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WO1997038968A1 - Syntheses of substituted amines - Google Patents

Syntheses of substituted amines Download PDF

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Publication number
WO1997038968A1
WO1997038968A1 PCT/US1997/006337 US9706337W WO9738968A1 WO 1997038968 A1 WO1997038968 A1 WO 1997038968A1 US 9706337 W US9706337 W US 9706337W WO 9738968 A1 WO9738968 A1 WO 9738968A1
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WO
WIPO (PCT)
Prior art keywords
formula
hydrocarbyl
amine
preparing
substituted
Prior art date
Application number
PCT/US1997/006337
Other languages
French (fr)
Inventor
Jeffrey John Scheibel
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to JP9537347A priority Critical patent/JPH11507953A/en
Priority to EP97920413A priority patent/EP0898560A1/en
Priority to BR9708718A priority patent/BR9708718A/en
Publication of WO1997038968A1 publication Critical patent/WO1997038968A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/50—Ethers of hydroxy amines of undetermined structure, e.g. obtained by reactions of epoxides with hydroxy amines
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Definitions

  • the present invention relates to processes for preparing substituted alkyl amines and surfactants therefrom.
  • laundry detergents and other cleaning compositions present a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates.
  • laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers, and the like all require the proper selection and combination of ingredients in order to function effectively.
  • such detergent compositions will contain one or more types of surfactants which are designed to loosen and remove soils and stains.
  • the removal of body soils, greasy/oily soils and certain food stains quickly and efficiently can be problematic. Indeed, while some surfactants and surfactant combinations exhibit optimal performance on certain types of soils and stains, they can actually diminish performance on other soils.
  • surfactants which remove greasy/oily soils from fabrics can sometimes be sub-optimal for removing particulate soils, such as clay.
  • particulate soils such as clay.
  • surfactants and surfactant combinations are available to the detergent manufacturer, the reality is that many such ingredients are specialty chemicals which are not suitable in low unit cost items such as home-use laundry detergents.
  • home-use products such as laundry detergents still mainly comprise one or more of the conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and the need to formulate compositions which function reasonably well with a variety of soils and stains and a variety of fabrics.
  • fatty tertiary amines are prepared from natural fatty acid feedstocks.
  • the present invention provides a commercial route to the use of synthetic alcohol feedstocks.
  • the present invention provides direct syntheses processes for substituted amines which involve the reaction of an alkyl sulfate with a mono-, or bis-alkoxy amine.
  • the processes have important commercial advantages in that they can be conducted in a water solvent at relatively modest temperatures and pressures.
  • the present invention encompasses a process (I) for preparing substituted tertiary amines ofthe formula:
  • R is C6-C22 hydrocarbyl (alkyl, alkenyl, linear or branched)
  • R' is C1-C22 hydrocarbyl
  • M is a water-solubilizing cation, especially sodium. Water or excess amine reactant can be used as the reaction solvent.
  • the invention also encompasses a process (II) for preparing substituted tertiary amines ofthe formula:
  • R is C6-C22 hydrocarbyl and M is a water- solubilizing cation.
  • M water- solubilizing cation.
  • the invention also encompasses a process (III) for preparing substituted tertiary amines ofthe formula:
  • the invention also encompasses a process for preparing ethoxylated tertiary amines ofthe formula:
  • the invention also encompasses a process for preparing ethoxylated tertiary amines of the formula:
  • the invention also encompasses processes for preparing cationic surfactants by quaternizing the tertiary amines prepared according to the above processes, (I), (II), (III) and (IV), respectively, and the ethoxylates thereof. This can be accomplished, for example, by reacting the ethoxylated tertiary amines with reactants R"Z, wherein R" is, for example C1-C5 (preferably methyl) hydrocarbyl, X-CH2CH2OH, and the like, wherein X is Cl, Br, methylsulfate, and the like.
  • R"Z reactants
  • the foregoing conventional steps (a)-(d) employ either high temperatures or multiple reactors or separation equipment or flammable metal catalysts such as Raney Ni (trademark), or use ammonia, or generate undesirable impurities, or limit the potential chain length flexibility, i. e., only natural oil based, all of which can result in processing complexity, high equipment costs and sub-optimal yields, with the net result of higher overall costs for the desired substituted amines.
  • Other conventional processes utilize fatty alkyl halides or fatty tertiary amines which can also produce undesirable impurities and by-products.
  • the present process directly converts alkyl sulfates into the desired substituted amines.
  • various steps of the present process can use water as the reaction solvent.
  • the sodium sulfate by-product remains in the water phase and helps "salt- out" the high purity substituted amine reaction product as a separate phase. Thus, recovery of the substituted amine reaction product is simple and inexpensive.
  • the sodium sulfate by-product can be recovered for use in the manufacture of detergent granules.
  • the present process can be conducted at relatively modest pressures, thereby avoiding the need for expensive, high pressure reactors. Although typically water is used, with sufficient excess amine reactant the water may not be necessary as amine can act as solvent and reactant.
  • reaction Process I for reaction Process I, hereinafter, the following parameters summarize the optional and preferred reaction conditions herein.
  • the reaction herein is preferably conducted in an aqueous medium.
  • Reaction temperatures are typically in the range of 100-230°C.
  • Reaction pressures are 50-1000 psig.
  • a base preferably sodium hydroxide, can be used to react with the HSO4- generated during the reaction, or an excess of the amine can be employed to also react with the acid.
