AU2399500A - Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants - Google Patents

Cationic gemini and related multiple hydrophilic/hydrophobic functional compounds and their use as surfactants Download PDF

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AU2399500A
AU2399500A AU23995/00A AU2399500A AU2399500A AU 2399500 A AU2399500 A AU 2399500A AU 23995/00 A AU23995/00 A AU 23995/00A AU 2399500 A AU2399500 A AU 2399500A AU 2399500 A AU2399500 A AU 2399500A
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alkyl
compound
group
integer
mixtures
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AU771929B2 (en
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Hee Cho
Stanley B. Mirviss
Peter J. Spellane
Dale Steichen
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Akzo Nobel NV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C219/00—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C219/02—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C219/04—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C219/06—Compounds containing amino and esterified hydroxy groups bound to the same carbon skeleton having esterified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having the hydroxy groups esterified by carboxylic acids having the esterifying carboxyl groups bound to hydrogen atoms or to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • 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
    • C07C233/36—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 having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Description

WO 00/39241 PCT/US99/31246 Cationic Gemini and Related Multiple Hydrophilic/Hydrophobic Functional Compounds and Their Use As Surfactants 5 Field of Invention The present invention generally relates to improved multiple hydrophilic/hydrophobic functional quaternary ammonium compounds 10 "multiple functional" surfactants, useful in detergents and personal care, mining, industrial, and catalyst products, in biocidal compositions at higher concentrations, and as emulsifiers. Background of The Invention 15 Conventional surfactants have one hydrophilic group and one hydrophobic group. Dimeric surfactants which are commonly called "Gemini" surfactants are those which comprise two hydrophilic functional groups and two hydrophobic functional groups. Gemini surfactants have 20 unique physical properties resulting from constraint of two hydrophilic groups in close proximity and the consequent micellar properties, which has led to an intensive study of Gemini surfactants as detergents, softeners, emulsifiers, phase transfer catalysts, biocides, and as components in skin care lotions, hair conditioning compositions and 25 cosmetics compositions. Their use is also being investigated in ore flotation, oil well drilling and in other industrial applications. It is therefore an object of the present invention to provide a novel class of cationic multiple functional surfactants that have application in the 30 treatment of textile fibers to provide softeners and static control. It is also an object to provide a class of multiple functional surfactants having improved detergency at extremely low concentrations, while at the same time being highly biodegradable. 35 WO 00/39241 PCT/US99/31246 It is also an object of the present invention to provide a class of multiple functional surfactants which are useful as emulsifiers, phase transfer catalysts, biocides, in ore flotation, in oil well drilling and in other related applications. 5 Finally, it is an object of the invention to provide a class of multiple functional surfactants which are useful in skin care lotions, hair conditioning compositions and cosmetics compositions at low concentrations. 10 These and other objectives are realized by the compositions and methods of the present invention. Summary of the Invention 15 The present invention generally relates to several new classes of cationic multiple functional surfactants and to compositions containing same. The invention also relates to various processes for preparing the multiple functional surfactants of the present invention. 20 Detailed Description of The Present Invention The present invention generally relates to multiple functional surfactants of the formulae I-IV, below, to compositions containing same 25 and to methods for their preparation. The beneficial features of the multiple functional surfactants of the present invention derive from their multiple functional character, i.e., the chemical species of the present invention contain two or more hydrophobic groups and two or more hydrophilic groups in each molecule. 2 WO 00/39241 PCT/US99/31246 1. Multiple functional guaternary ammonium compounds containing ester or amide spacer group(s) of the general formula: 5 R3 (I) I I R, - N*- (A)n- N*- R 2 I I
R
5
R
6 10 2Z wherein R, and R 2 are the same or different and are selected from straight or branched chain, substituted or unsubstituted C-C22 alkyl or 15 alkenyl groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof;
R
3 , R 4 , R 5 ,and R. are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C22 alkyl or alkenyl groups wherein said alkyl or alkenyl groups optionally contain at least one 20 ester linkage, at least one amide linkage, or mixtures thereof; and A is a spacer selected from the group consisting of: 0 0 0 25 (CH 2 )x - C - 0 - (CH 2 )y , (CH 2 )x - 0 -C - (CH 2 )y - C-O-(CH 2 )z, 0 0 Il 11
(CH
2
CH
2 O)x-C - (CH 2 )y - C -( OCH 2
CH
