JP2001181242A - Method for synthesizing substituted amine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for simply and economically producing a substituted tertiary amine which is a raw material of surfactant. SOLUTION: This method for producing a substituted tertiary amine represented by formula (1) comprises (a) a step for forming a substituted secondary amine represented by formula (3) by reacting an alkylsulfate of the formula: RSO3-M+ (R is a 6-22C hydrocarbyl and M+ is a water-soluble cation) with an amine reacting agent represented by formula (2) and (b) a step for reacting the resultant substituted secondary amine represented by formula (3) with chloroethanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD BACKGROUND OF THE INVENTION The present invention relates to a process for the preparation of substituted alkylamine and the then surfactant.

CROSS REFERENCE This application claims priority from provisional patent application Ser. No. 60 / 015,584, filed Apr. 18, 1996, under 35 USC 119 (e), Code 35. are doing.

[0003] Current composition of the present invention because it possible to remove various soils and stains from diverse substrates are required, the time of formulation of laundry detergents and other cleaning compositions presents a considerable challenge. Therefore, in laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers, etc., all have the right choice of ingredients to work effectively. And a combination. Generally, such detergent compositions contain one or more types of surfactants designed to occasionally remove stains and stains. However, removing body soils, fat / oil stains and certain food stains quickly and efficiently is problematic. In fact, some surfactants and surfactant combinations perform best on certain soils and stains, but they can actually diminish performance on other soils. For example, surfactants that remove fat / oil stains from fabrics are sometimes not the best at removing particulate soils such as clay. Although the literature seems to indicate that a wide choice of surfactants and surfactant combinations can be made to detergent manufacturers, in fact, many such ingredients are found in household laundry detergents. It is a special chemical that is not suitable for low-cost products. Most of these household products, such as laundry detergents, are probably due to economic considerations and the need to formulate compositions that perform reasonably well on various soils and stains and various fabrics. The fact remains that one or more conventional ethoxylated nonionic and / or sulfated or sulfonated anionic surfactants are still mainly contained.

The literature suggests that various nitrogen-containing surfactants will be useful in various cleaning compositions.
Such materials are often designed for special uses, typically in the form of amino, amide, or quaternary ammonium or imidazolinium compounds.
For example, various amino and quaternary ammonium surfactants have been suggested for shampoo compositions and are said to impart a cosmetic effect to hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide fabric softening and antistatic effects. However,
In most cases, the commercial use of such materials is rather limited, with the nonionic and anionic surfactants remaining the primary surfactant component in current laundry compositions. Therefore, there is a need for a simple and economical method for producing raw substituted amines that can be converted to the desired N-based surfactants.

[0005] Most fatty tertiary amines are made from natural fatty acid raw materials. The present invention provides a commercial route using synthetic alcohol raw materials. The present invention provides a process for the direct synthesis of substituted amines involving the reaction of an alkyl sulfate with a mono- or bisalkoxyamine. The processes have important commercial advantages in that they can be performed in aqueous solvents at relatively mild temperatures and pressures.

[0006] U. of A.Mehreteab issued in the background August 15, the date 1995 and FJLoprest S. Patent 5,441,541 relates to anionic / cationic surfactant mixtures. 19
APMurphy, RJMSmith issued on September 3, 1980
And MPBrooks, U.S.A. K. 2,040,990 relates to ethoxylated cationic systems in laundry detergents. G
B2,266,889A and EP0569904A2
See also.

[0007]

SUMMARY OF THE INVENTION SUMMARY OF THE INVENTION The invention includes a process (I) for producing a substituted tertiary amine of the following formula.

Embedded image This process has the formula RSO ₃ ^- made by reacting M ⁺ alkyl sulfates, an amine reactant of the formula.

[0008]

Embedded image In the above formula, R is C ₆ -C ₂₂ hydrocarbyl (alkyl, alkenyl, linear or branched) and R ′ is C ₁
-C ₂₂ hydrocarbyl, wherein M is a water-soluble cation, especially sodium. Water or excess amine reactant can be used as the reaction solvent.

The present invention also includes a process (II) for producing a substituted tertiary amine of the formula

Embedded image This process has the formula RSO ₃ ^- made by reacting M ⁺ alkyl sulfates, an amine reactant of the formula.

[0010]

Embedded image In the above formula, R is C ₆ -C ₂₂ hydrocarbyl and M is a water-soluble cation. Moreover, water or excess amine reactant can be used as the reaction solvent.

