerol-1,3-distearate. Mixed glycerides avail-:
able from mixed tallowalkyl fatty acids, i.e., 1,2-ditallow-alkyl glycerol and 1,3-ditallowalkyl glycerol, are economically attractive for use herein. The foregoing ester-alcohols are preferred for use herein due to their ready availability from natural fats and oils. ~ ~
Mono- and dl-ether alcohols, ~especially the C10-C18 di-ether~alcohols having at least one free~-OH graup,~ also fall within the definition of alcohols useful as fabric anti-stat/softener materials herein. The ether-alcohols can be -prepared by the classic Williamson ether synthesis. As with the ester-alcohols, the reaction conditions are chosen such :
that at least one ree, unetherified -OH group remains in the molecule.;~
~ Ether-alcohols useful herein include glycerol-1,2-3`0 ~ ~ dllauryI ether; glycerol-1,3-distearyl ether; and butane :
t~etra-ol-1,2,3-trioctanyl ether.
~ ~ ~ ` ' . .
~36~
The fabric antistat/softeners rnentioned above can be used alone or as mix-tures in combination with the imidazol-inium compound in the practice of the present invention.
The ayents when present ;n the co~positions of the present invention are normally present in amount ranging from about 1 to 12~ by weight of the composition, preferably from about 1 to about 8%. Preferred mixtures are mixtures of the quat-ernary imidazolinium salt with a sorbitan ester, a fatty -alcohol, or a quaternary ammonium compound. A most preferred mixture is the quaternary imidazolinium salt with ditallow dimethyl ammonium chloride (DTDMAC). These two compounds are pre-ferably used in a weight ratio of ~rom about 80/20 to about 20/80 and most preferably in a weight ratio of from 30/70 to 70/30 imidazolinium/DTDMAC.
Conventional liquid fabric conditioning composition components may be dissolved or dispersed in the composition.
These conventional components include clay materials, aldehyde -preservatives, emulsifiers, thickeners, opacifiers, coloring agents, brightenersj fluorescers~ pH adjustment agents and perfume materials. Such optional materials generally comprise about 0.01~ to 10~ by weight of the composition.
~ Proc e s s lng The aqueous fabric conditioning compositions herein can be prepared by adding the~fabric softening and static :-control agents to water using conventional techniques. For examplel the agent or agents can be heated to form a liquid oily phase and can be added wlth mixing to water maintained at elevated temperatures. Optional ingredients can be added according to methods known in the art. The composition is then adjusted to a pH of from about 3 to about 9, preferably, from about 4.5 to 7.
- - ~
~ 23 -s~
composition Usage The compositions o~ the pre~ent invention are pre-ferably used in the rinse cycle of the conventional automatic laundry operations. Generally, rinse water has a temperature of from about 15C to about 60C.
When compositions of the present invention are added to the rinse cycle, the fabric conditioning agents are generally present at levels of from about 2 ppm to about 500 ppm, preferably from about 10 ppm to about 100 ppm. These concentration levels achieve superior fabric softening and static control.
In general, the invention herein in its fabric conditioning method aspect comprises: (a) washing fabrics in a conventional automatic washing machine with a deter-gent composition (normally containing a detersive surfactant or mixture of surfactants selected from the group consisting of anionic, nonionic, amphoteric or ampholytic surfactants), (b) rinsing the fabrics, and (c3 adding during the rinse stage of the operation the above-described levels of the fabric conditioning agents. Preferably, a final step (dl includes drying the fabrics in an automatic dryer at a tem-perature of at least about 38C. This drying stage facili-tates spreading of the fabric conditioning materials herein across the fabric surfaces and is especially useful when the particulate sorbitan ester material is utilized.
The following exemplifies the fabric conditioning -~
compositions and methods of this invention and the benefits -achleved by the utilization of such compositions and methods.
These examples are illustrative of the invention herein and ~30~ are not necessarily considered as limiting thereof.
.: :
`il f ~ .