2 )z, 30 0 0 0 || II II
(CH
2 )x N - C -(CH 2 )y - C-N-(CH 2 )z, (CH 2 )x - C- N (CH 2 )y 0 0 35 || ||
(CH
2
CH
2
CH
2 N)x- C-(CH 2 )y-C(NCH 2
CH
2
CH
2 )z or other ester - or amide-functional alkyl groups in the spacer, 3 WO 00/39241 PCTIUS99/31246 wherein each of x, y and z can independently be an integer of 1-20; and n is an integer of from 1-20; ll. Multiple functional quaternary ammonium compounds with ester or 5 amide spacer group(s) of the general formula:
R
8
R
9 (R1) I I I 10 R- Ne - (A) -Ne - (A),- NeD -R1
RR
13 3Z 15 wherein R., R 8 ,R,, R 1 0
R
11 , R 12
,R
3 , and R 1 , are the same or different and are selected from straight or branched chain, substituted or unsubstituted
C,-C
22 alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, 20 or mixtures thereof; and A is a spacer group as defined above, and wherein x, y and z are each independently an integer of 1-20; and n is an integer of from 1-20; or 111. Asymmetric multiple functional quaternary ammonium compounds: 25
R
1 6 (ll) I I
R
15 - N*- (CH 2 )n- N+- R 20 30
R
1 R1 2Z wherein R.. and R 2 0 are different and are selected from straight or 35 branched chain, substituted or unsubstituted C-C22 alkyl or alkenyl groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof; R, 6 , R 1 , R 1 8 4 WO 00/39241 PCT/US99/31246 and R,, are the same or different and are selected from straight or branched chain, substituted or unsubstituted C,-C 22 alkyl or alkenyl groups wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof; and n is an 5 integer of from 1-20. IV. Symmetric "gemini" guaternary ammonium compounds prepared in the reaction of alkyl multiple amine compounds with long chain aldehyde or alcohols of the general formula IV 10 R22
R
2 3 R2
R
21 - N - (CH 2 )x - N - (CH 2 )y - N-- R25 15 R28 R27
R
2 6 n (2+n)Z- IV wherein R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , and R 2 , are the same or different and are selected from straight or branched chain, substituted, or 20 unsubstituted C1-C22 alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage or mixtures thereof, and where x an y are each independently an integer of from 1-20 and n is an integer from 0-20; wherein in each of 1, 11, 111 and IV, Z- is an anion. 25 In each of formulae I-Ill, above, R 1 , R 2 , R 7 , R 14 , R 1 , and R 2 0 are preferably selected from C8-C, alkyl groups, optionally containing an ester linkage. It is also preferred that x, y and z are 0-5 and that n is 1 10. 30 In formula IV above R 2 1 and R 25 are preferably selected from 2 ethylhexyl. nonyl-alkyl, or a C1C15 mixed alkyl group, and R 22 , R 23 , R 24 ,
R
2 5
R
26 , R 2 7 , and R2. independently selected from methyl, ethyl, or propyl, and n = 0,1, or 2. 5 WO 00/39241 PCT/US99/31246 Concerning the multiple functional quaternary ammonium compounds of formula I, it is preferred that R, and R 2 be selected from 2 ethylhexyl, nonyl-alkyl, a C13 - C15 mixed alkyl group, or from the group 5 consisting of dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalkyl ; that R 3 , R 4 , R, and R. be independently selected from methyl, ethyl, propyl, 2 ethylhexyl, nonyl-alkyl, or a C13 - C1 mixed alkyl group; and that n be an integer of from 1 to 5. 10 In the multiple functional quaternary ammonium compounds of formula 11, it is preferred that each of R 7 , R 8 , R 9 , R,,, R 1 , R 12 , R 13 and R 14 are independently selected from from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13 - C1 mixed alkyl group, or from the group consisting of 15 dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalky; and that n be an integer of from 1 to 5. Finally, it is preferred that, in the asymmetrical multiple functional 20 quaternary ammonium compounds of formula Ill, R, 5 , R 16 , R 17 , R 1 8 , R 1 9 ,and R 2 e be selected from methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13 - C, mixed alkyl group, or from the group consisting of dodecylalkyl, hexadecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, or hydrogenated tallowalky or other long chain fragment with the proviso 25 that the group of substituents on one N' be not identical to the group of substituents which surround the other N' center and that n is an integer of from 1 to 20. The ester or amide containing multiple functional compounds of 30 the present invention exhibit enhanced biodegradability which is extremely desirable for obvious environmental reasons. For example, enhanced biodegradability is a desired attribute in fabric softening 6 WO 00/39241 PCT/US99/31246 compositions and in other uses where the content and volume of waste water effluent streams needs to be controlled. When used in a fabric softening composition, the compounds of 5 the present invention are preferably delivered to the textile to be softened in amounts effective to impart the desired softness and/or anti-static properties to said textile(s). Said effective amount typically ranges in an amount of from about 0.5 to 3 grams of softening compound(s) per average load of laundry. 