Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C233/00—Carboxylic acid amides
  • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
  • C07C233/34—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
  • C07C233/35—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/22—Agents rendering paper porous, absorbent or bulky
  • D21H21/24—Surfactants

Definitions

• compositions useful for treating various surfaces including fibers, textiles, paper, hair, and human skin. More particularly, it relates to compositions and methods for treating metal, paper, and textiles which compositions comprise an amphoteric surfactant derived from ethyleneamines, long-chain fatty acids, and acrylic acid.
• the ethyleneamine used as a raw material from which the surfactant is derived is tetraethylenepentamine.
• U.S. Pat. No. 5,322,630 provides a method of acidizing a subterranean formation with an acqueous acid solution wherein the acid solution contains corrosion inhibiting amounts of an amine derivative prepared by reacting an unsaturated carboxylic acid with (a) fatty amine or polyamine, or (b) a fatty amido amine or polyamine, or (c) a fatty imidazoline amine or polyamine.
• the derivative is characterized by the absence of primary amino groups, and preferably contains only tertiary amino groups.
• amphoteric derivatives of a broad range of fatty polyamines, fatty amidoamines, fatty imidazolines and polyamines which are disclosed as being useful as oilfield corrosion inhibitors.
• U.S. Pat. Nos. 6,004,914; 6,200,938; and 6,369,007 teach amphoteric derivatives of aliphatic polyamines, such as diethylenetriamine or triethylenetetramine reacted with long chain fatty acids, esters or triglycerides from various natural or synthetic sources are effective in the softening/texture modification of substrates such as paper, textiles, human skin surfaces and hair tresses, as well as in applications for metal working and lubrication.
• the polyamines are first reacted with fatty acids, esters or triglycerides derived from various animal, vegetable or synthetic sources ranging in molecular distribution from butyric through erucic acids (e.g.
• milkfat, soy bean oil, rapeseed oil to form polyamines or imidazolines; they are then further reacted with unsaturated or halogenated carboxylic acids, carboxylated epoxy compounds or acid anhydrides (e.g. acrylic acid, itaconic acid, chloroacetic acid, maleic anhydrides octadecenyl anhydride) to form the various amphoteric structures.
• unsaturated or halogenated carboxylic acids e.g. acrylic acid, itaconic acid, chloroacetic acid, maleic anhydrides octadecenyl anhydride
• the present invention relates to amphoteric surfactants that are useful in various applications including paper softener, fabric softener, metal working and lubrication.
• An amphoteric surfactant of the present invention may be made by reacting tetraethylene pentamine (“TEPA”) with 2.5 to 3.0 moles of a fatty acid to form an intermediate amide compound which is then converted to an amphoteric compound by reacting it with 1 to 2 moles of an unsaturated acid species selected from the group consisting of: maleic acid, maleic anhydride, vinyl sulfonic acid, 2-methyl vinyl sulfonic acid, allylsulfonic acid, and acrylic acid.
• TEPA tetraethylene pentamine
• an unsaturated acid species selected from the group consisting of: maleic acid, maleic anhydride, vinyl sulfonic acid, 2-methyl vinyl sulfonic acid, allylsulfonic acid, and acrylic acid.
• x is any integer selected from the group consisting of 4, 5, and 6;
• R 1 in each occurrence is independently any alkyl group having between 5 and 25 carbon atoms, whether straight-chain, branched, cyclic, saturated or unsaturated;
• R 2 in each occurrence is independently selected from the group consisting of: 1) hydrogen; 2) any saturated or unsaturated aliphatic mono- or di-carboxylic acid moiety having one or more carboxyl functional groups and having one or more straight-chain or branched, saturated or un-saturated aliphatic chains containing from 2 to 20 carbon atoms; 3) any saturated or unsaturated aliphatic mono sulfonic acid moiety having one or more —SO 3 H functional groups and having one or more straight-chain or branched, saturated or un-saturated aliphatic chains containing from 2 to 20 carbon atoms; and 4) a radical of the formula:
• R 1 has the same meaning as that ascribed to it above.