The present invention also includes a process (III) for producing a substituted tertiary amine of the formula

Embedded image This process comprises the following steps (a) and (b).

[0012] (a) reacting a compound of formula _RSO ³ - and ^{M +} alkyl sulfates, by reacting with an amine reactant of the formula,

Embedded image Forming a secondary substituted amine of the formula:

Embedded image (B) reacting the substituted amine with chloroethanol. In the above formula, R is C ₆ -C ₂₂ hydrocarbyl and M is a water-soluble cation.

The present invention also includes a process (IV) for producing an ethoxylated tertiary amine of the formula

Embedded image This process consists of the uncatalyzed monoethoxylation of a substituted secondary amine prepared by step (a) of process (III) with ethylene oxide.

In the above formula, “EO” is —CH ₂ CH ₂ O—
And R is C ₆ -C ₂₂ hydrocarbyl.

The present invention also includes a process for producing an ethoxylated tertiary amine of the formula:

Embedded image This process consists in ethoxylating the substituted tertiary amine produced by process (I) in the presence of a base catalyst.

In the above formula, R and R 'are the same as those in the process (I).
In being as above, EO is _-CH 2 _CH 2 O-
And x is 1 to 30.

The present invention also includes a process for producing an ethoxylated tertiary amine of the formula:

Embedded image This process consists in ethoxylating a substituted tertiary amine prepared by process (II) in the presence of a base catalyst.

In the above formula, R is as described above for process (II), EO is -CH ₂ CH ₂ O-, and each x is independently 1-30, identical or different. You may.

The present invention also includes a process for producing an ethoxylated tertiary amine of the formula:

Embedded image This process consists in ethoxylating the tertiary amine produced by process (III) in the presence of a base catalyst.

In the above formula, R is as described above in process (III), and EO and x are each as described immediately above.

The present invention relates to the above processes (I), (II),
It also provides a process for preparing cationic surfactants by quaternizing the tertiary amines and their ethoxylates prepared according to (III) and (IV), respectively. This, for example, the ethoxylated tertiary amine reactant R "Z (R" is for example _C 1 -C ₅ (preferably methyl) _hydrocarbyl, etc. _{X-CH 2 CH 2 OH,} X is Cl, Br, Methyl sulfate, etc.).

The present invention also includes novel compounds of the formula:

Embedded image (In the above formula, x is 1 to 30, R is C ₆ -C ₂₂ , and E is
O is _-CH 2 _CH 2 O- and is), and

Embedded image (In the above formula, x is 1 to 30, R is C ₆ -C ₂₂ , and E is
O is _-CH 2 _CH 2 O-, R 'is _C 1 -C ₂₂ hydrocarbyl) A ROSO ₃ ^- M ⁺ reactive agents have been specifically described herein with reference to alkyl sulfates (AS) However, the reaction of the same system may be carried out using an alkyl ethoxy sulfate (AES) of the formula R (EO) _y SO ₃ ⁻ M ⁺ ,
Where R and M are as described above, and EO is -CH
₂ CH ₂ O—, and y is 1 to about 20, preferably 1 to
It is about 5. When the substituent R- is various compounds, the substituent R (E
The corresponding amines, ethoxylated amines and quaternary compounds are obtained which have been replaced by O) _y- . Thus, the present method provides a method for preparing these new classes of surfactant precursors and their corresponding surfactants, ie, compounds of the formula:

[0023]

Embedded image In the above formulas (i) to (iv), EO is -CH ₂ CH ₂
O- and R is C ₆ -C ₂₂ hydrocarbyl;
R ′ is C ₁ -C ₂₂ hydrocarbyl; R ″ is C ₁ -C _22.
C ₅ (preferably methyl) hydrocarbyl, X is a counter ion including anions such as Cl ⁻ , Br ⁻ , methyl sulfate, etc., and y is 1 to 20, preferably 1 to 5, provided that In the compound of type (iv), y may be 0, x is 1 to 30, and z is 0 to 30.

[0024] All percentages, ratios and proportions are on a molar basis unless otherwise indicated. All documents cited herein are, in relevant part, incorporated herein by reference.

[0025]

DETAILED DESCRIPTION OF THE INVENTION have been used so far to produce a detailed description substituted amines invention,
Conventional processes that are generally multi-step typically comprise the following (a)-(b).