10 Delivery of the compounds of the present invention to the textile to be treated can be conducted by various means. For example, the compounds of the present invention can be formulated into liquid softening compositions, solid formulations and/or solid articles. In a liquid 15 formulation, the compounds of the present invention are dissolved and/or suspended in water, wherein said formulation optionally also contains other conventional softeners as well as other ingredients and diluents such as detergents, optical brighteners, viscosity aids, soil release agents, fragrance, and the like, in the requisite amounts so to provide an 20 effective amount of the compounds of the present invention to the textile to be treated. With solid formulations, the multiple functional surfactants of the present invention are formed into small flowable particles or beads on a 25 water-soluble carrier such as a solid detergent, which is optionally compounded with builders, brighteners, fragrance and the like. Finally, the multiple functional surfactants of the present invention can be combined with a distribution agent and applied, or coated on a 30 solid carrier such as a woven, or non-woven fabric or bonded polyester 7 WO 00/39241 PCT/US99/31246 sheet. Alternatively, the composition can be inserted into a container designed for insertion into a clothes dryer. The present invention also relates to various methods for the 5 preparation of multiple functional surfactants. For example, the multiple functional surfactants of formula I which contain ester spacer groups can be prepared by reacting a dialkylalkanol amine of formula Q, 10
Q
2 - N - Q 3 -OH wherein each of Q,,Q 2 and Q. is independently selected from the group consisting of C-C22 alkyl groups and a dicarboxylic acid of the formula HOOC - (CH 2 )n - COOH 15 wherein n is an integer of from 1-12, to form a reaction mixture, or a diester of same, and thereafter quaternizing the reaction mixture. The dialkylalkanol amine is preferably prepared by ethoxylating a fatty amine compound of the formula z N- H 25 Y Wherein Z is a C 12
-C
22 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a C1C22 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group. 30 Preferably, the fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenatedtallowalkyl amine, dicocoalkylamine, ditallowalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine,and mixtures thereof. 35 The dicarboxylic acid employed is preferably selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and 8 WO 00/39241 PCT/US99/31246 mixtures thereof. The most preferred dicarboxylic acid is adipic acid, or mixed short chain di-acids which are commercially available from, for example, DuPont. 5 The multiple functional surfactants of formula I which contain an amine-functional spacer group can be prepared in the reaction of an N alkylamino fatty amine compound
R-N(H)(CH
2 )n NH 2 with a dicarboxylic acid or mixtures of dicarboxylic acids(or diesters of same). 10 The multiple functional quaternary ammonium compounds of Formula IV can be prepared by reacting a bis-primary amine alkane (e.g., hexamethylenediamine) with two equivalents of aldehyde, e.g., 2 ethylhexanal, or other long chain aldehydes such as nonanal or mixed 15 C 1 3 -Cl aldehydes (which are commercially available). Other multiple functional quaternary ammonium surfactants of general Formula IV of the present invention can be prepared by reaction of aliphatic triamines of formula: 20
H
2 N - R -N- R -NH 2 , wherein R is a saturated or unsaturated hydrocarbon group, with 25 aldehyde, e.g., 2-ethylhexanal, or longer chain aldehyde such as nonanal or mixed C 13
-C
15 aldehydes (which are commercially available), or an alcohol. For example, tris-quaternary ammonium surfactants can be prepared by reaction of bis(hexamethylene) trimine with alkylaldehyde, such as 2-ethylhexanal, followed by methylation and quaternization. 30 The cationic gemini and related multiple functional hydrophilic/hydrophobic functional compounds of the present invention can be employed alone, or in combination with typical surfactants, 9 WO 00/39241 PCT/US99/31246 including mono-quaternary ammonium compounds. When employed in combination with mono-quaternary ammonium compounds, it has been found that as little as 5-10% of the compounds of the present invention can reduce the Critical Micelle Concentration (CMC) from 10 up to 100 5 fold. CMC is a measurement employed to determine the effectiveness of a surfactant composition. The lower the CMC values, the better the surfactant. Thus, by using small amounts of the surfactants of the present invention in combination with conventional surfactants, the addition rates of the conventional surfactants can be greatly reduced. 10 The present invention shall now be illustrated by the following non limiting examples. Example 1 - Preparation of a Multiple Functional Quaternary Ammonium 15 Compound with Ester-functional Spacer Groups H3 C1 0 C 6 3
OH
3
CH
3
H
33
C
16 -N +~
O;H
3 2Br- 0 OH 3 Preparation of (CH 2 )(C0 2
_CH
2 _CHNMe ) from adipic acid and dimethylethanolamine in toluene 20 Procedure - A 1 L round bottom flask was charge with 14.6 g of adipic acid (1.00 mole), 196.0 g of dimethylethanolamine (2.20 mole - 10% excess), 300 mL toluene and 1.5 g of p-toluenesulfonic acid. The reaction mixture was heated to reflux with stirring. A Dean-Stark trap was 25 attached to one neck of the 4-neck flask and to a water condenser. The reaction was heated at reflux for a total of 22 hours as 54.5 mL H 2 0 distilled. The product was stripped of solvent on a rotary evaporator at 800 C and 15 mm Hg. The product weighed 270.6 g. Infrared spectroscopy of product indicated only the ester. 30 Reaction of (CHrC.
2 CHl 2
CH_
2 NMe 2 with hexadecyl bromide 10 WO 00/39241 PCT/US99/31246 Procedure - A 1 L Morton flask was charged with 57.6 g of
(CH
2
)
4
(CO
2
CH
2
CH
2 NMe 2
)