• a composition according to the invention comprises a mixture of at least two components each of which comprise different amphoteric surfactants which are represented by the formula:
• R 1 in each occurrence is independently any alkyl group having between 5 and 25 carbon atoms, whether straight-chain, branched, cyclic, saturated or unsaturated
• R 2 in each occurrence is independently selected from the group consisting of: 1) hydrogen; 2) any saturated or unsaturated aliphatic mono- or di-carboxylic acid moiety having one or more carboxyl functional groups and having one or more straight-chain or branched, saturated or un-saturated aliphatic chains containing from 2 to 20 carbon atoms; 3) any saturated or unsaturated aliphatic mono sulfonic acid moiety having one or more —SO 3 H functional groups and having one or more straight-chain or branched, saturated or un-saturated aliphatic chains containing from 2 to 20 carbon atoms; and 4) a radical of the formula:
• R 1 has the same meaning as that ascribed to it above.
• the above-described mixture comprises:
• amphoteric surfactant being present in any amount between 8.0% and 20.0%; the second amphoteric surfactant being present in any amount between 25.0% and 45.0%; and the third amphoteric surfactant being present in any amount between 35.0% and 60.0%, with all percentages being calculated on a weight basis with respect to all of the amphoteric surfactants present which are defined by the above formula.
• An amphoteric surfactant of the present invention is exemplified by the use of TEPA as a raw material, and other amphoteric surfactants according to the invention are readily prepared using the same general procedure but with ethyleneamines such as pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, etc.
• An amphoteric surfactant according to the invention may be prepared by first reacting TEPA as a starting material with 2.5 to 3 moles fatty acids, to form an intermediate substituted TEPA polyamide. According to one preferred form of the invention, 3 moles of fatty acid are reacted with 1 mole of TEPA to yield the triamide.
• the polyamide is subsequently reacted with 1 to 2 moles of an unsaturated acid species such as acrylic acid or vinylsulfonic acid to form an amphoteric surfactant.
• an unsaturated acid species such as acrylic acid or vinylsulfonic acid
• 2 moles of acrylic acid are reacted with one mole of polyamide, which is preferably a triamide.
• the resulting amphoteric compounds are useful as softeners for tissue paper, fabrics, hair and skin.
• the resulting amphoteric compounds are also useful as lubricants in metalworking.
• reaction (I) one mole of tetraethylenepentamine is caused to be reacted with three moles of the mono-carboxylic acid in which R may be any C 1 through C 25 alkyl group, whether straight-chain, branched, cyclic, saturated or unsaturated.
• R may be any C 1 through C 25 alkyl group, whether straight-chain, branched, cyclic, saturated or unsaturated.
• the present invention contemplates the use of both cis- and trans-isomers.
• the reactant carboxylic acid is oleic acid, although any other carboxylic acid having between about 7 and 25 carbon atoms may be used, or mixtures thereof.
• the product of the reaction between three moles of the carboxylic acid and TEPA is the triamide shown in formula (II):
• This structure represents the predominant product of such reaction according to the invention.
• a mixture of positional isomers is formed with the carboxylic acid residue being substituted upon the various possible positions of substitution having an active hydrogen atom at which the acid function of the carboxylic acid is capable of reacting, as is known to those skilled in the art.
• the resulting product is a mixture of isomers substituted at the first and second; first and third; first and fourth; first and fifth; second and third; and second and fourth positions.
• the present invention embraces all such positional isomers and mixtures thereof.
• acrylic or other unsaturated carboxylic or sulfonic acid When more than one mole of acrylic or other unsaturated carboxylic or sulfonic acid is reacted, more than one of the possible positions is substituted.
• the present invention embraces all such positional isomers.
