Claims
- 1. An aqueous fabric softening composition comprising from about 1% to about 50% of the reaction mixture produced in a process wherein said reaction product mixture contains di-substituted imidazoline compounds useful as fabric conditioning agents, said process comprising:
- a) forming a liquid reaction mixture containing (1) an acylating agent selected from fatty acids of the formula RCOOH, fatty acid halides of the formula RC(O)Y, fatty acid anhydrides of the formula (RC(O)).sub.2 O, or fatty acid short chain esters of the formula RC(O)OR.sup.1, wherein, in said formulas, R is a C.sub.7 -C.sub.21 hydrocarbyl group, R.sup.1 is a C.sub.1 -C.sub.4 alkyl group, and Y is a halide, and (2) a polyamine having the formula NH.sub.2 --(CH.sub.2).sub.m --NH--(CH.sub.2).sub.n --X--H, wherein m and n are, independently, integers from 2-6, and X is O, S, O(R.sup.3)p, or S(R.sup.3)p, wherein R.sup.3 is an alkoxy group and p is an integer from 1 to 100, the molar ratio of the acylating agent to the polyamine ranging from about 0.75:1 to 0.90:1;
- b) maintaining said liquid reaction mixture at a temperature of from about 100.degree. C. to 240.degree. C. for a period of time sufficient to convert at least about 50 percent of the polyamine in the mixture to a mono-substituted imidazoline of the formula: ##STR10## wherein R, m, n and X are as hereinbefore defined; the improvement comprising:
- c) adding to said liquid reaction mixture formed in step (b), after drying if necessary to form an anhydrous mixture, both an esterifying agent and a catalytically effective amount of an esterification catalyst, said esterifying agent being selected from C.sub.1 -C.sub.4 mono-esters of C.sub.12 -C.sub.22 fatty acids and C.sub.12 -C.sub.22 fatty acid mono-, di-, and tri-glycerides;
- said esterifying agent being present in an amount sufficient to provide a molar ratio of esterifying agent to acylating agent originally present in step (a) of from about 0.75:1 to 1.2:1;
- said esterification catalyst being selected from transition metal alkoxides of the formula Ti(OR.sup.6).sub.4, wherein R.sup.6 is a C.sub.1 -C.sub.4 alkyl group, transition metal alkyl alkoxides, transition metal halides, transition metal alkyl halides, stannous salts, dialkyltin chlorides and SnT.sub.2, wherein T is, independently, a C.sub.1 -C.sub.8 hydrocarbyl group, a hydroxyl group, or a halide; and subsequently;
- d) maintaining said anhydrous liquid reaction mixture at a temperature of from about 100.degree. C. to 200.degree. C. for a period of time ranging from about 1 to 5 hours to form a reaction product mixture which contains one or more di-substituted imidazolines of the formula: ##STR11## wherein R, m, n and X are as hereinbefore defined, and wherein R.sup.4 is a C.sub.11 -C.sub.21 hydrocarbyl.
- 2. An aqueous fabric softening composition comprising from about 1% to about 50% of the reaction mixture produced in a process wherein said reaction product mixture contains di-substituted imidazoline compounds useful as fabric conditioning agents, said process comprising:
- a) forming a liquid reaction mixture containing (1) an acylating agent selected from fatty acids of the formula RCOOH, fatty acid halides of the formula RC(O)Y, fatty acid anhydrides of the formula (RC(O)).sub.2 O, or fatty acid short chain esters, of the formula RC(O)OR.sup.1, wherein, in said formulas, R is a C.sub.7 -C.sub.21 hydrocarbyl group, R.sup.1 is a C.sub.1 -C.sub.4 alkyl group, and Y is a halide, and (2) a polyamine having the formula "NH.sub.2 --(CH.sub.2).sub.m --NH--(CH.sub.2).sub.n 13 X--H", wherein m and n are, independently, integers from 2-6, and X is O, S, O(R.sup.3).sub.p, or S(R.sup.3).sub.p, wherein R.sup.3 is an alkoxy group and p is an integer from 1 to 100, the molar ratio of the acylating agent to the polyamine ranging from about 0.75:1 to 0.90:1;
- b) maintaining said liquid reaction mixture at a temperature of from about 100.degree. C. to 240.degree. C. for a period from about 4 hours to about 18 hours at atmospheric pressure under an inert gas, converting at least 90 percent of the polyamine in the mixture to a mono-substituted imidazoline of the formula: ##STR12## wherein R, m, n and X are as hereinbefore defined; the improvement comprising:
- c) adding to said liquid reaction mixture formed in step (b), after drying if necessary to form an anhydrous mixture, both an esterifying agent and a catalytically effective amount of an esterification catalyst, said esterifying agent being of the formula: ##STR13## wherein R.sup.4 is a C.sub.11 -C.sub.21 hydrocarbyl group and R.sup.5 is a C.sub.1 -C.sub.4 alkyl group;
- said esterifying agent being present in an amount sufficient to provide a molar ratio of esterifying agent to acylating agent originally present in step (a) of from about 0.75:1 to 1.2:1;
- said esterification catalyst being selected from Ti(OR.sup.6).sub.4, wherein R.sup.6 is a C.sub.1 -C.sub.4 alkyl group, TiY.sub.4, wherein Y is a halide; wherein T is, independently, a C.sub.1 -C.sub.8 hydrocarbyl group, a hydroxyl group, or a halide and a dialkyltin chloride; and a dialkyltin chloride; and subsequently
- d) maintaining said anhydrous liquid reaction mixture at a temperature of from about 100.degree. C. to 200.degree. C. for a period of from about 1 to about 5 hours under an inert gas, producing a reaction product mixture containing one or more di-substituted imidazolines of the formula: ##STR14## wherein R, R.sup.4, m, n and X are as hereinbefore defined.
- 3. An aqueous fabric softening composition comprising from about 1% to about 50% of the reaction mixture produced in a process wherein said reaction product mixture contains di-substituted imidazoline compounds useful as fabric conditioning agents, said process comprising:
- a) forming a liquid reaction mixture containing (1) an acylating agent selected from fatty acids of the formula RCOOH, fatty acid halides of the formula RC(O)Y, fatty acid anhydrides of the formula (RC(O)).sub.2 O, or fatty acid short chain esters of the formula RC(O)OR.sup.1, wherein, in said formulas, R is a C.sub.7 -C.sub.21 hydrocarbyl group, R.sup.1 is a C.sub.1 -C.sub.4 alkyl group, and Y is a halide, and (2) a polyamine having the formula NH.sub.2 --(CH.sub.2).sub.m --NH--(CH.sub.2).sub.n --X--H, wherein m and n are, independently, integers from 2-6, and X is O, S, O(R.sup.3)p, or S(R.sup.3)p, wherein R.sup.3 is an alkoxy group and p is an integer from 1 to 100, the molar ratio of the acylating agent to the polyamine ranging from about 0.75:1 to 0.90:1;
- b) maintaining said liquid reaction mixture at a temperature of from about 100.degree. C. to 240.degree. C. for a period of from about 4 hours to about 18 hours at atmospheric pressure under an inert gas, converting at least 90 percent of the polyamine in the mixture to a mono-substituted imidazoline of the formula: ##STR15## wherein R, m, n and X are as hereinbefore defined; the improvement comprising:
- c) adding to said liquid reaction mixture formed in step (b), after drying if necessary to form an anhydrous mixture, both an esterifying agent and a catalytically effective amount of an esterification catalyst, said esterifying agent being selected from triglycerides of the formula: ##STR16## wherein the R.sup.4 s are, independently, C.sub.11 -C.sub.21 hydrocarbyl groups;
- said esterifying agent being present in an amount sufficient to provide a molar ratio of esterifying agent to acylating agent originally present in step (a) of from about 0.75:1 to 1.2:1;
- said esterification catalyst being selected from Ti(OR.sup.6).sub.4, wherein R.sup.6 is a C.sub.1 -C.sub.4 alkyl group, TiY.sub.4, wherein Y is a halide; SnT.sub.2 wherein T is, independently, a C.sub.1 -C.sub.8 hydrocarbyl group, a hydroxyl group, or a halide; and a dialkyltin chloride; and subsequently
- d) maintaining said anhydrous liquid reaction mixture at a temperature of from about 100.degree. C. to 200.degree. C. for a period of from about 1 hour to about 5 hours under an inert gas, producing a reaction product mixture containing one or more di-substituted imidazolines of the formula: ##STR17## wherein R, R.sup.4, m, n and X are as hereinbefore defined.