2 (0.2 mole) and 300 mL of monoglyme. 122.0 g C,,H,,Br (0.4 mole) were added with stirring. The mixture was heated to 850 C with stirring under an N 2 atmosphere and maintained for 73 hours. 5 No solid was evident at the conclusion of heating but did form on standing over several days. The total product was suction filtered and the beige solid was sucked dry. It was then washed twice with diethylether and again sucked dry, then let stand in a crystallization dish overnight. The solid product weighed 135.5 g (theoretical yield: 179.6 g). Another 30.8 g 10 solid product was reclaimed from the filtrate for an overall yield of 92.6%. NMR analysis of product indicated 80 mole % purity of diquaternary compound, 14 mole % mono-quaternary and 6 mol % mono-quatenary monoacid product. A composition was prepared comprising 90% Arquad@ 12 15 (available from Akzo Nobel Chemicals Inc., Chicago, IL) and 10% of the compound of example 1. This composition exhibited a 50 fold reduction of CMC values compared to a composition comprising 100% Arquad@ 12. Example 2 - Preparation of Multiple Functional Quaternary Ammonium 20 Compound in Reaction of Aldehyde with Alkyl-diamine: reaction of 1.6 hexanediamine with mixed Cj/Cj, aldehyde, followed by reduction. methylation, and quaternization Summary: H2N(CH 2
)
6
NH
2 + 2 RCHO - RCH=N(CH 2
)
6 N=CHR sodium borohydride
CH
3
CH
3 I I I meh lto
RCH
2
N(CH,)
6 NCHR :thylat
RCH
2
NH(CH
2
)
6
NHCH
2 R
JCH
3 CI RC HO = CI3-C15 aldehyde
CH
3 CH 3 RCH2N(CH 2
)
6
NCH
2 R
H
3
H
3 2C 25 11 WO 00/39241 PCT/US99/31246 1. Reaction of 1,6-hexanediamine with mixed C 1
/C
15 aldehyde. The mixed aldehyde was used as obtained from Celanese Ltd. Chemicals Division (Dallas, TX); the average molecular weight was estimated to be 211. The aldehyde mixture (400 g., 1.89 moles) 5 was added in portions to melted 1,6-hexanediamine (107 g., 0.92 mole). The reaction was exothermic and was therefore cooled occasionally. The product was washed with water; after solvent was removed by evaporation, a oily yellow liquid (428 g.) was obtained. 10 2. Sodium borohydride (32 g.) was added as powder to a solution of the bis-imine compound (404 g., product in 1 above). The reduction reaction was followed by observing disappearance of the imine carbon's "C NMR. The reaction mixture was washed 15 thoroughly with water before solvent was removed by evaporation. The product was a pale yellow liquid (400 g.) 3. Methylation of the bis-secondary-amine by Eschweiler-Clarke procedure (see also Leukhart Reaction, Organic Reactions, 20 Volume 5, p. 323). To the bis-sec-amine (360 g., 0.71 mole) 90% formic acid was added slowly, forming a light brown solution as the reaction temperature increased to 750 C and then cooled to 50-60' C. The 37% formaldehyde (66 g., 0.814 mole) was slowly added as CO2 gas evolved. The mixture was heated until gas evolution 25 ceased. Ca. 80 g. of concentrated HCI was added, and the formic acid and any excess formaldehyde were removed at 650 C on a rotary evaporator. The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 g.). The product was washed with water and dried. A pale yellow liquid (440 g.) was 30 obtained and identified as the bis-tertiary amine. 12 WO 00/39241 PCT/US99/31246 4. Quaternization of the bis-tertiary amine compound prepared in 3 above. In a 1-liter titanium autoclave, a solution of bis-tertiary amine in methanol (150 g) with sodium bicarbonate was purged with nitrogen and heated with methyl chloride at about 80'C until 5 all amine had been consumed (in about 10 hours). Filtration and evaporation yielded a brownish yellow thick paste (215 g.) that was identified as the bis-quaternary ammonium compound. 10 Example 3 - Preparation of Asymmetric Multiple Functional Quaternary Ammonium Surfactant Compounds Asymmetric dimeric- or higher oligomeric surfactant compounds are prepared from Duomeen@, Triameen@, and Tetrameen@ compounds 15 available from Akzo Nobel Chemicals Inc., Chicago, IL, using an amine aldehyde condensation reaction. H H H H + 2-ethylhexanal -> -> R-N, N-ethyhexyl Duomeen 20 where R = coco-, tallow-, or oleylalkyl H H I I R--N N-ethyhexyl + methylation, quaternization -> 25
CH
3 CH 3 1+ 1+ R-N. N-ethyhexyl
CH
3
OH
3 2Br 30 Example 4 - Preparation of Multiple Functional Quaternary Ammonium Compound in the reaction of bis(hexamethylenetriamine with mixed _C, aldehyde followed by reduction methlation. and uaternization 13 WO 00/39241 PCT/US99/31246 1. The mixed aldehydes were added in portions to melted bis(hexamethylene)triamine; and the exothermic reaction was cooled. The reaction mixture was washed with water, then solvent removed by evaporation to yield the bis-imine mono -secondary 5 amine compound, a pale yellow liquid. 2. Reduction of the bis-imine-mono-sec-amine compound with sodium borohydride. The bis-imine compound (283 g.) prepared in 1 above was dissolved in 150 g. methanol. To this 25 g. sodium 10 borohydride was added in small portions until the reduction was complete. The reduction reaction was followed by observing disappearance of the imine carbon's 13C NMR. The reaction mixture was washed thoroughly with water before solvent was removed by evaporation. The product was a pale yellow liquid 15 (247 g.) 3. Methylation of the tris-secondary amine compound prepared in 2 above. The tris-sec-amine compound (245.6 g., 1.17 mole). To this solution, formic acid was added slowly, forming a light brown 20 solution as the reaction temperature increased to 750 C and was then cooled to 50-600 C. The 37% formaldehyde (66 g., 0.814 mole) was slowly added as CO2 gas evolved. The mixture was heated until gas evolution ceased. Ca. 80 g. of concentrated HCI was added, and the formic acid and any excess formaldehyde 25 were removed at 650 C on a rotary evaporator. The residue was dissolved in water and neutralized with 25% aqueous NaOH (ca. 65 g.). The product was washed with water and dried. A pale yellow liquid (247 g.) was obtained and identified as the tris-tertiary amine. 