Classifications

• • 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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• 1997
  • 1997-04-16 EP EP97920413A patent/EP0898560A1/de not_active Ceased
  • 1997-04-16 JP JP9537347A patent/JPH11507953A/ja active Pending
  • 1997-04-16 CA CA002251847A patent/CA2251847A1/en not_active Abandoned
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• 2000
  • 2000-11-09 JP JP2000342421A patent/JP2001181242A/ja active Pending
• 2001
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