(A) the synthesis of fatty acids from a suitable source, such as the coconut oil saponification, (b) the conversion of fatty acids to alkyl nitriles, (c) the conversion of nitriles to amines,
And (d) conversion of the amine to a substituted amine of formula I or II.

In the above conventional steps (a) to (d),
Use high temperatures, multiple reactors, separators or combustible metal catalysts such as Raney Ni, use ammonia, create undesirable impurities, or limit possible chain length flexibility Thus, they limit themselves to only the base natural oils, all of which lead to processing complexity, high equipment costs and sub-optimal yields, and ultimately increase the overall cost of the desired substituted amine. Other conventional processes utilize fatty alkyl halides or fatty tertiary amines, which can also produce undesirable impurities and by-products. Conversely, the process converts the alkyl sulfate directly to the desired substituted amine. Importantly, water can be used as a reaction solvent in various steps of the method. The sodium sulfate by-product remains in the aqueous phase and, as a separate phase, aids in the "salting out" of the high purity substituted amine reaction product. Therefore, the recovery of the substituted amine reaction product is simple and inexpensive. The sodium sulfate by-product can be recovered for use in making detergent granules. Thanks to the nature of the reactants and reaction medium (water), the process can be performed at relatively moderate pressures, thus avoiding the need for expensive high pressure reactors. Typically, water is used, but if there is a sufficient excess of the amine reactant, water may not be necessary because the amine can act as a solvent and reactant.

In reaction process I, the following parameters summarize optional and preferred reaction conditions. This reaction is preferably performed in an aqueous medium. Reaction temperatures typically range from 100 to 230 <0> C. Reaction pressure is 5
0-1000 psig. Base, preferably HSO ₄ sodium hydroxide produced during the reaction ^- used to react or used to react with, or excess amine and the acid. The molar ratio of amine to alkyl sulfate is typically 10: 1 to 1: 1.5, preferably 5: 1 to 1: 1.1, more preferably 2: 1 to 1: 1.
It is one. In the product recovery step, the desired substituted amine can be easily separated as a separate phase from the aqueous reaction medium in which it is insoluble.

In the case of bishydroxyethylamine of process II, the water and organic phases are not possible with certain chain length alkyl sulfates, so the entire reaction mixture is dried as a heavy duty granular detergent product. May be added. The process is preferably performed using a C ₁₂ -C ₁₃ alkyl sulfate, sodium salt and N-methyl monoethanolamine.

In reaction process II, the following parameters summarize optional and preferred reaction conditions. This reaction is preferably performed in an aqueous medium. Reaction temperatures typically range from 140 to 200 <0> C. Reaction pressure is 5
0-1000 psig. A base catalyst, preferably sodium hydroxide, can be used. The molar ratio of the reactants is 2: 1 to 1
It is a 1: 1 amine: alkyl sulfate. In the product recovery step, the desired substituted amine can be easily separated as a separate phase from the aqueous reaction medium in which it is insoluble. The process is preferably carried out using a C ₁₂ -C ₁₃ alkyl sulfate, sodium salt.

Under some circumstances, reaction process II results in a product that is sufficiently soluble in the aqueous reaction medium, where a gel may form. Although the desired product can be recovered from the gel, another two-step synthesis process III described below
Is even more desirable in some commercial settings. The first step of Process III is performed as in Process I. The second step (ethoxylation) is preferably carried out using an acid such as ethylene oxide and HCl to provide a quaternary surfactant. As described below, chlorohydrone, ie, chloroethanol, can also be reacted to obtain the desired bishydroxyethyl derivative.

Process IV is carried out using ethylene oxide under standard ethoxylation conditions without a catalyst and is monoethoxylated as described below.

The following shows the overall process, where "EO" stands for -CH ₂ CH ₂ O- unit. Process I
In to III, it is used for an inorganic or organic base or an excess amine reactant to neutralize the HSO ₄ produced.

[0034]

Embedded image

Embedded imageThe amines of processes (I) to (IV) are updated using a base catalyst.
And optionally quaternized. Process
In the case of bismuth III,
Gives a quaternary product of droxy material. In addition, the process I
The product is ethoxylated under base catalyzed conditions to give RN
(CH₃) (CH₂CH₂O)_x-H, this is C
H₃Quaternized with Cl to form RN (CH₃)₂(CH₂C
H₂O) _x-H⁺Cl⁻Give or ethylene
Novel monoethoxy quaternized with oxides and HCl
Provides silylated monohydroxyethyl quaternary surfactant.