  • the mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1 :1.1 ; more preferably from 2:1 to 1:1.
  • the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble.
  • reaction mixture may be dried and added to the heavy duty granular detergent product since separation of the water and organic phase may not be possible with some chain length of alkylsulfates.
  • the process herein is preferably conducted using C12-C13 alkyl sulfate, sodium salt and N-methyl monoethanolamine.
  • reaction Process II hereinafter, the following parameters summarize the optional and preferred reaction conditions herein.
  • the reaction herein is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 140-200°C. Reaction pressures are 50-1000 psig.
  • a base catalyst, preferably sodium hydroxide can be used.
  • the mole ratio of reactants are 2:1 to 1 :1 amine to alkyl sulfate.
  • the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble.
  • the process herein is preferably conducted using C12-C13 alkyl sulfate, sodium salt.
  • the reaction Process II results in products which are sufficiently soluble in the aqueous reaction medium that gels may form.
  • an alternate, two-step synthesis Process III hereinafter, may be more desirable in some commercial circumstances.
  • the first step in Process III is conducted as in Process I.
  • the second step is preferably conducted using ethylene oxide and an acid such as HCl which provides the quaternary surfactant.
  • HCl an acid
  • chlorohydrin i.e., chloroethanol
  • chloroethanol can also be reacted to give the desired bishydroxyethyl derivative.
  • Process IV is conducted using ethylene oxide under standard ethoxylation conditions, without catalyst, to achieve monoethoxylation as shown below.
  • EO represents the -CH2CH2O- unit.
  • Process I-III either an inorganic base or an organic base or excess amine reactant is used to neutralize generated HSO4.
  • PROCESS (ID R— OSO 3 " Na + + H-N— [(EO)H] 2 - ⁇ AL ⁇ .
  • Processes (I)-(IV) can be further ethoxylated using base catalyst and optionally quatted.
  • Process III gives a quaternary product of the bishydroxy material with a methyl group and Cl counterion.
  • the product of Process I can be ethoxylated under base catalyzed conditions to give R-N(CH3)(CH2CH2O) x -H which can be quatted with CH3C1 to give R-N(CH3)2(CH2CH2O) x -H+ Cl- or quatted with ethylene oxide and HCl to give new monoethoxylated monohydroxyethyl quaternary surfactants. While the above Processes (I), (II), (III) and (IV) are illustrated with reactants carrying the preferred EO units, propoxy, iso-propoxy, butoxy, and mixtures thereof, and mixtures with EO units, can also be used.
  • parent R- or R(EO)x-substituted mono- or bis-hydroxyethyl amine can be further alkoxylated (preferably ethoxylated using conventional ethylene oxide reactions. Following ethoxylation, the resulting amines can be quaternized using standard reactants and conditions.
  • the glass liner is sealed into 3 L, stainless steel, rocking autoclave, purged twice with 260 psig nitrogen and then heated to 160-180°C under 700-800 psig nitrogen for 3 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 1 L separatory funnel. The mixture is separated into a clear lower layer, turbid middle layer and clear upper layer.
  • the clear upper layer is isolated and placed under full vacuum ( ⁇ 100 mm Hg) at 60-65°C with mixing to remove any residual water.
  • the clear liquid turns cloudy upon removing residual water as additional salts crystallizes out.
  • the liquid is vacuum filtered to remove salts to again obtain a clear, colorless liquid. After a few days at room temperature, additional salts crystallize and settle out.
  • the liquid is vacuum filtered to remove solids and again a clear, colorless liquid is obtained which remains stable.
  • the isolated clear, colorless liquid is the title product by NMR analysis and is >90% by GC analysis with a typical recovery of >90%.
  • Example II Preparation of N.N-Bis(2-hvdroxyethvDdodecylamine (Process II) To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of diethanolamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H2O. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours.
  • the mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform.
  • the funnel is shaken well for a few minutes and then the mixture is allowed to separate.
  • the lower chloroform layer is drained and the chloroform evaporated off to obtain product.
  • Example III Preparation of N.N-Bis(2-hvdroxyemvDdodecylamine (Process III) 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of base in the manner described in Example (II). The resulting 2- hydroxyethyldodecylamine is recovered and reacted with 1-chloroethanol to prepare the title compound.
  • the glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a Tew minutes and then allowed mixture to separate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120- 130°C to produce the desired final product.
  • Example VI Preparation of Dodecyl Dimethyl Pentaethylene glycol Ammonium Chloride
  • 100 g of N-(2-hydroxyethyl)-N- methyldodecylamine (0.4108 moles prepared according to process I) and 0.47 of sodium (0.0204 moles).
  • the reaction mixture is heated to 120-130°C and mixed under ethylene oxide atmosphere until 72.37 g (1.643 moles) of ethylene oxide has been absorbed.
  • the reaction is purged with nitrogen and 170 g of 2-propanol is added.
  • reaction mixture is added to glass autoclave liner, sealed liner in 3 L, stainless steel, rocking autoclave, purged once with 250 psig nitrogen, once with 50 psig methyl chloride and is charged to 65-70 psig with methyl chloride and heated to 75-80°C with mixing for 15 hours.
  • the reaction is cooled reaction to 50°C, removed from the autoclave and 2-propanol is evaporated off to obtain product.
  • Example VII Preparation of Bis(2-hvdroxyethyl > ) Dodecyl Methyl Ammonium Chloride To a 1 L round bottom flask equipped with magnetic stir bar, water cooled condenser and nitrogen line is added 200 g of N-(2-hydroxyethyl)-N- methyldodecyiamine (0.8216 moles prepared according to process I), 66.15 g of 2- chloroethanol (0.8216 moles) and 200 g of ethanol. The mixture is heated to reflux for 24 hours and then evaporated off ethanol to obtain product.
  • the reaction is purged with nitrogen.
  • the reaction mixture is ready for use as an aqueous stock solution of product.
  • the tertiary amines and/or alkoxylated tertiary amines can also be oxidized to form the corresponding amine oxide surfactants.