30 14 WO 00/39241 PCT/US99/31246 4. Quaternization of the tris-tertiary amine compound. The tris-tert amine prepared in 3 above was quaternized in a procedure like those described elsewhere in this application. In a 1-liter titanium autoclave, a solution of tris-tertiary-amine in methanol (155 g. 5 compound in 150 g. methanol) with sodium bicarbonate was purged with nitrogen and heated with methyl chloride at about 80 0 C until all amine had been consumed (in about 10 hours). Filtration and evaporation yielded a brownish yellow thick paste (210 g.). 10 Example 5 - Preparation of Amido-Bridged Multiple Functional Quaternary Ammonium Surfactant Compounds 15 Dimeric - or higher multiple functional surfactant compounds with amide groups in the spacer groups are prepared from Duomeen@, Triameen@, and Tetrameen@ compounds from Akzo Nobel Chemicals, Inc. in the following manner: H H R N 2 R-N N-H + dicarboxylic acid to form the bis-amido 20 compound -4 followed by methylation, and then quaternization where R = coco-, tallow-, or oleylalkyl
CH
3 H 0 1+I
OH
3 R- N N+
OH
3 N 0 2X- H
OH
3 25 R = coco-, tallow-, or oleylalkyl Example 6 -- Preparation of Multiple Functional Quaternary Ammonium Surfactant Compounds With Ester-Groups in the Spacer from Ethoxylated Fatty Amine Compounds 30 Various mono- and di-alkyl fatty amine compounds are available from Akzo Nobel Chemicals, Inc. and are useful as starting materials. The 15 WO 00/39241 PCT/US99/31246 following route to a di-ester linked multiple functional quaternary ammonium compound can usefully be employed. H OH Cocoalkyl-N + CH20CH2 Cocoalkyl-N OH I Ethylene oxide M Me Me OH + 2 Cocoalkyl-N COOH condensation methylation Me Me 0 1 + Me Cocoalkyl-N,. 0 1+ I N-Cocoalkyl MeI 0 Me 5 Example 7: Reaction of Ethoxylated Armeen 2HT with Succinic Acid, Followed by Quaternization 10 Ethoxylation of dialkylamine, followed by reaction with dicarboxylic acid and methylation, will yield the bis-ester-spaced bis(methyldialklyammmonium) compound. 1. Ethoxylation of Armeen 2HT 15 In a 1-liter autoclave, Armeen 2HT (234.7 g, 0.5 mole) was dissolved in isopropyl alcohol (80 g) by heating. After nitrogen purging, ethylene oxide (22g, 0.5 mole) was introduced. The mixture was heated at 80 0 C for two hours. The 13 C NMR indicated that the reaction was good except 20 that some starting amine remained unreacted (HN-CH 2 - at 50.24 ppm). Additional 11 g of ethylene oxide was added, and the heating at 80 0 C continued for two more hours. After evaporation, a white solid paste (250 g) was obtained. The product, ethoxylated Armeen 2HT, consisted of monoethoxylated amine, 71.3 mole %; polyethoxylated amine, 26.0 mole 25 % with n = 2.7; and unreacted amine, 2.7 mole %. 16 WO 00/39241 PCT/US99/31246 2. Reaction of Ethoxylated Armeen 2HT with Succinic Acid Under an atmosphere of nitrogen, a mixture of ethoxylated Armeen 2HT (172 g, 0.3 mole), succinic acid (17.84 g, 0.15 mole) and 50% aqueous 5 hypophosphorous acid (0.74 g) was heated with stirring at 180-5 0 C for 5 hours. An off-white thick paste was obtained. The product consisted of the desired diamine esters 90% and monoamines which accounted for 10% by weight. 10 3. Quaternization of Bis-(ethoxylated Armeen 2HT) Succinate Diester To a solution of bis-(ethoxylated Armeen 2HT) succinate (89 g, 0.14 equiv) in isopropyl alcohol (20 g) at 75-801C, dimethyl sulfate (about 17 g, 0.135 mole) was slowly added. Free amine should be about 2% 15 indicating substantial completion of quaternization. Evaporation yielded the neat ester diquaternary ammonium compound. Example 8 PREPARATION OF BIS(2- ETHYLHEXYLDIMETHYLAMMONIUM) 1.6-HEXANE DI(CHLORIDE) VIA BIS(SCHIFF BASE) INTERMEDIATE 20 Summary H +NH2 N-=C8H16 + NaBH4 (I) H HNIC3H17 + CH20/HCOOH (ll) H H17C--NCBHi + CH3CI + +H0 (111) H17C8--N81 I N-C8Hi7 2 Cl 17 WO 00/39241 PCTIUS99/31246 1. Reaction of 2-Ethylhexanal with 1,6-Hexanediamine To the melt 1,6-hexanediamine (58.1 g, 0.5 mole) at ca. 50 C, 2 ethylhexanal (128.2 g, 1 mole) was slowly added with stirring over three 5 hours. Cooling in an ice-water bath occasionally was necessary because the reaction was exothermic. The reaction was completed as indicated by the disappearance of the aldehyde carbon in the "C NMR spectrum. The reaction product was washed several times with deionized water. Evaporation yielded a yellow liquid (ca 160 g) in nearly quantitative yield. 10 2. Reduction of Diimine with Sodium Borohydride To a solution of the diimine (1) (141.6 g, 0.38 mole) in methanol (150 g) sodium borohydride (ca 20 g)was added in small portions. During the 15 addition, the reaction flask was cooled in an ice water bath from time to time. The reaction was completed as indicated by the disappearance of the imine carbon line at 168 ppm in the "C NMR spectrum. The reaction mixture was washed with deionized water several times. Evaporation gave a yellowish liquid (ca 138 g). 