EXA~PLE I
~ n imidazolinium salt essentially free of amines, amine salts and propoxylated imidazolinium salts is prepared in the following manner:
A. Diethylenetriamine and hardened tallow triglyceride in a molar ratio of amine/triglyceride of approximately 1.4/1 are added to a reaction vessel.
B. The amine and triglyceride are reacted for a period of three hours at a temperature of approximately 185C and a-tmospheric pressure.
C. The pressure in the reaction vessel is reduced to approxi-mately 10 mm mercury and kept at that condition for a period of two hours. The product at this point is the imidazoline intermediate for the desired imidazolinium salt plus unreactants and primary and secondary amines from intermediate amide products. The reaction mixture - -is analyzed using conventional analytical techniques for the amount of imidazoline and primary and secondary amines. -D. The reaction vessel is cooled to 80C and isopropyl alcohol is added to the vessel in an amount equal to ,~
:::
approximately 20% of the vessel's contents. The solvent aids in keeping the reaction medium fluid.
E. Propylene oxide is added to the reaction vessel in an amount equal to approximately 2% o~ the imidazoline and unreactants. This amount is sufficient to convert the unreacted primary and secondary amines to propoxylated tertiary amine. ~ -. The reaction vessel is subjec-ted to a vacuum of approxi- -mately 10 mm mercury for a period of 1 hour. ~-.: ~: ' :, f~ '' ' ,.
~' ~ . ' , ~ . - ~ - . . . : . . - . - . .; - . . .. .
~ 7SiO
G. The propoxylated reaction mixture is finally charged with an alkylating a~ent in the form of dimethylsul- .
fate. The amount of alkylating agent originally used is slightly less than the number of moles of imidazoline formed after step C above. As the alkylation proceeds the pH of the reaction medium is monitored and additional dimethylsulfate is added until the pH is in the 5-7 range.
The product formed in the above reaction is l-methyl-l-tallow-amidoethyl-2-tallow imidazolinium methylsulfate which is essentially free of amines and amine salts.
EXAMPLE II
The following compositions are prepared:
A B
Imidazolinium salt of 26.25 grams --Example 1 Imidazolinium salt of -- 26.25 grams Example I made without employing the propylene oxide step Aldehyde source 0.55 grams0.55 grams Water g.s. to 1000 grams-~.s. to 1000 grams '~. .
The pH of both samples are adjusted to 5.8 with sodium hydroxide.
Compositions A and B are analyzed for remaining aldehyde after one week at the temperatures shown below. The amount of aldehyde o~iginally in the compositions is 550 ppm.
:' -.
26 - ~
i7SI~
Temperature A B
70F 510 ppm 470 ppm The above figures demonstrate the improved aldehyde stability with the imidazolinium essentially free of amines and amine salts. Similar results are obtained with other imidazolinium salts made using polyamines and acylating or ~
esterifying agents other than the diethylenetriamine and ~. .
tal1ow triglyceride of Example I.
. ~
"
"
:
' ,, ~..
:.
.. .
:` ~: :, , ~ ~: ' :. .
...
:- ... .
Claims (26)
1. A process for making quaternary imidazolinium salts, essentially free of amines, amine salts and alkoxylated forms of the imidazolinium salts, having the following structure:
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps:
A. Forming a mixture of an acylating or esterifying agent having an aliphatic or cycloaliphatic hydro-carbon group containing from about 10 to about 22 carbon atoms associated with each acyl group and an alkylene or polyalkylene polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 to about 1.5:1;
B. Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100°C to about 250°C and then drawing a vacuum of from about 0.4 mm mercury to about 10 mm mercury for from about 1 to about 8 hours to form an imidazoline product in a mixture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B
with an alkoxylating agent in an amount equal to from about 1% to about 5% by weight of the imidazoline product mixture while maintaining the temperature at from about 80°C to about 140°C for a period of from about 0.5 to about 8 hours; and D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least 1:1.