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Abstract

Hydrocarbyl sulfates are reacted with alkoxy amines. The resulting substituted amines can be ethoxylated, quaternized and/or oxidized to form detersive surfactants.

Description

SYNTHESES OF SUBSTITUTED AMINES
TECHNICAL FIELD The present invention relates to processes for preparing substituted alkyl amines and surfactants therefrom.
CROSS REFERENCE This application claims priority under Title 35, United States Code 119(e) from Provisional Application Serial No. 60/015,584, filed April 18, 1996. BACKGROUND OF THE INVENTION
The formulation of laundry detergents and other cleaning compositions presents a considerable challenge, since modern compositions are required to remove a variety of soils and stains from diverse substrates. Thus, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers, and the like, all require the proper selection and combination of ingredients in order to function effectively. In general, such detergent compositions will contain one or more types of surfactants which are designed to loosen and remove soils and stains. However, the removal of body soils, greasy/oily soils and certain food stains quickly and efficiently can be problematic. Indeed, while some surfactants and surfactant combinations exhibit optimal performance on certain types of soils and stains, they can actually diminish performance on other soils. For example, surfactants which remove greasy/oily soils from fabrics can sometimes be sub-optimal for removing particulate soils, such as clay. While a review ofthe literature would seem to indicate that a wide selection of surfactants and surfactant combinations is available to the detergent manufacturer, the reality is that many such ingredients are specialty chemicals which are not suitable in low unit cost items such as home-use laundry detergents. The fact remains that most such home-use products such as laundry detergents still mainly comprise one or more of the conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and the need to formulate compositions which function reasonably well with a variety of soils and stains and a variety of fabrics.
The literature does suggest that various nitrogen-containing surfactants would be useful in a variety of cleaning compositions. Such materials, typically in the form of amino-, amido-, or quaternary ammonium or imidazolinium compounds, are often designed for specialty use. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to provide cosmetic benefits to hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide a fabric softening and anti-static benefit. For the most part, however, the commercial use of such materials is rather limited, and the aforementioned nonionic and anionic surfactants remain the major surfactant components in today's laundry compositions. Accordingly, there is a need for a simple, economical method to produce the feedstock substituted amines which can be converted into the desirable N-based surfactants.
Most fatty tertiary amines are prepared from natural fatty acid feedstocks. The present invention provides a commercial route to the use of synthetic alcohol feedstocks. The present invention provides direct syntheses processes for substituted amines which involve the reaction of an alkyl sulfate with a mono-, or bis-alkoxy amine. The processes have important commercial advantages in that they can be conducted in a water solvent at relatively modest temperatures and pressures. BACKGROUND ART
U.S. Patent 5,441,541, issued August 15, 1995, to A. Mehreteab and F. J. Loprest, relates to anionic/cationic surfactant mixtures. U.K. 2,040,990, issued 3 Sept., 1980, to A. P. Murphy, R.J.M. Smith and M. P. Brooks, relates to ethoxylated cationics in laundry detergents. See also: GB 2,266,889A and EP 0569904A2. SUMMARY OF THE INVENTION
The present invention encompasses a process (I) for preparing substituted tertiary amines ofthe formula:
Figure imgf000004_0001
by reacting an alkyl sulfate of the formula RSO3"M+ with an amine reactant of the formula:
XH2CH2OH
H-ϊ< ^R wherein in the above formulas, R is C6-C22 hydrocarbyl (alkyl, alkenyl, linear or branched), R' is C1-C22 hydrocarbyl and M is a water-solubilizing cation, especially sodium. Water or excess amine reactant can be used as the reaction solvent. The invention also encompasses a process (II) for preparing substituted tertiary amines ofthe formula:
XH2CH2OH
R-r<
CH2CH2OH by reacting an alkyl sulfate ofthe formula RSO3"M+ with an amine reactant of the formula
^C H2C H 2O H
H -N C
C H2C H2O H wherein in the above formulas, R is C6-C22 hydrocarbyl and M is a water- solubilizing cation. Again, water or excess amine reactant can be used as the reaction solvent.
The invention also encompasses a process (III) for preparing substituted tertiary amines ofthe formula:
Figure imgf000005_0001
comprising the steps of:
(a) reacting an alkyl sulfate ofthe formula RSOβ'M"1" with an amine reaction of the formula
.CH2CH2OH
H— N ^ H to form a secondary substituted amine ofthe formula:
Figure imgf000005_0002
(b) reacting said substituted amine with chloroethanol, wherein, in the above formulas, R is C6-C22 hydrocarbyl and M is a water-solubilizing cation. The invention also encompasses a process (IV) for preparing ethoxylated tertiary amines ofthe formula r^CH2CH2OH
R-N v., ΕOH by the uncatalyzed monoethoxylation with ethylene oxide of a substituted secondary amine prepared according to Step (a) of process (III), wherein "EO" is - CH2CH2-O and R is Cg-C22 hydrocarbyl.
The invention also encompasses a process for preparing ethoxylated tertiary amines ofthe formula:
Figure imgf000005_0003
by ethoxylating a substituted tertiary amine prepared according to process (I) in the presence of base catalyst, wherein R and R' are as above in process (I), EO is -CH2CH2O- and x is 1-30.
The invention also encompasses a process for preparing ethoxylated tertiary amines of the formula:
.CH2CH2O(EO)xH
R-r<
CH2CH2O(EO)xH by ethoxylating a substituted tertiary amine prepared according to process (II) in the presence of base catalyst, wherein R is as above in process (II), EO is -CH2CH2O- and each x is independently 1-30, and may be the same or different. The invention also encompasses a process for preparing ethoxylated tertiary amines ofthe formula:
R_N^CH2CH2O(EO)χH
^CH2CH20(EO)χH by ethoxylating a tertiary amine prepared according to process (III) in the presence of base catalyst, wherein R is as in process (III) and EO and x are each as noted immediately above.
The invention also encompasses processes for preparing cationic surfactants by quaternizing the tertiary amines prepared according to the above processes, (I), (II), (III) and (IV), respectively, and the ethoxylates thereof. This can be accomplished, for example, by reacting the ethoxylated tertiary amines with reactants R"Z, wherein R" is, for example C1-C5 (preferably methyl) hydrocarbyl, X-CH2CH2OH, and the like, wherein X is Cl, Br, methylsulfate, and the like. The invention also encompasses novel compounds ofthe formula:
CH2CH2OH R— N .
^(EO)xH wherein x is 1-30, R is C6-C22 and EO is-CH2CH2θ- and
+ ,R' R-N— CH2CH2OH X
N(EO)xH wherein x is 1-30, R is C6-C22> EO is -CH2CH2O-, and R' is C1-C22 hydrocarbyl.
While the present invention has been illustrated herein using the ROSO3"M+ reactant, especially alkyl sulfates (AS), the same series of reactions can be conducted using alkylethoxy sulfates (AES) of the formula R(EO)ySO3"M+, wherein R and M are as above, EO is -CH2CH2O- and y is from 1 to about 20, preferably 1 to about 5. The corresponding amines, ethoxylated amines and quaternary compounds are secured, wherein substituent R- is replaced by substituent R(EO)y- in the various compounds. Thus, the process herein provides a method for preparing these new classes of surfactant precursors and their corresponding surfactants, i.e., compounds ofthe formula:
Figure imgf000007_0001
compounds ofthe formula:
Figure imgf000007_0002
compounds ofthe formula:
Figure imgf000007_0003
compounds ofthe formula:
(iv)
Figure imgf000007_0004
wherein, in the above formulas (i) through (iv), EO is -CH2CH2O., R is C6-C22 hydrocarbyl, R' is C1-C22 hydrocarbyl, R" is C1-C5 (preferably methyl) hydrocarbyl, X is a counterion, including anions such as Cl", Br, methylsulfate, or the like, y is 1-20, preferably 1-5, with the proviso that in compounds of type (iv) y can be 0, x is 1-30 and z can be 0-30. All percentages, ratios and proportions herein are on a mole basis, unless otherwise specified. All documents cited herein are, in relevant part, incoφorated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION The overall, multi-step conventional processes which were used heretofore to prepare substituted amines typically comprise:
(a) Synthesis of fatty acids from a suitable source, e.g., saponification of coconut oil;
(b) Conversion ofthe fatty acid into an alkyl nitrile; (c) Conversion ofthe nitrile into an amine; and
(d) Conversion of the amine into substituted amines of Formula I or II.
The foregoing conventional steps (a)-(d) employ either high temperatures or multiple reactors or separation equipment or flammable metal catalysts such as Raney Ni (trademark), or use ammonia, or generate undesirable impurities, or limit the potential chain length flexibility, i. e., only natural oil based, all of which can result in processing complexity, high equipment costs and sub-optimal yields, with the net result of higher overall costs for the desired substituted amines. Other conventional processes utilize fatty alkyl halides or fatty tertiary amines which can also produce undesirable impurities and by-products. By contrast, the present process directly converts alkyl sulfates into the desired substituted amines. Importantly, various steps of the present process can use water as the reaction solvent. The sodium sulfate by-product remains in the water phase and helps "salt- out" the high purity substituted amine reaction product as a separate phase. Thus, recovery of the substituted amine reaction product is simple and inexpensive. The sodium sulfate by-product can be recovered for use in the manufacture of detergent granules. By virtue of the nature of the reactants and reaction medium (water) herein, the present process can be conducted at relatively modest pressures, thereby avoiding the need for expensive, high pressure reactors. Although typically water is used, with sufficient excess amine reactant the water may not be necessary as amine can act as solvent and reactant.
For reaction Process I, hereinafter, the following parameters summarize the optional and preferred reaction conditions herein. The reaction herein is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 100-230°C. Reaction pressures are 50-1000 psig. A base, preferably sodium hydroxide, can be used to react with the HSO4- generated during the reaction, or an excess of the amine can be employed to also react with the acid. The mole ratio of amine to alkyl sulfate is typically from 10:1 to 1:1.5; preferably from 5:1 to 1 :1.1 ; more preferably from 2:1 to 1:1. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble.
In the case of the bishydroxyethylamine of Process II, the entire reaction mixture may be dried and added to the heavy duty granular detergent product since separation of the water and organic phase may not be possible with some chain length of alkylsulfates. The process herein is preferably conducted using C12-C13 alkyl sulfate, sodium salt and N-methyl monoethanolamine. For reaction Process II, hereinafter, the following parameters summarize the optional and preferred reaction conditions herein. The reaction herein is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 140-200°C. Reaction pressures are 50-1000 psig. A base catalyst, preferably sodium hydroxide can be used. The mole ratio of reactants are 2:1 to 1 :1 amine to alkyl sulfate. In the product recovery step, the desired substituted amine is simply allowed to separate as a distinct phase from the aqueous reaction medium in which it is insoluble. The process herein is preferably conducted using C12-C13 alkyl sulfate, sodium salt. Under some circumstances the reaction Process II results in products which are sufficiently soluble in the aqueous reaction medium that gels may form. While the desired product can be recovered from the gel, an alternate, two-step synthesis Process III, hereinafter, may be more desirable in some commercial circumstances. The first step in Process III is conducted as in Process I. The second step (ethoxylation) is preferably conducted using ethylene oxide and an acid such as HCl which provides the quaternary surfactant. As shown below, chlorohydrin i.e., chloroethanol, can also be reacted to give the desired bishydroxyethyl derivative.
Process IV is conducted using ethylene oxide under standard ethoxylation conditions, without catalyst, to achieve monoethoxylation as shown below. The following illustrates the overall processes herein, wherein "EO" represents the -CH2CH2O- unit. In the processes I-III, either an inorganic base or an organic base or excess amine reactant is used to neutralize generated HSO4.
PROCESS (D
R— OSO3W H2CH2-OH + Na2S04 + H20
Figure imgf000009_0001
PROCESS (ID R— OSO3 "Na+ + H-N— [(EO)H]2 -^AL^. R-N— [(EO)H]2 + Na2SO4 + H2O
PROCESS (IIP
R— OS03 "Na+ + _>-CH2CH2-OH ► R-N-CH2CH2-OH + Na2S04 + H20
H
^ ,CH2CH2OH
R-NCH2CH2OH + CICH2CH2OH »► RNs
SCH2CH2OH PROCESS (TVX O
H ^ ,CH2CH2OH R-N-CH2CH2OH Nf^talysr R-N^
EOxH