The above processes (I), (II), (III) and (IV) have been described with respect to the reagents having a preferred EO unit, but are described as propoxy, isopropoxy, butoxy and mixtures thereof with EO units. May be used as a mixture.

[0036]

The following shows the experimental procedure, but not by way of limitation. As above, parent R- or R (EO)
_{The x} -substituted mono or bishydroxyethylamine can be further alkoxylated (preferably ethoxylated) using a conventional ethylene oxide reaction. After ethoxylation, the resulting amine can be quaternized using standard reactants and conditions.

Example I N- (2-hydroxyethyl) -N-methyldodecylua
Production of Min (Process I) 156.15 g (0.5415 mol) of sodium dodecyl sulfate was added to a glass autoclave liner.
-(Methylamino) ethanol 81.34 g (1.08
34.5 g), 324.5 g of distilled H ₂ O and 44.3 g of a 50 wt% sodium hydroxide solution (0.553 NaOH).
8 mol). Enclose the glass liner in a 3 liter stainless steel locking autoclave,
Purge twice with 260 psig nitrogen, then 700-800
Heat to 160-180 ° C under psig nitrogen for 3 hours. Allow the mixture to cool to room temperature and pour the liquid contents of the glass liner into a 1 liter separatory funnel. The mixture separates into a clear lower layer, a cloudy middle layer and a clear upper layer. The clear upper layer is isolated and placed under high vacuum (<100 mmHg) at 60-65 ° C. with mixing to remove residual water. The clear liquid becomes turbid when residual water is removed, and more salt crystallizes out. The liquid is vacuum filtered to remove the salts and a clear colorless liquid is obtained again. After several days at room temperature, the salt crystallizes further and precipitates. Vacuum filter the liquid to remove solids and again obtain a clear, colorless liquid, which remains stable. The isolated clear, colorless liquid is the title product by NMR analysis,> 90% by GC analysis, and a typical recovery> 90%.

Example II N, N-bis (2-hydroxyethyl) dodecylamine
Production (Process II) In a glass autoclave liner, 19.96 g (0.06921 mol) of sodium dodecyl sulfate, 14.55 g (0.1384 mol) of diethanolamine,
Add 72g of 50 wt% sodium hydroxide solution 7.6 g (0.095 mol) and distilled _{H 2} O. The glass liner was sealed in a 500 ml stainless steel locking autoclave and 3-4 under 300-400 psig nitrogen.
Heat to 160-180 ° C over time. The mixture was allowed to cool to room temperature and the liquid content of the glass liner was reduced to 250
Pour into 80 ml chloroform with 80 ml chloroform. The funnel is shaken well for a few minutes, after which the mixture is allowed to separate. Drain the chloroform lower layer and evaporate the chloroform to obtain the product.

Example III N, N-bis (2-hydroxyethyl) dodecylamine
Preparation (Process III) 1 mol of sodium dodecyl sulfate is converted to ethanolamine 1 in the presence of a base as described in Example (II).
React with moles. The resulting 2-hydroxyethyldodecylamine is recovered and reacted with 1-chloroethanol to give the title compound.

[0040]Example IV N, N-bis (2-hydroxyethyl) dodecylamine
Manufacturing (Process IV) Sodium dodecyl on glass autoclave liner
19.96 g (0.06921 mol) of sulfate,
Tanolamine 21.37 g (0.3460 mol), 5
7.6 g of 0 wt% sodium hydroxide solution (0.095
Le) and distilled H ₂72 g of O are added. Glass liner
-500ml stainless steel locking autoclave
Sealed in a reave and under 300-400 psig nitrogen
Heat to 160-180 ° C for 4 hours. The mixture
Allow to cool to room temperature and remove the liquid contents of the glass liner to 25
Pour into a 0 ml separatory funnel with 80 ml of chloroform.
The funnel is shaken well for a few minutes, after which the mixture is allowed to separate.
Drain the chloroform lower layer and evaporate the chloroform
To obtain the product. The product is then removed in the absence of a base catalyst.
1 mole equivalent of ethylene oxide at 120-130 ° C
In response, the desired end product is obtained.

[0041] In Example V the following examples I-IV, of sodium dodecyl sulphate significant amount of dodecyl _{^{(EO) y SO 3 - Na}} + (y 1 to 20 (average) in the range) replaced by. Corresponding R (E
O) _Y ^- substituted amines are obtained.