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of wherein n is a number from 1 to about 6, and X is an anion;
said process comprising the following steps:
A. Forming a mixture of an acylating or esterifying agent having an aliphatic or cycloaliphatic hydro-carbon group containing from about 10 to about 22 carbon atoms associated with each acyl group and an alkylene or polyalkylene polyamine having two or three amino groups, one of which is a primary or secondary amino group in the 2 position to a primary amino group, the molar ratio of acyl groups to primary amine and hydroxyl groups being from about 0.33 to about 1.5:1;
B. Reacting the mixture of step A for a period of from about 3 to about 24 hours at a temperature of from about 100°C to about 250°C and then drawing a vacuum of from about 0.4 mm mercury to about 10 mm mercury for from about 1 to about 8 hours to form an imidazoline product in a mixture with starting materials and intermediates;
C. Treating the imidazoline product mixture of step B
with an alkoxylating agent in an amount equal to from about 1% to about 5% by weight of the imidazoline product mixture while maintaining the temperature at from about 80°C to about 140°C for a period of from about 0.5 to about 8 hours; and D. Treating the mixture of step C with an alkylating agent in an amount such that the molar ratio of alkylating agent to imidazoline is at least 1:1.
2. The process of Claim 1 wherein the molar ratio of acyl groups to primary amine and hydroxyl groups in step A is from about 0.33 to 0.66 and the following step is inserted between steps B and C:
Reacting the imidazoline product mixture of step B
with an acylating or esterifying agent of the type in step A in a molar ratio of acyl groups to imidazoline product from about 1:1 to about 1.5:1, at a tempera-ture of from about 100°C to about 250°C and for a period of from about 1 to about 24 hours.
Reacting the imidazoline product mixture of step B
with an acylating or esterifying agent of the type in step A in a molar ratio of acyl groups to imidazoline product from about 1:1 to about 1.5:1, at a tempera-ture of from about 100°C to about 250°C and for a period of from about 1 to about 24 hours.
3. The process of Claim 1 wherein the molar ratio of acyl groups to primary amine and hydroxyl groups is from about 0.67 to about 1.50.
4. The process of Claim 3 wherein an organic solvent in an amount equal to from about 1% to about 25% by weight of the imidazoline product mixture of step B is added along with the alkoxylating agent in step C.
5. The process of Claim 4 wherein the aliphatic or cycloaliphatic hydrocarbon group associated with the acylating or esterifying agent in step A has from about 14 to about 20 carbon atoms.
6. The process of Claim 5 wherein the alkylene or poly-alkylene polyamine in step A has the formula:
wherein X is selected from the group consisting of ?CH2-CH?nOH , ?CH2-CH2?nCH3 , hydrogen and ?CH2-CH2?nNH2 wherein n is a number from 1 to about 6.
wherein X is selected from the group consisting of ?CH2-CH?nOH , ?CH2-CH2?nCH3 , hydrogen and ?CH2-CH2?nNH2 wherein n is a number from 1 to about 6.
7. The process of Claim 6 wherein the alkoxylating agent in step C is selected from the group consisting of propylene oxide, ethylene oxide, butylene oxide, glycide and cyclohexane oxide.
8. The process of Claim 7 wherein the acylating or esterifying agent in step A is a glyceride ester of tallow fatty acid.
9. The process of Claim 8 wherein the alkylene or polyalkylene amine in step A is diethylenetriamine.
10. The process of Claim 9 wherein the alkylating agent is dimethylsulfate.
11. A fabric conditioning composition comprising a fabric conditioning amount of a quaternary imidazolinium salt of the following structure:
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of ?CnH2N? , and wherein n is a number from 1 to about 6, and X is an anion;
said composition containing a total tertiary amine salts based on the weight of the imidazolinium salt; the balance of said composition consisting essentially of ingredients which are conventionally employed in fabric conditioning compositions.
wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of ?CnH2N? , and wherein n is a number from 1 to about 6, and X is an anion;
said composition containing a total tertiary amine salts based on the weight of the imidazolinium salt; the balance of said composition consisting essentially of ingredients which are conventionally employed in fabric conditioning compositions.
12. The composition of claim 11 wherein the composition is in aqueous liquid form and the imidazolinium salt is present at a level of from about 1 to about 15% by weight.