20 3. Methylation of NN'-Di(2-ethylhexyl)-1 .6-hexanediamine The addition of 90% formic acid with stirring to the diamine (11) (126.3 g, 0.37 mole) yielded a light brown solution as the temperature rose to 750 25 C. Having been cooled to room temperature the mixture was treated with 37.1% formaldehyde solution (65.8 g, 0.814 mole) by adding the formaldehyde in small portions with stirring. The resulting mixture was evaporated on a rotary evaporator at ca 650 C for 2 hours. About 72 g of concentrated HCI was then added. The mixture was heated at 700 C for 3 30 hours and was then neutralized with 25% aqueous NaOH solution. The product was washed with water several times and evaporated to yield a pale yellow liquid (ca 150 g). 18 WO 00/39241 PCTIUS99/31246 4. Quaternization of the di-tertiary-amine (1ll) with Methyl Chloride A solution of di(tertiary amine) (147.5 g, 0.4 mole) was quaternized with 5 methyl chloride in the presence of sodium bicarbonate (1 .5 g), at 800 C for about 10 hours. The reaction was completed as indicated by the disappearance of the peak of the methyl carbon on nitrogen at 42.7 ppm in the 1C NMR spectrum. The reaction mixture was filtered and the filtrate was evaporated to yield the desired diquaternary ammonium salt, a pale 10 yellow paste (189 g). Example 9 - Preparation of bis(2-ethylhexyldimethylammonium) (dimethylammonium) dihexane trichloride Summary H O H N H + 2 H +I H H H H C=N N catalytic hydrogenation H CH-NH NNH-CH ductive methvlation (VI)
CH
3 quaternization wNith CH3CI CH-N NC L;3(VII)
O;H
3
CH
3 -C
CH
3 -CH-H OHNI
CH
3 + N-O O/ H 3 O l H 3 15 (VimI) 19 WO 00/39241 PCT/US99/31246 1. Reaction of di(hexamethylene)triamine with 2-Ethylhexanal Note that the "triamine" is actually a mixture of triamine and 1,6 hexanediamine. NE (neutralization equivalent) of primary amine = 96.46; 5 NE(secondary amine) = 341.76. 86% triamine, 14% diamine. The mixture of "triamine" (101.4 g, 1.05 equivalents primary amine) and 2-ethylhexanal (134.7g, 1.05 moles) was heated at 70* C for 4 hours. The crude product was washed with water and evaporated to yield the diimine 10 (V) (220 g). 2. Reduction of the Diimine (V) with Sodium Borohydride To a solution of 220 g dimine (V) in methanol (220 g) was added in small 15 portions sodium borohydride powder (20 g) until the reaction was complete as indicated by the disappearance of the imine carbon (168 ppm) in the "C NMR spectrum. The product was washed with water and evaporated. 20 3. Methylation of Tris(secondary amine) compound (VI) To compound VI was added with stirring 90% formic acid (149 g, 2.9 moles). The temperature was maintained at 50-60' C with cooling. A 37.1% formaldehyde solution (104 g, 1.286 moles) was added in small 25 portions. The resulting mixture was then evaporated on a rotary evaporator to remove the excess formic acid and formaldehyde. After the addition of concentrated HCI (1.4 mole), the mixture was heated at 700 C for 3 hours and was then neutralized with 25% aqueous NaOH solution. The product was separated, washed with water and evaporated. A pale 30 yellow liquid (208 g) was obtained. 4. Quaternization of the Tris(tertiary amine) Compound (VII) Compound VII (140 g, 0.3 mole) dissolved in methanol (140 g), with 35 added NaHCO 3 , was quaternized with methyl chloride at 800 C for 10 20 WO 00/39241 PCT/US99/31246 hours. The reaction was completed as indicated by disappearance of the methyl carbon (CH 3 -N) peak in the 13C NMR spectrum. Filtration and evaporation of solvent yielded a pale yellow solid (VIII) (ca. 185 g). 5 Example 10 - Preparation of Multiple Functional Amidoamine Quaternary Ammonium Compounds: Reaction of Duomeen CD with dimethylsuccinate to form bis-Duomeen CD succinate [a bis(secondary amido-secondary amine) compound] 0 0 Il l
RNHCHCH
2
CH
2 NH, + CH 3 0CCH 2
CHCOCH
3 0 0 RNH(CH2) 3
NHC(CH
2
)
2
CNH(CH
2
)
3 NHR, (XX0 0 0
RN(CH
2
)
3 N HC (CH2) 2
CNH(CH
2
)
3 NHR
C(CH
2 )2CNH(CH 2
)
3 NHR, il || 0 0
RNH(CH
2
)
3
NH
2 , 10 R = Coco A mixture of Duomeen@ CD (490.8 g, 2 equivalents of primary amine) and dimethyl succinate (136.08 g, 0.93 mole) was heated at 125-1301C under nitrogen for 5 hours. Additional dimethyl succinate (6.8 g, 0.046 15 mole) was added and the heating was continued for another 5 hours. The bis-Duomeen succinate (XXI), an off-white solid, was obtained. The product consisted of the bis-sec-amines (95% by weight) and unreacted Duomeen (4%). 20 Methylation and quaternization of this bis-sec amine product can be performed in processes like those which have been described elsewhere in this application, to yield the bis(amido-amine) quaternary ammonium compound. 21 WO 00/39241 PCTIUS99/31246 Example 11 - Alternative Route to Multiple Functional "Internal ester" Quaternary Ammonium Compounds Step 1: Reaction of a primary fatty amine compound with formaldehyde 5 will form the hexahydrotriazine intermediate;
RNH
2 + 3 HCHO + hexahydrotriazine Step 2: hexahydrotriazine is reduced to form secondary amine; Hexahydrotriazine + RNH(Me) Step 3: secondary amine is ethoyxlated to form alcohol amine compound; 10 RNH(Me) + ethylene oxide + RN(Me)CH 2
CH
2 OH Step 4: two equivalents of ethoxylated amine react with dicarboxylic acid to form Gemini tertiary amine; 2 RN(Me)CH 2
CH
2 OH + HOOC(CH 2
)
2 COOH 4 RN(Me)CH 2
CH
2 0OC(CH 2
)
2
COOCH
2
CH
2 N(Me)R 15 Step 5: Gemini tertiary amine quaternized in reaction with methylating agent (methyl chloride or methylsulfate). RN(Me)CH 2
CH
2 0OC(CH 2
)
2
COOCH
2
CH
2 N(Me)R + methylating agent 4 20 Gemini "internal ester" quaternary ammonium compound Example 12 - Preparation of Ester - functional tris-quaternary ammonium Compound step I preparation of diesteramine 25 CH 3 N (CH 2