The amines of Processes (I)-(IV) can be further ethoxylated using base catalyst and optionally quatted. Process III gives a quaternary product of the bishydroxy material with a methyl group and Cl counterion. Furthermore, the product of Process I can be ethoxylated under base catalyzed conditions to give R-N(CH3)(CH2CH2O)x-H which can be quatted with CH3C1 to give R-N(CH3)2(CH2CH2O)x-H+ Cl- or quatted with ethylene oxide and HCl to give new monoethoxylated monohydroxyethyl quaternary surfactants. While the above Processes (I), (II), (III) and (IV) are illustrated with reactants carrying the preferred EO units, propoxy, iso-propoxy, butoxy, and mixtures thereof, and mixtures with EO units, can also be used.
The following illustrates the experimental procedures, but is not intended to be limiting thereof. As discussed hereinabove, parent R- or R(EO)x-substituted mono- or bis-hydroxyethyl amine can be further alkoxylated (preferably ethoxylated using conventional ethylene oxide reactions. Following ethoxylation, the resulting amines can be quaternized using standard reactants and conditions.
Example I Preparation of N-(2-hvdroxyethylVN-methyldodecylamine (Process I) To a glass autoclave liner is added 156.15 g of sodium dodecyl sulfate
(0.5415 moles), 81.34 g of 2-(methylamino)ethanol (1.083 moles), 324.5 g of distilled H2O, and 44.3 g of 50 wt. % sodium hydroxide solution (0.5538 moles NaOH). The glass liner is sealed into 3 L, stainless steel, rocking autoclave, purged twice with 260 psig nitrogen and then heated to 160-180°C under 700-800 psig nitrogen for 3 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 1 L separatory funnel. The mixture is separated into a clear lower layer, turbid middle layer and clear upper layer. The clear upper layer is isolated and placed under full vacuum (<100 mm Hg) at 60-65°C with mixing to remove any residual water. The clear liquid turns cloudy upon removing residual water as additional salts crystallizes out. The liquid is vacuum filtered to remove salts to again obtain a clear, colorless liquid. After a few days at room temperature, additional salts crystallize and settle out. The liquid is vacuum filtered to remove solids and again a clear, colorless liquid is obtained which remains stable. The isolated clear, colorless liquid is the title product by NMR analysis and is >90% by GC analysis with a typical recovery of >90%. Example II Preparation of N.N-Bis(2-hvdroxyethvDdodecylamine (Process II) To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate (0.06921 moles), 14.55 g of diethanolamine (0.1384 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H2O. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a few minutes and then the mixture is allowed to separate. The lower chloroform layer is drained and the chloroform evaporated off to obtain product.
Example III Preparation of N.N-Bis(2-hvdroxyemvDdodecylamine (Process III) 1 Mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of base in the manner described in Example (II). The resulting 2- hydroxyethyldodecylamine is recovered and reacted with 1-chloroethanol to prepare the title compound.
Example IV Preparation of N.N-Bis(2-hydroxyethvDdodecylamine (Process IV) To a glass autoclave liner is added 19.96 g of sodium dodecyl sulfate
(0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6 g of 50 wt. % sodium hydroxide solution (0.095 moles) and 72 g of distilled H2O. The glass liner is sealed into a 500 ml, stainless steel, rocking autoclave and heated to 160-180°C under 300-400 psig nitrogen for 3-4 hours. The mixture is cooled to room temperature and the liquid contents of the glass liner are poured into a 250 ml separatory funnel along with 80 ml of chloroform. The funnel is shaken well for a Tew minutes and then allowed mixture to separate. The lower chloroform layer is drained and the chloroform is evaporated off to obtain product. The product is then reacted with 1 molar equivalent of ethylene oxide in the absence of base catalyst at 120- 130°C to produce the desired final product.
Example V
In the foregoing Examples I through IV, the sodium dodecyl sulfate is replaced by an equivalent amount of dodecyl (EO)ySO3_Na+, wherein y is in the 1-
20 (average) range. The corresponding R(EO)y_ substituted amines are secured. The following illustrates means for quaternizing substituted amines prepared herein, but is solely for purposes of illustration and not by way of limitation. The processes can also be employed to quaternize the corresponding R(EO)y-substituted amines.
Example VI Preparation of Dodecyl Dimethyl Pentaethylene glycol Ammonium Chloride To a 500 ml, 3-necked round bottom flask equipped with mechanical stirrer, thermometer and gas inlet line is added 100 g of N-(2-hydroxyethyl)-N- methyldodecylamine (0.4108 moles prepared according to process I) and 0.47 of sodium (0.0204 moles). The reaction mixture is heated to 120-130°C and mixed under ethylene oxide atmosphere until 72.37 g (1.643 moles) of ethylene oxide has been absorbed. The reaction is purged with nitrogen and 170 g of 2-propanol is added. The reaction mixture is added to glass autoclave liner, sealed liner in 3 L, stainless steel, rocking autoclave, purged once with 250 psig nitrogen, once with 50 psig methyl chloride and is charged to 65-70 psig with methyl chloride and heated to 75-80°C with mixing for 15 hours. The reaction is cooled reaction to 50°C, removed from the autoclave and 2-propanol is evaporated off to obtain product.
Example VII Preparation of Bis(2-hvdroxyethyl>) Dodecyl Methyl Ammonium Chloride To a 1 L round bottom flask equipped with magnetic stir bar, water cooled condenser and nitrogen line is added 200 g of N-(2-hydroxyethyl)-N- methyldodecyiamine (0.8216 moles prepared according to process I), 66.15 g of 2- chloroethanol (0.8216 moles) and 200 g of ethanol. The mixture is heated to reflux for 24 hours and then evaporated off ethanol to obtain product.
Example VI Preparation of Dodecyl Methyl 2-Hvdroxyethyl Pentaethylene glvcol Ammonium Chloride
To a 500 ml, 3-necked round bottom flask equipped with mechanical stirrer, thermometer and gas inlet line is added 100 g of N-(2-hydroxyethyl)-N- methyldodecylamine (0.4108 moles prepared according to Example I) and 0.47 of sodium (0.0204 moles). The reaction mixture is heated to 120-130°C and mixed under ethylene oxide atmosphere until 72.37 g (1.643 moles) of ethylene oxide is absorbed. The reaction is purged with nitrogen and 170 g of distilled H2O is added . 40.49 g of 37 wt. % HCl (0.4108 moles) is added and mixed under ethylene oxide atmosphere until 18.1 g (0.4108 moles) of ethylene oxide is absorbed. The reaction is purged with nitrogen. The reaction mixture is ready for use as an aqueous stock solution of product. The tertiary amines and/or alkoxylated tertiary amines (including R- and R(EO)y- compounds) can also be oxidized to form the corresponding amine oxide surfactants.