13. The composition of claim 11 wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 14 to 20 carbon atoms.
14. The composition of claim 13 wherein R3 and R4 are hydrogen.
15. The composition of claim 14 wherein R and R1 are derived from tallow fatty acid.
16. The composition of claim 15 wherein R2 is methyl and X is methylsulfate.
17. The composition of claim 16 wherein D is , the concentration of the imidazolinium salt is from about 2 to about 8% by weight, and the pH of the composition is from about 4.5 to 7.
18. The composition of claim 11 wherein the concentration of the imidazolinium salt is from 2 to about 8%
by weight and the composition additionally contains another organic fabric conditioning agent which is free of primary amines, secondary amines, and cyclic tertiary amine salts in an amount equal to from about 1 to about 12% by weight.
by weight and the composition additionally contains another organic fabric conditioning agent which is free of primary amines, secondary amines, and cyclic tertiary amine salts in an amount equal to from about 1 to about 12% by weight.
19. The composition of claim 18 wherein the additional fabric conditioning agent is selected from the group consisting of fatty nonionic and cationic materials.
20. The composition of claim 19 wherein the additional fabric conditioning agent is selected from the group consisting of quaternary ammonium compounds, fatty alcohols and sorbitan esters.
21. The composition of claim 20 wherein the imidazolinium salt D is , R1 and R2 contain from 14 to 20 carbon atoms and R3 and R4 are hydrogen.
22. The composition of claim 21 wherein on the imidazolinium salt R and R1 are tallow, R2 is methyl and X is methylsulfate.
23. The composition of claim 22 wherein the additional fabric conditioning agent is dimethyl ditallow ammonium chloride and the weight ratio of imidazolinium salt to dimethyl ditallow ammonium chloride is from about 20/80 to about 80/20.
24. A method for conditioning fabrics comprising the steps:
(a) washing fabrics in an aqueous detergent bath containing a detergent;
(b) rinsing the fabrics in an aqueous rinse bath;
(c) adding to said rinse bath from about 2 ppm to about 500 ppm of a fabric conditioning agent having the structure wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of ?CnH2n? , and wherein n is a number from 1 to about 6, and X is an anion;
said imidazolinium salt containing a total less than about 4% of primary amines, secondary amines and cyclic tertiary amine salts;
(d) drying said fabrics.
(a) washing fabrics in an aqueous detergent bath containing a detergent;
(b) rinsing the fabrics in an aqueous rinse bath;
(c) adding to said rinse bath from about 2 ppm to about 500 ppm of a fabric conditioning agent having the structure wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 10 to about 22 carbon atoms, R2 is an alkyl group having from 1 to about 8 carbon atoms or an aralkyl group, R3 and R4 are hydrogen, hydroxy, short chain alkyl having from 1 to about 4 carbon atoms or hydroxy short chain alkyl having from 1 to about 4 carbon atoms, D is optional and, where present, is selected from the group consisting of ?CnH2n? , and wherein n is a number from 1 to about 6, and X is an anion;
said imidazolinium salt containing a total less than about 4% of primary amines, secondary amines and cyclic tertiary amine salts;
(d) drying said fabrics.
25. The method of claim 24 wherein R and R1 are aliphatic or cycloaliphatic hydrocarbon groups having from about 14 to about 20 carbon atoms and R3 and R4 are hydrogen.