The following is an example of a means for quaternizing the substituted amines prepared herein, but this is for purposes of illustration only and not limitation. The method corresponding R (EO) _y ^- can also be used to quaternized substituted amines.

Example VI Dodecyldimethylpentaethylene glycol ammonium
Production of Muchloride In a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and gas introduction line, 100 g of N- (2-hydroxyethyl) -N-methyldodecylamine (0.4108 mol produced by Process I) And 0.47 (0.0204 mol) of sodium. The reaction mixture is heated to 120-130 ° C. and mixed under an ethylene oxide atmosphere until 72.37 g (1.643 mol) of ethylene oxide have been absorbed. The reaction is purged with nitrogen and 170 g of 2-propanol are added. The reaction mixture was added to a glass autoclave liner, sealed in a 3 liter stainless steel locking autoclave, purged once with 250 psig nitrogen and once with 50 psig methyl chloride, loaded with methyl chloride at 65-70 psig, and mixed for 15 hours. While heating to 75-80 ° C. The reaction is cooled to 50 ° C., removed from the autoclave and the 2-propanol is evaporated to give the product.

Example VII Bis (2-hydroxyethyl) dodecylmethyl ammonium
Preparation of Um Chloride In a 1 liter round bottom flask equipped with a magnetic stir bar, water-cooled condenser and nitrogen line, 200 g of N- (2-hydroxyethyl) -N-methyldodecylamine (0.8216 mol prepared by Process I), 66.15 g (0.8216 mol) of 2-chloroethanol and 200 g of ethanol are added. The mixture is heated at reflux for 24 hours, after which the ethanol is evaporated to give the product.

EXAMPLE VI Dodecylmethyl 2-hydroxyethylpentaethylene glycol
Production of Licol Ammonium Chloride In a 500 ml three-necked round bottom flask equipped with a mechanical stirrer, thermometer and gas introduction line, N- (2-hydroxyethyl) -N-methyldodecylamine (0.4108 mol produced according to Example I) ) 100 g and sodium 0.47 (0.0204 mol) are added. The reaction mixture is heated to 120-130 ° C and ethylene oxide 7
Mix under ethylene oxide until 2.37 g (1.643 mol) is absorbed. The reaction was purged with nitrogen, added 170g of distilled _{H 2} O. 37wt% HCl 4
Add 0.49 g (0.4108 mol) and mix under an ethylene oxide atmosphere until 18.1 g (0.4108 mol) of ethylene oxide is absorbed. The reaction is purged with nitrogen. The reaction mixture is ready to use as an aqueous stock solution of the product.

Tertiary amine and / or alkoxylation
Tertiary amines (R- and R (EO) _y-Including compounds)
Is used to form the corresponding amine oxide surfactant
Can also be oxidized.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C07B 61/00 300 C07B 61/00 300 (71) Applicant 592043805 ONE PROCTER & GANBL E PLAZA, CINCINNAT OHIO, UNITED STATES OF AMERICA

Claims (6)

[Claims] 1. A method for producing a substituted tertiary amine of the following formula: (A) Formula _RSO ³ - and ^{M +} alkyl sulfates, by reacting with an amine reactant of the formula, ## STR2 ## Forming a substituted secondary amine of the formula: and (B) reacting the substituted secondary amine with chloroethanol. (Wherein R is C ₆ -C ₂₂ hydrocarbyl;
Is a water-soluble cation) 2. A process for preparing an ethoxylated tertiary amine of the following formula by uncatalyzed monoethoxylation of a substituted secondary amine prepared according to (a) according to claim 1. Embedded image (Where EO is —CH ₂ CH ₂ O— and R is C
₆ -C ₂₂ hydrocarbyl) 3. A method for producing an ethoxylated substituted tertiary amine of the following formula by ethoxylating a substituted tertiary amine produced according to claim 1 in the presence of a base catalyst. Embedded image (Above wherein EO is _-CH 2 _CH 2 O-, each x is from 1 to 30 independently) 4. A method for producing a cationic surfactant by quaternizing the ethoxylated substituted tertiary amine produced according to claim 3. 5. A compound of the following formula: Embedded image (Wherein R is C ₆ -C ₂₂ hydrocarbyl, x
Is 1 to 30) 6. A compound of the following formula: Embedded image (Wherein R is C ₆ -C ₂₂ hydrocarbyl;
R 'is a _C 1 -C ₂₂ hydrocarbyl, x is from 1 to 30
And X ⁻ is an anion)