Claims

WHAT IS CLAIMED IS:
1. A process for preparing substituted tertiary amines ofthe formula:
Figure imgf000014_0001
by reacting an alkyl sulfate of the formula RSO3"M+ with an amine reactant of the formula:
XH2CH2OH H-N^ R' wherein in the above formulas, R is Cg-C22 hydrocarbyl, R' is C1-C22 hydrocarbyl and M is a water-solubilizing cation.
2. A process according to Claim 1 which uses water as the reaction solvent.
3. A process according to Claim 1 which uses excess amine reactant as the reaction solvent.
4. A process for preparing substituted tertiary amines ofthe formula:
XH2CH2OH R-t<
^CH2CH2OH by reacting an alkyl sulfate of the formula RSO3"M+ with an amine reactant of the formula
XH2CH2OH
H-r<
^CH2CH2OH wherein in the above formulas, R is C6-C22 hydrocarbyl and M is a water- solubilizing cation.
5. A process according to Claim 4 which uses water as the reaction solvent.
6. A process according to Claim 4 which uses excess amine reaction as the reaction solvent.
7. A process for preparing substituted tertiary amines ofthe formula:
Figure imgf000015_0001
comprising the steps of:
(a) reacting an alkyl sulfate of the formula RSO3"M+ with an amine reaction of the formula
XH2CH2OH
H— N ^ H to form a substituted secondary amine ofthe formula:
^CH2CH2OH
R— N ^ and
H
(b) reacting said substituted amine with chloroethanol, wherein, in the above formulas, R is C6-C22 hydrocarbyl and M is a water-solubilizing cation.
8. A process for preparing ethoxylated tertiary amines ofthe formula
XH2CH2OH R-t< xEOH by the uncatalyzed monoethoxylation of a substituted secondary amine prepared according to Step (a) of Claim 7, wherein EO is -CH2CH2O-, R is C6-C22 hydrocarbyl.
9. A process for preparing ethoxylated tertiary amines of the formula
R_N^CH2CH2(EO)xH
by ethoxylating a substituted tertiary amine prepared according to Claim 1 in the presence of base catalyst, wherein EO is -CH2CH2O- and x is 1-30.
10. A process for preparing ethoxylated tertiary amines ofthe formula:
R_N/CH2CH2O(EO)χH xCH2CH20(EO)χH by ethoxylating a substituted tertiary amine prepared according to Claim 4 in the presence of base catalyst, wherein EO is -CH2CH2O- and each x is independently 1- 30.
11. A process for preparing ethoxylated tertiary amines of the formula:
^CHoCH20(EO)xH R-N^ "
CH2CH20(EO)xH by ethoxylating a tertiary amine prepared according to Claim 7 in the presence of base catalyst, wherein EO is -CH2CH2O-, and each x is independently 1-30.
12. A process for preparing cationic surfactants by quaternizing the ethoxylated tertiary amine prepared according to Claim 9.
13. A process for preparing cationic surfactants by quaternizing the ethoxylated tertiary amine prepared according to Claim 10.
14. A process for preparing cationic surfactants by quaternizing the ethoxylated tertiary amine prepared according to Claim 11.
15. A process for preparing cationic surfactants by quaternizing the ethoxylated tertiary amine prepared according to Claim 9.
16. Compounds of the formula:
Figure imgf000016_0001
wherein R is Cg-C22 hydrocarbyl and x is 1-30.
17. Compounds of the formula:
Figure imgf000016_0002
wherein R is Cg-C22 hydrocarbyl, R' is Q-C22 hydrocarbyl, x is 1-30 and X" is an anion.
18. Compounds of the formula:
R „C/Eι™O)y-N χTΛBO)rfI
K. wherein R is Cg-C22 hydrocarbyl, R' is C1-C22 hydrocarbyl, y is 1-20 and x is 1- 30.
19. Compounds of the formula:
RfEOJy-NKEOJxHt X
R' wherein R is C6-C22 hydrocarbyl, R* is C1-C22 hydrocarbyl, R" is C1-C5 hydrocarbyl, y is 1-20, x is 1-30 and X" is an anion.
20. Compounds ofthe formula:
RfΕO^-NKEO^H], * R' wherein R is Cg-C22 hydrocarbyl, R' is C1-C22 hydrocarbyl, x is 1-30 and y is 1- 20.
21. Compounds of the formula:
Figure imgf000017_0001
wherein R is C6-C22 hydrocarbyl, R' is C1-C22 hydrocarbyl, y is 0-20, x is 1-30, z is 0-30 and X" is an anion.
22. Amine oxide surfactants prepared by oxidation of any of the tertiary amines herein.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6333433B1 (en) * 1998-11-09 2001-12-25 Council Of Scientific Industrial Research Process for synthesis of novel cationic amphiphiles containing N-hydroxyalkl group for intracellular delivery of biologically active molecules
FR2967899A1 (en) * 2010-11-25 2012-06-01 Oreal Composition, useful for treating, preferably dyeing and bleaching keratin fibers, comprises at least one amine compound, at least one oxidizing agent, and at least one dye comprising oxidation dye precursors, and/or direct dyes
US8247482B2 (en) * 2007-11-20 2012-08-21 Perstorp France Hydrophilic polyisocyanate compositions based on phosphate esters
US9605163B2 (en) 2011-07-28 2017-03-28 Angus Chemical Company Aminoalcohol compounds and their use as zero or low VOC additives for paints and coatings