- 4. A solid fabric softening composition comprising from about 50% to 100% of the reaction mixture according to claim 1 wherein said composition being releasably affixed to a solid carrier.
TECHNICAL FIELD
This is a division of application Ser. No. 07/440,841, filed on Dec. 1, 1989, which is a Continuation-in-part of Ser. No. 07/287,922 filed Dec. 22, 1988, both now abandoned.
The present invention relates to a process for the preparation of a reaction product mixture containing di-substituted imidazoline fabric softening compounds. In particular, it relates to a process which results in a high yield of the desired di-substituted products through the use of a catalyst and minimizes the production of acrylic (open chain) amine/amide by-products and nonesterified imidazolines. Aqueous dispersions containing these di-substituted imidazoline compounds possess desirable storage stability, viscosity, concentratability and fabric conditioning properties and are especially suitable for use in the rinse cycle of a textile laundering operation.
Many different types of fabric conditioning agents have been used in rinse-cycle fabric treatment compositions. One class of compounds frequently used as the active component for such compositions includes substantially water-insoluble quaternary nitrogenous compounds having two long alkyl chains. Typical of such materials are ditallow dimethyl ammonium chloride and imidazolinium compounds substituted with two tallow groups.
These materials are normally prepared in the form of a dispersion in water. It is generally not possible to prepare such aqueous dispersions with more than about 10% of cationic softener without encountering severe product viscosity and storage-stability problems. Although more concentrated dispersions of softener materials can be prepared as described in European Patent Application 0,000,406, Goffinet, published Jan. 24, 1979, and United Kingdom Patent Specification 1,601,360, Goffinet, published Oct. 28, 1981, by incorporating certain nonionic adjunct softening materials therein, product viscosity and stability problems become increasingly unmanageable in more concentrated aqueous dispersions and effectively limit the maximum commercial range of applicability to softener active levels in the range from about 15% to about 20%.
The use of substituted imidazoline compounds as fabric conditioning agents is known. Imidazoline salts have been used by themselves or in combination with other agents in the treatment of fabrics. British Patent Specification 1,565,808, Apr. 23, 1980, assigned to Hoechst Aktiengesellschaft, discloses a textile fabric softener composition consisting of an aqueous solution or dispersion of an imidazoline or a salt thereof, or a mixture of such imidazolines or salts thereof. U.S. Pat. No. 4,724,089, Feb. 9, 1988, to Konig, et al., discloses fabric treatment compositions containing di-alkyl imidazoline compounds, or salts thereof, which may have one alkyl chain interrupted by an ester linkage.
The use of imidazolinium salts as fabric conditioning agents is also known. U.S. Pat. No. 2,874,074, Feb. 17, 1969, to Johnson discloses using imidazolinium salts to condition fabrics. U.S. Pat. No. 3,681,241, Aug. 1, 1972, to Rudy, and U.S. Pat. No. 3,033,704, May 8, 1962, to Sherrill, et al., disclose fabric conditioning compositions containing a mixture of imidazolinium salts and other fabric conditioning agents.
Recent patents also disclose processes for making substituted imidazoline compounds. U.S. Pat. No. 4,233,451, Nov. 11, 1980, to Pracht discloses a process to form the imidazoline precursor of an imidazolinium salt by reacting acylating or esterifying agents with alkylene or polyalkylene polyamines. U.S. Pat. No. 4,189,593, Feb. 19, 1980, to Wechsler, et al., discloses a process for making monoalkyl imidazolines involving contacting aminoethylethanolaine with a methyl carboxylate at an elevated temperature, optionally in the presence of a catalyst, and thereafter subjecting the reaction product to two successive heat treatments. The process disclosed in the Wechsler, et al., patent is aimed at maximizing the production of monoalkyl imidazoline and minimizing the esterification of the monoalkyl imidazoline. The product monoalkyl imidazoline is said to be a useful starting material for making amphoteric surfactants. Japanese Laid Open Publication 61-291571 discloses a process for the manufacture of 1,2-di-substituted imidazolines by reacting fatty acids or their esters with dialkylenetriamines.