• Monomers other than acrylic acid may of course be employed in the role just described for acrylic acid, including unsaturated acid species selected from the group consisting of maleic acid, maleic anhydride, vinyl sulfonic acid, 2-methyl vinyl sulfonic acid, and allylsulfonic acid.
• oleic acid is reacted with TEPA at 144° C. for about 6-10 hours and is subsequently reacted with acrylic acid in the presence of propylene glycol or polyethylene glycol at about 105° C. for about 8 hours, or until the reaction is complete.
• the structures of the reaction product are easily confirmed using NMR and IR spectroscopy.
• any polyalkylene polyamine can be reacted with a fatty acid to yield an amide which is subsequently reacted with acrylic acid to yield an amphoteric surfactants useful in treating hair, skin, paper, textiles and fibers according to the invention.
• TEPA tetraethylene pentamine
• the reaction is considered to be complete when the acid number is below 10 meq/gram (acid numbers referred to in this specification are measured by titrating an aqueous sample using aqueous base which is about 0.1 N to a phenolphthalein end point and calculating the acid number using the relation:
• N the Normality of the base used.
• Ethyleneamine E-100 (Huntsman Corp.) is a mixture of tetraethylenepentamine (10-15% TEPA), pentaethylenehexamine (33-38% PEHA) and hexaethyleneheptamine (45-54% HEHA). 516.4 grams of tall oil fatty acid (“TOFA”) is charged to a 1 L round bottom flask. under nitrogen purge. 162.6 grams of Ethylenamine E-100 is slowly added with stirring under nitrogen, the temperature being kept below 120° C. throughout the addition. Following the addition, the temperature of the contents of the flask is maintained at 120° C. for 30 minutes. Then the temperature is increased to 144° C. and maintained at 144° C. for an additional six hours. The reaction is considered to be complete when the acid number is below 10.
• TOFA tall oil fatty acid
• tissue paper for use in personal care such as facial tissue and bathroom tissue is the softness of such papers.
• test solutions were made up as follows:
• Sample 1 48% (TEPA+3 moles oleic acid+2 moles acrylic acid) 52% propylene glycol.
• Sample 2 48% (TEPA+2.5 moles oleic acid+1.5 moles acrylic acid) 52% propylene glycol.
• Sample 3 48% (TEPA+2 moles oleic acid+2 moles acrylic acid) 52% propylene glycol.
• Sample 4 48% (TEPA+2 moles oleic acid+1 moles acrylic acid) 52% propylene glycol.
• Sample 5 48% (TEPA+3 moles oleic acid+1 moles acrylic acid) 52% propylene glycol.
• Sample 6 70% of sample 1 mixed with 30% of SURFONIC® E-400 MO (“monooleate”).
• Sample 7 70% of sample 2 mixed with 30% of SURFONIC® E-400 MO.
• Sample 8 70% of sample 3 mixed with 30% of SURFONIC® E-400 MO.
• Sample 9 70% of sample 4 mixed with 30% of SURFONIC® E-400 MO.
• Sample 10 70% of sample 5 mixed with 30% of SURFONIC® E-400 MO.
• Sample 11 pure SUFRONIC® E-400 MO (SURFONIC® products are available from Huntsman Corporation)
• Control 1 48% (diethylenetetramine “DETA”+2 moles TOFA (tall oil fatty acid)+1 mole acrylic acid)+52% propylene glycol.
• Control 2 70% of control 1+30% SUFRONIC® E-400 MO.
• (TEPA+2 moles oleic acid+2 moles acrylic acid) means the amphoteric surfactant produced by reacting TEPA with 2 moles of oleic acid, and subsequently reacting the product thereof with 2 moles of acrylic acid.
• the various compositions descried above in samples 1-5 were prepared by simple mixing of the specified amount of glycol and amphoteric surfactant. Similarly, for examples 6-10 the specified amounts of materials were blended together.
• SUFRONIC® E-400 MO is an ethoxylated oleic acid surfactant available from Huntsman Company LLC of Houston, Tex.

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Citations (20)

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• 2003
  • 2003-02-18 US US10/369,263 patent/US20040159415A1/en not_active Abandoned
• 2004
  • 2004-02-13 EP EP04711213A patent/EP1594601A4/en not_active Withdrawn
  • 2004-02-13 WO PCT/US2004/004337 patent/WO2004074572A2/en not_active Application Discontinuation
  • 2004-02-13 CA CA002516297A patent/CA2516297A1/en not_active Abandoned
  • 2004-02-13 JP JP2006503569A patent/JP2006518014A/ja active Pending
  • 2004-02-13 US US10/545,858 patent/US20060247324A1/en not_active Abandoned
  • 2004-12-15 US US11/013,079 patent/US20050153866A1/en not_active Abandoned

Patent Citations (23)

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