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN106905171B (en) * 2017-03-31 2018-12-11 浙江大学 The preparation method of 2- [2- tert-butoxyethoxy]-ethamine

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1923178A (en) * 1930-03-20 1933-08-22 Ig Farbenindustrie Ag Hydroxy alkyl ethers of tertiary amines and process of preparing same
DE837532C (en) * 1950-06-25 1952-04-28 Schuelke & Mayr Ag Process for the preparation of quaternary ammonium compounds containing a carboxamide group
US2597260A (en) * 1951-02-16 1952-05-20 Armour & Co Preparation of nu-aliphatic morpholines
GB1084134A (en) * 1964-07-14 1967-09-20 Mafchon Products Ltd Novel quaternary ammonium salts, their preparation and use as surface-active agents
GB1087414A (en) * 1963-06-25 1967-10-18 Marchon Products Ltd Improvements in or relating to amine oxides as surfaceactive agents
DE2646595A1 (en) * 1976-10-15 1978-04-20 Hoechst Ag SINTERABLE FINE-PART POLYVINYL CHLORIDE MOLDS
EP0102140A1 (en) * 1982-05-12 1984-03-07 The Procter & Gamble Company Catalyzed preparation of amines from alkyl sulfates
JPS61209245A (en) * 1985-03-14 1986-09-17 Denki Kagaku Kogyo Kk Thermoplastic resin composition
US4650865A (en) * 1985-02-08 1987-03-17 Henkel Kommanditgesellschaft Auf Aktien Process for preparing tertiary ether amines
JPS6364701A (en) * 1986-09-05 1988-03-23 花王株式会社 wood preservative
JPS63227643A (en) * 1987-03-18 1988-09-21 Kao Corp Antistatic styrenic resin composition
DE3906096A1 (en) * 1989-02-27 1990-09-06 Henkel Kgaa Process for the preparation of ether amine sulphates and their use as low-foam surfactants
JPH05178731A (en) * 1991-12-27 1993-07-20 New Japan Chem Co Ltd Shampoo composition
EP0569904A2 (en) * 1992-05-11 1993-11-18 ALBRIGHT &amp; WILSON UK LIMITED Process for the preparation of carbohydrate derived surfactants and their precursors
JPH06107524A (en) * 1992-03-04 1994-04-19 New Japan Chem Co Ltd Hair treating agent composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3379763A (en) * 1964-09-01 1968-04-23 Armour & Co Preparation of primary and secondary amines from alkyl sulfates
US3378588A (en) * 1964-09-01 1968-04-16 Armour Ind Chem Co Preparation of tertiary amines from alkyl sulfates

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1923178A (en) * 1930-03-20 1933-08-22 Ig Farbenindustrie Ag Hydroxy alkyl ethers of tertiary amines and process of preparing same
DE837532C (en) * 1950-06-25 1952-04-28 Schuelke & Mayr Ag Process for the preparation of quaternary ammonium compounds containing a carboxamide group
US2597260A (en) * 1951-02-16 1952-05-20 Armour & Co Preparation of nu-aliphatic morpholines
GB1087414A (en) * 1963-06-25 1967-10-18 Marchon Products Ltd Improvements in or relating to amine oxides as surfaceactive agents
GB1084134A (en) * 1964-07-14 1967-09-20 Mafchon Products Ltd Novel quaternary ammonium salts, their preparation and use as surface-active agents
DE2646595A1 (en) * 1976-10-15 1978-04-20 Hoechst Ag SINTERABLE FINE-PART POLYVINYL CHLORIDE MOLDS
EP0102140A1 (en) * 1982-05-12 1984-03-07 The Procter & Gamble Company Catalyzed preparation of amines from alkyl sulfates
US4650865A (en) * 1985-02-08 1987-03-17 Henkel Kommanditgesellschaft Auf Aktien Process for preparing tertiary ether amines
JPS61209245A (en) * 1985-03-14 1986-09-17 Denki Kagaku Kogyo Kk Thermoplastic resin composition
JPS6364701A (en) * 1986-09-05 1988-03-23 花王株式会社 wood preservative
JPS63227643A (en) * 1987-03-18 1988-09-21 Kao Corp Antistatic styrenic resin composition
DE3906096A1 (en) * 1989-02-27 1990-09-06 Henkel Kgaa Process for the preparation of ether amine sulphates and their use as low-foam surfactants
JPH05178731A (en) * 1991-12-27 1993-07-20 New Japan Chem Co Ltd Shampoo composition
JPH06107524A (en) * 1992-03-04 1994-04-19 New Japan Chem Co Ltd Hair treating agent composition
EP0569904A2 (en) * 1992-05-11 1993-11-18 ALBRIGHT &amp; WILSON UK LIMITED Process for the preparation of carbohydrate derived surfactants and their precursors