It has been found that in addition to the imidazoline compounds formed in the above described reactions, acyclic amines/amides are also present. It has also been found that the presence of such acyclic amines in aqueous dispersions containing substituted imidazoline fabric softening compounds can lead to lower phase stability and undesirable viscosity characteristics. Furthermore, rigorous reaction conditions are currently required to form substituted imidazoline fabric softening compounds. Even at high temperatures the esterification is slow and the product yield ranges from 10-35 percent. Therefore, there is a need for a new and improved process for preparing di-substituted imidazolines that minimizes the product of acyclic amines/amides and monoalkyl imidazolines (i.e. nonesterified) and increases the reaction rate and product yield.
It is therefore the object of the present invention to provide a process for making di-substituted imidazoline compounds that minimizes the product of acyclic amine/amide by-products and monoalkyl imidazolines.
It is another object of this invention to provide a high yield process for preparing reaction product mixtures containing these di-substituted imidazoline compounds at a decreased reaction time through the use of a catalyst.
It is another object of this invention to provide fabric conditioning compositions comprising the di-substituted imidazoline compounds prepared using the improved process of this invention.
It is another object of this invention to provide a method for conditioning fabrics by treating them with aqueous dispersions containing the desired di-substituted imidazoline fabric conditioning compounds.
It is still another object of this invention to provide a method for conditioning fabrics by treating them with particular fabric softening and antistatic compositions which have been prepared by the improved process herein and which are in solid form. Such solid compositions are releasably affixed to sheet materials which can be used in hot air clothes dryers.
These and other objects are realized by the present invention.
The present invention is directed to a process for preparing a reaction product mixture containing di-substituted imidazoline compounds useful as fabric conditioning agents. Such a process comprises:
(a) forming a liquid reaction mixture containing (1) an acylating agent selected from fatty acids of the formula RCOOH, fatty acid halides of the formula RC(O)Y, fatty acid anhydrides of the formula (RC(O)).sub.2 O, or fatty acid short chain esters of the formula RC(O)OR.sup.1, wherein, in these formulas, R is a C.sub.7 -C.sub.21 hydrocarbyl group, R.sup.1 is a C.sub.1 -C.sub.4 alkyl group, and Y is a halide, and (2) a polyamine having the formula NH.sub.2 --(CH.sub.2).sub.m --NH--(CH.sub.2).sub.n --X--H, wherein m and n are, independently, integers from 2-6, and X is O, S, NR.sub.2, wherein R.sup.2 is H or a C.sub.1 -C.sub.4 alkyl group, O(R.sup.3).sub.p, NH(R.sup.3).sub.p, or S(R.sup.3).sub.p, wherein R.sup.3 is an alkoxy group and p is an integer from 1 to 100, the molar ratio of the acylating agent to the polyamine ranging from about 0.5:1 to 2.0:1;
(b) maintaining this liquid reaction mixture at a temperature of from about 100.degree. C. to 240.degree. C. for a period of time sufficient to convert at least about 50 percent of the polyamine in the mixture to a mono-substituted imidazoline of the formula: ##STR1## wherein R, m, n and X are as hereinbefore defined; and thereafter
(c) adding to the liquid reaction mixture formed in step (b), after drying the liquid reaction mixture if necessary to render it anhydrous, both an esterifying agent and a catalyst, said esterifying agent being selected from C.sub.1 -C.sub.4 mono-esters of C.sub.12 -C.sub.22 fatty acids and C.sub.12 -C.sub.22 fatty acid mono-, di-, and tri-glycerides; said esterifying agent being present in an amount sufficient to provide a molar ratio of esterifying agent to acylating agent originally present in step (a) of from about 0.3:1 to 1.5:1; said esterification catalyst being selected from alkali metal alkoxides, transition metal alkoxides, metal halides, transition metal alkyl akoxides, metal alkyl halides, metal carboxylate salts, and tin complexes; and subsequently
(d) maintaining this anhydrous liquid reaction mixture at a temperature of from about 1000.degree. C. to 200.degree. C. for a period of time sufficient to form a reaction product mixture which contains a di-substituted imidazoline of the formula: ##STR2## wherein R, m, n, and X are as hereinbefore defined, and wherein R.sup.4 is a C.sub.11 -C.sub.21 hydrocarbyl.
The present invention also relates to the preparation of aqueous and solid fabric softening compositions using the reaction product mixture formed by the foregoing process and to methods of conditioning fabrics using such compositions.
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Divisions (1)
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| Parent |
440841 |
Dec 1989 |
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Continuation in Parts (1)
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287922 |
Dec 1988 |
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Patent Grant
5154841