CH
2
OH)
2 + excess HOOC (CH 2
)
4 COOH 0 CH 3 0 HOOC -(CH 2
)
4 - C -0- CH 2
CH
2 N - CH 2
CH
2 0 C -(CH 2
)
4 COOH (1) 30 step 2 Ethoxylation of long chain amino compound (see Example 7, step 1) cocoalkyl - N + CH 2 0 CH 2 4 cocoalkyl -N OH 35 H
CH
3 22 WO 00/39241 PCT/US99/31246 step 3 Reaction of ethoxylated amine compound 1i with dicarboxylic acid I, (see Example 7, step 2) 1 + 2 II -> followed by reductive methylation 5
CH
3 0 0 CH 3 0 0 CH 3 | || | I il I cocoalkyl - N -(CH 2
)
2 0 C (CH 2
)
4 C 0 CH 2
CH
2 - N - CH 2
CH
2 0 C (CH 2
)
4 CO (CH 2
)
2 N 10 cocoalkyl step 4 quaternization of Ill (see Example 7, step 3) 23

Claims (32)

1. A compound of general formula I, il or Ill: 5 R 3 R4() I I R, - N*- (A)n- N' - R2 10 R 5 R6 2Z 15 R 8 (II) I II R 7 - N* - (A)n-N *- (A)n- N* - R1 I 1I 20 R12 R 13 3Z R 1 6 R 1 7 25I R- N- (CH 2 )n - N - R 20 1 | 0 R18 R, 2Z 30 - - wherein each of R, through R 20 are independently selected from straight or branched chain, substituted or unsubstituted C,-C22 alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide linkage, or mixtures thereof; A is a 35 spacer group of the formula: 0 0 0 I1 I II (CH 2 )x - C - 0 - (CH 2 )y , (CH 2 )x - 0-C- (CH 2 )y - C-0-(CH 2 ), 40 24 WO 00/39241 PCTIUS99/31246 0 0 (CH 2 CH 2 0)x -C - (CH 2 )y - C -( OCH 2 CH 2 ) 5 0 0 0 Il 1l I1 (CH 2 )x N - C -(CH 2 )y - C-N-(CH 2 )z, (CH 2 )x-C-N-(CH 2 )y 0 0 1l 1l 10 (CH 2 CH 2 CH 2 N)xC-(CH 2 )YC-(NCH 2 CH 2 CH 2 )z or other ester- or amide-functional alkyl group, where x, y and z are each independently selected from an integer of from 1 to 20 and wherein in each of formulae 1, 11 and 111, Z~ is an anion, with the proviso that R 1 , and 15 R 20 are not the same.
2. The compound of claim 1 wherein that R, , R,, R 1 4 R 1 , and R 2 0 are each independently selected from the group consisting of C2-C alkyl groups, C 12 - C alkyl groups containing an ester linkage and C12 - C 18 20 alkyl groups containing an amide linking group.
3. The compound of claim 1 wherein each of R, , R 2 ,R 3 , R 4 ,R 5 , and R a re selected from the group consisting of methyl, ethyl, propyl, 2 ethylhexyl, nonyl-alkyl, C13 - C, mixed alkyl group, dodecylalkyl, 25 octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and mixtures thereof; and n is an integer of from 1 to 5.
4. The compound of claim 1 wherein each of R 7 , R, ,R 9 , R, 0 , R, ,R 12 , 30 R, 3 and R 1 , are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13 - C mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and mixtures thereof, and that n is an integer of from 1 to 5. 25 WO 00/39241 PCTIUS99/31246
5. The compound of claim 1 wherein each of R, 5 ,R 16 , R 17 , R 1 8 ,R 1 9 and R 20 is independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, a C13 - C15 mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenated 5 tallowalkyl and mixtures thereof with the proviso that R 15 is not the same as R 20 ; and n is an integer of from 1-20.
6. A surfactant composition which comprises at least one of the compounds of claim 1. 10
7. A process for preparing the multiple functional quaternary ammonium compounds of general Formula I which comprises reacting a dialkylalkanol amine of formula Q, 1 15 Q2 - N - Q 3 -OH wherein each of Q1, Q 2 and Q is independently selected from the group consisting of C1-C22 alkyl groups and a dicarboxylic acid of the formula HOOC - (CH 2 )n - COOH 20 wherein n is an integer of from 1-10, to form a reaction mixture and thereafter quaternizing the reaction mixture.
8. The process of claim 7 wherein said dialkylalkanol amine is prepared by ethoxylating a fatty amine compound of the formula z N- H 30 Y wherein Z is a C12-C22 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group, and Y is a C,-C22 substituted or unsubstituted, saturated or unsaturated, straight or branched chain alkyl group. 35 26 WO 00/39241 PCT/US99/31246
9. The process of claim 8 wherein said fatty amine compound is selected from the group consisting of dodecylamine, hexadecylamine, octadecylamine, oleylamine, cocoalkylamine, soyaalkylamine, tallowalkylamine, hydrogenatedtallowalkyl amine, dicocoalkylamine, 5 ditallowalkylamine, dihydrogenated tallowalkylamine, dioctadecylamine,and mixtures thereof, and the quaternizing agent is a methylating agent.
10. The process of claim 7 wherein the dialkylalkanol amine is 10 selected from the group consisting of dimethylethanolamine, diethylethanol amine, and mixtures thereof; and the dicarboxylic acid is selected from the group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof, and the quaternizing agent is a long chain alkylhalide reagent. 15
11. The process of claim 10 wherein the dialkylalkanolamine is dimethylethanolamine and the dicarboxylic acid is adipic acid.
12. A process for preparing multiple functional hydrophilic/hydrophobic 20 compounds which comprises reacting a diamine of the formula: Z - NH - (CH 2 )n- NH 2 or a triamine or tetramine of the formula: Z - NH - (CH 2 CH 2 CH 2 NH)m CH 2 CH 2 CH 2 NH 2 where Z is a C, - C22 saturated or unsaturated alkyl group and m is 1 or 2, 25 with a dicarboxylic acid of the formula: HOOC - (CH 2 )n - COOH wherein n is an integer of from 1-10.
13. The process of claim 12 wherein Z is selected from cocoalkyl, 30 tallow alkyl, or oleylalkyl, and the dicarboxylic acid is selected from the 27 WO 00/39241 PCT/US99/31246 group consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof.