Non-Patent Citations (16)

* Cited by examiner, † Cited by third party
Title
ABH. AKAD. WISS. DDR, ABT. MATH., NATURWISS., TECH. (1987), VOLUME DATE 1986, (1N), 589-94 *
ANTICANCER RES., vol. 8, no. 6, 1988, pages 1361 - 6 *
CHEM. ANAL. (WARSAW) (1981), 26(3), 469-75 *
CHEMICAL ABSTRACTS, vol. 101, no. 22, 26 November 1984, Columbus, Ohio, US; abstract no. 198626, IKEDA, ISAO ET AL: "Structural effects of the isomeric hydrophilic groups of surfactants on their properties. I. Monodisperse poly(oxyethylene) alkylamines" XP002035395 *
CHEMICAL ABSTRACTS, vol. 106, no. 10, 9 March 1987, Columbus, Ohio, US; abstract no. 68304, MAEDA, TETSUO: "Rubber-containing styrene polymer compositions" XP002035399 *
CHEMICAL ABSTRACTS, vol. 108, no. 11, 14 March 1988, Columbus, Ohio, US; abstract no. 94034, WEDLER, C. ET AL: "Preparation and some properties of amine oxides derived from defined ethylene oxide adducts" XP002035404 *
CHEMICAL ABSTRACTS, vol. 109, no. 15, 10 October 1988, Columbus, Ohio, US; abstract no. 124403, IWASAKI, TETSUHARU ET AL.: "Quaternary ammonium salt-containing wood preservatives" XP002035398 *
CHEMICAL ABSTRACTS, vol. 110, no. 14, 3 April 1989, Columbus, Ohio, US; abstract no. 116034, HORIBATAKE ET AL.: "Antistatic styrene resin composition" XP002035397 *
CHEMICAL ABSTRACTS, vol. 110, no. 19, 8 May 1989, Columbus, Ohio, US; abstract no. 165558, S. C. CRUMPTON ET AL.: "Novel lipid analogs with cytostatic and cytocidal activity" XP002035400 *
CHEMICAL ABSTRACTS, vol. 111, no. 10, 4 September 1989, Columbus, Ohio, US; abstract no. 86206, SZCZEPANIAK, STANISLAW ET AL: "Bath for electrodeposition of tin and tin-cadmium coatings" XP002035403 *
CHEMICAL ABSTRACTS, vol. 115, no. 12, 23 September 1991, Columbus, Ohio, US; abstract no. 118389, SZCZEPANIAK, STANISLAW: "Quaternary ammonium salt-containing pickling bath for precision steel parts" XP002035402 *
CHEMICAL ABSTRACTS, vol. 120, no. 2, 10 January 1994, Columbus, Ohio, US; abstract no. 14633, AOYANAGI, KENJI ET AL: "Shampoos containing hair-conditioning surfactants" XP002035405 *
CHEMICAL ABSTRACTS, vol. 121, no. 12, 19 September 1994, Columbus, Ohio, US; abstract no. 141214, AOYANAGI, KENJI ET AL: "Hair preparations containing cationic surfactants" XP002035401 *
CHEMICAL ABSTRACTS, vol. 97, no. 12, 20 September 1982, Columbus, Ohio, US; abstract no. 103650, SZYMANOWSKI, JAN ET AL: "Analysis of the content of the positional isomers of oxyethylated hexylamines by gas chromatography-mass spectrometry" XP002035396 *
KUO, P. L. ET AL: "Long chain N-alkyl monoaza crown ethers", J. AM. OIL CHEM. SOC. (1980), 57(7), 227-9, XP002035394 *
TENSIDE DETERG. (1984), 21(5), 252-4 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6333433B1 (en) * 1998-11-09 2001-12-25 Council Of Scientific Industrial Research Process for synthesis of novel cationic amphiphiles containing N-hydroxyalkl group for intracellular delivery of biologically active molecules
US6541649B2 (en) 1998-11-09 2003-04-01 Council Of Scientific & Industrial Research Process for synthesis of novel cationic amphiphiles containing N-hydroxyalkyl group for intracellular delivery of biologically active molecules
US8247482B2 (en) * 2007-11-20 2012-08-21 Perstorp France Hydrophilic polyisocyanate compositions based on phosphate esters
FR2967899A1 (en) * 2010-11-25 2012-06-01 Oreal Composition, useful for treating, preferably dyeing and bleaching keratin fibers, comprises at least one amine compound, at least one oxidizing agent, and at least one dye comprising oxidation dye precursors, and/or direct dyes
US9605163B2 (en) 2011-07-28 2017-03-28 Angus Chemical Company Aminoalcohol compounds and their use as zero or low VOC additives for paints and coatings

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