26. The method of claim 25 wherein R2 is methyl, X is methylsulfate and R and R1 are tallow.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68795176A | 1976-05-20 | 1976-05-20 | |
| US687,951 | 1976-05-20 | ||
| US05/708,980 US4127489A (en) | 1976-05-20 | 1976-07-27 | Process for making imidazolinium salts, fabric conditioning compositions and methods |
| US708,980 | 1976-07-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1086750A true CA1086750A (en) | 1980-09-30 |
Family
ID=27104119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA277,088A Expired CA1086750A (en) | 1976-05-20 | 1977-04-27 | Process for making imidazolinium salts, fabric conditioning compositions and methods |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS6042315B2 (en) |
| AT (1) | AT384629B (en) |
| CA (1) | CA1086750A (en) |
| CH (1) | CH639444A5 (en) |
| DE (1) | DE2721847A1 (en) |
| ES (1) | ES458979A1 (en) |
| FR (1) | FR2351968A1 (en) |
| GB (1) | GB1574496A (en) |
| IT (1) | IT1078951B (en) |
| NL (1) | NL7705487A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0013780B2 (en) * | 1979-01-11 | 1988-08-31 | THE PROCTER & GAMBLE COMPANY | Concentrated fabric softening composition |
| DE3618944A1 (en) * | 1986-06-05 | 1987-12-10 | Henkel Kgaa | QUARTAERE 2-ALKYLIMIDAZOLINIAL SALTS, METHOD FOR THE PRODUCTION AND USE THEREOF |
| JP2504741Y2 (en) * | 1993-03-22 | 1996-07-10 | 株式会社日光製作所 | Chip saw for siding material |
| DE102013219046A1 (en) * | 2013-09-23 | 2015-03-26 | Rudolf Gmbh | Polysiloxanes with quaternized heterocyclic groups |
| JP6651556B2 (en) * | 2017-03-07 | 2020-02-19 | 三洋化成工業株式会社 | Softener base and softener |
| CN114736352B (en) * | 2022-05-11 | 2023-07-11 | 江苏南方包装有限公司 | Imidazoline polymer and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2355837A (en) * | 1942-03-17 | 1944-08-15 | Carbide & Carbon Chem Corp | Substituted glyoxalidines |
| US2468180A (en) * | 1948-03-11 | 1949-04-26 | Petrolite Corp | Process for breaking petroleum emulsions |
| US2713583A (en) * | 1952-04-10 | 1955-07-19 | Petrolite Corp | Derivatives of imidazolines and pyrimidines |
| US2874074A (en) * | 1956-05-08 | 1959-02-17 | Nat Aluminate Corp | 1, 2-substituted imidazolinium salt and treatment of cellulosic fibrous materials therewith |
| DE2210087B2 (en) * | 1972-03-02 | 1980-11-27 | Hoechst Ag, 6000 Frankfurt | Imidazolinium salts and fabric softeners containing them |
| US3933871A (en) * | 1973-11-12 | 1976-01-20 | Armstrong Chemical Company, Inc. | Fabric softener compound and processes for preparing and using the same |
-
1977
- 1977-04-27 CA CA277,088A patent/CA1086750A/en not_active Expired
- 1977-05-14 DE DE19772721847 patent/DE2721847A1/en active Granted
- 1977-05-18 NL NL7705487A patent/NL7705487A/en not_active Application Discontinuation
- 1977-05-18 FR FR7715418A patent/FR2351968A1/en active Granted
- 1977-05-18 CH CH618977A patent/CH639444A5/en not_active IP Right Cessation
- 1977-05-18 AT AT359177A patent/AT384629B/en not_active IP Right Cessation
- 1977-05-19 GB GB2111777A patent/GB1574496A/en not_active Expired
- 1977-05-19 IT IT2377977A patent/IT1078951B/en active
- 1977-05-20 JP JP52058608A patent/JPS6042315B2/en not_active Expired
- 1977-05-20 ES ES458979A patent/ES458979A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| ATA359177A (en) | 1987-05-15 |
| NL7705487A (en) | 1977-11-22 |
| GB1574496A (en) | 1980-09-10 |
| JPS537670A (en) | 1978-01-24 |
| DE2721847A1 (en) | 1977-12-01 |
| CH639444A5 (en) | 1983-11-15 |
| FR2351968B1 (en) | 1981-12-18 |
| JPS6042315B2 (en) | 1985-09-21 |
| DE2721847C2 (en) | 1991-04-11 |
| IT1078951B (en) | 1985-05-08 |
| ES458979A1 (en) | 1978-10-01 |
| FR2351968A1 (en) | 1977-12-16 |
| AT384629B (en) | 1987-12-10 |
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