14. The process of claim 13 wherein the amine is selected from the 5 group consisting of N-coco 1,3 - diaminopropane, N-tallow -1,3 diaminopropane, N,N,N' - trimethyl-N-tallow-1,3 diaminopropane, N-oleyl 1,3 diaminopropane, 3 -tallowalkyl-1,3-hexahydropyrimidine, N tallowalkyl dipropylene triamine, N-tallowalkyl tripropylene tetramine and mixtures thereof, and the dicarboxylic acid is selected from the group 10 consisting of oxalic, malonic, succinic, glutaric, adipic, maleic, fumaric and mixtures thereof.
15. The compound of claim 1 wherein R, and R 20 are each independently selected from the group consisting of C, 2 -C, 8 alkyl groups, 15 methyl, ethyl, propyl, 2-ethylhexyl, nonylalkyl, and C13-C5 mixed alkyl group, dodecylalkyl, octadecylalkyl, oleylalkyl, cocoalkyl, soyaalkyl, tallowalkyl, hydrogenatedtallowalkyl and C12-Cj alkyl groups containing an ester or amide function ; and n is an integer of from 2 to 3. 20
16. The compound of claim 1 wherein R 1 6 , R
17 , R 18 , R 1 9 are independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-C1 mixed alkyl group; and n is an integer of from 2 to 3. 25 17. A viscosity modifying agent comprising the compound of claim 15.
18. A viscosity modifying agent comprising the compound of claim 16.
19. The compound of claim 1 wherein R 15 and R 20 are each 30 independently selected from the group consisting of C12-Cl. alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-Ci mixed alkyl 28 WO 00/39241 PCT/US99/31246 group and C12-Ci alkyl groups containing an ester or amide function; and n is an integer of from 5 to 8.
20. The compound of claim 1 wherein R 1 6 , R 1 , R 18 , R 1 . are 5 independently selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C 1 2 -C 1 8 mixed alkyl group; and n is an integer of from 5 to 8.
21. The compound of claim 1 wherein R, 5 and R 20 are each 10 independently selected from the group consisting of C12-Cl. alkyl groups, methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, and a C12-C1, mixed alkyl group and C12-C18 alkyl groups containing an ester or amide function, and n is an integer of from 2 to 20. 15
22. An ore flotation aid comprising the compound of claim 21.
23. The ore flotation aid of claim 22 wherein in said compound R, and R 20 are each independently selected from the group consisting of C12-C,8 alkyl groups, and C12-C, alkenyl groups, and C 1 2 -Cjalkyl groups 20 containing an ester or amide function; R 1 ., R 17 , R 1 8 , R 1 are methyl groups; and n is an integer of from 2 to 12.
24. A calcium ore flotation aid comprising the compound of claim 23.
25 25. A process for the preparation of compounds of general formula IV R22 R 2 3 R2 R 21 - N - (CH 2 )x - N - (CH 2 )y - N'- R 2 1 30 R 2 8 R 2 7 R 2 6 n (2+n)Z- (IV) 29 WO 00/39241 PCT/US99/31246 wherein R 21 , R 22 , R 2 , R 24 , R 25 , R 2 3, R 27 , and R 2 , are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C,-C22 alkyl or alkenyl groups, wherein said alkyl or alkenyl groups optionally contain at least one ester linkage, at least one amide 5 linkage or mixtures thereof, and where x an y are each independently an integer of from 1-20, n isl-20 and Z- is an anion, said process comprising the reaction of a polyaminoalkyl compound with multiple equivalents of alkyl or alkenyl aldehyde or alcohol compounds. 10
26. The process of claim 25 wherein the diaminoalkyl compound is a compound of the formula: H 2 N-(CH 2 )n-NH 2 and the aldehyde or alcohol compound is selected from the group consisting of methyl, ethyl, propyl, 2-ethylhexyl, nonyl-alkyl, C12-Ci mixed 15 alkyl groups and mixtures thereof and n is an integer of from 1 to 5.
27. The process of claim 25 wherein the diaminoalkyl compound is hexamethylenediamine. 20
28. A compound of formula IV R2 R 2 3 R24 25 R 21 - N - (CH2).- N'-- (CH 2 )y- N-- R 2 5 (2+n)Z R 2 8 R R 2 6 _ __ _ n IV 30 wherein R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 2 1, and R 2 , are the same or different and are selected from straight or branched chain, substituted, or unsubstituted C-C22 alkyl or alkenyl groups, wherein said alkyl or alkenyl 30 WO 00/39241 PCTIUS99/31246 groups optionally contain at least one ester linkage, at least one amide linkage or mixtures thereof, and where x an y are each independently an integer of from 1-20, n is greater than 1 and Z- is an anion. 5
29. A surfactant composition which comprises at least one compound of claim 1 in combination with at least one conventional surfactant.
30. The composition of claim 29 wherein said conventional surfactant is a mono- quaternary ammonium compound. 10
31. A surfactant composition which comprises at least one compound of claim 28 in combination with at least one conventional surfactant.
32. The composition of claim 31 wherein said conventional surfactant is a 15 mono- quaternary ammonium compound. 31
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CN110845357A (en) * 2019-11-22 2020-02-28 华东理工大学 Quaternary ammonium salt type hydrazide compound, quaternary ammonium salt type hydrazone compound prepared from same and application of quaternary ammonium salt type hydrazone compound
CN110845357B (en) * 2019-11-22 2022-09-30 华东理工大学 Quaternary ammonium salt type hydrazide compound, quaternary ammonium salt type hydrazone compound prepared from same and application of quaternary ammonium salt type hydrazone compound

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CA2357756A1 (en) 2000-07-06
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ZA200105408B (en) 2002-09-30
CN1346395A (en) 2002-04-24
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WO2000039241A1 (en) 2000-07-06
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