WO2008022062A1 - Process for preparing quaternary alkylammonium halides - Google Patents

Process for preparing quaternary alkylammonium halides Download PDF

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Publication number
WO2008022062A1
WO2008022062A1 PCT/US2007/075775 US2007075775W WO2008022062A1 WO 2008022062 A1 WO2008022062 A1 WO 2008022062A1 US 2007075775 W US2007075775 W US 2007075775W WO 2008022062 A1 WO2008022062 A1 WO 2008022062A1
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Prior art keywords
epihalohydrin
percent
alkylamine
amine
mixture
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PCT/US2007/075775
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French (fr)
Inventor
Joseph L. Deavenport
Rhonda C. Posey
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Dow Global Technologies Inc.
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Priority to AT07814019T priority Critical patent/ATE501112T1/en
Priority to MX2009001633A priority patent/MX2009001633A/en
Priority to US12/377,488 priority patent/US8217201B2/en
Priority to BRPI0714492A priority patent/BRPI0714492B1/en
Priority to EP07814019A priority patent/EP2054371B1/en
Priority to AU2007286075A priority patent/AU2007286075A1/en
Priority to DE602007013063T priority patent/DE602007013063D1/en
Priority to CA002660131A priority patent/CA2660131A1/en
Priority to JP2009524752A priority patent/JP5221538B2/en
Priority to PL07814019T priority patent/PL2054371T3/en
Publication of WO2008022062A1 publication Critical patent/WO2008022062A1/en

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/04Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02Compounds 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
    • C07C215/04Compounds 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
    • C07C215/06Compounds 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
    • C07C215/08Compounds 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 with only one hydroxy group and one amino group bound to the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere

Definitions

  • the present invention relates to high purity quaternary alkylammonium halides and methods for preparing the same.
  • the present invention concerns methods of producing alkylammonium halides of the formula (I): [(R) y -N-[CH 2 -CH(OH)-CH 2 -Z]4-y] + X "
  • alkyl as used herein is intended to include hydrocarbon-containing groups having 1 to 18 carbon atoms including linear alkyl groups, substituted alkyl groups, branched alkyl groups, and cyclic alkyl groups. Preferred alkyl groups are linear or branched.
  • Preferred alkylammonium halides of formula (I) include those wherein y is 2.
  • Preferred alkylammonium halides of formula (I) include those wherein Z is chloro.
  • Preferred alkylammonium halides of formula (I) include those wherein R is Ci-Ci 2 alkyl. More preferably, R is Ci-C 6 alkyl, even more preferably C 1 -C 3 alkyl.
  • a particularly preferred R group is methyl. While the R group at each occurrence may be the same or different, it is preferred that, when more than one R groups are present, all the R groups are the same.
  • each R group (when more than one is present ) is the same alkyl group, for example, providing a dimethylammonium-, diethylammonium-, or di- n-propylammonium compound.
  • a preffered quaternary alkylammonium compound is bis(3-chloro-2-hydroxypropyl)dialkylammonium chloride.
  • Preferred alkylammonium halides of formula (I) include those wherein X is chloride.
  • An especially preferred alkylammonium halide of formula (I) is bis(3-chloro-2- hy droxypropy l)dimethy lammonium chloride .
  • the present invention provides methods of making the alkylammonium halide of formula (I) wherein the alkylammonium halide of formula (I) is prepared by reacting an alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin.
  • the alkylamine is a mono -alkylamine or a di- alkylamine.
  • the process is suitable for any mono- or di-alkylamine and the corresponding hydrohalide, such as methylamine, dimethylamine, n-propyl-amine, di-n-propylamine, n- butylamine, di-n-butylamine, n-hexylamine, di-n-hexylamine, and other primary and secondary amines having linear, branched, or cyclic hydrocarbon groups each independently containing from 1 to 18 carbon atoms. More preferably, the process is suitable for dimethylamine and its hydrohalides, particularly its hydrochloride.
  • the mono- and di-alkylamines and their salts are commercially available, or are formed in reactions within the skill in the art such as the reaction of the corresponding free mono- or di-alkylamine with an acid, preferably a hydrohalic acid, to form the amine hydrohalide salt.
  • an acid preferably a hydrohalic acid
  • the pH of the combined alkylamine hydrohalide salt and its corresponding free amine is below about 10, preferably below about 9, and more preferably below about 8.
  • sufficient amine is admixed with or otherwise present with the amine salt, preferably hydrohalide, to reach an initial pH (before addition of epihalohydrin) of from about 7 to about 10, preferably from 7 to 9, more preferably from 7-8.
  • the corresponding free mono- or di-alkylamine is treated with an acid, more preferably with hydrochloric acid to lower the pH and form the salt. While the hydrohalide is preferred, any acid would sufficiently neutralize the base to be useful in the practice of the invention.
  • the alkylamine hydrohalide salt and its corresponding free amine are combined before addition of the epihalohydrin to form a pre -mixture.
  • the pre-mixture is admixed just prior to reaction with epihalohydrin.
  • the pre-mixture is prepared in advance or obtained commercially. If the pre- mixture is stored, it is advantageous to store the pre-mixture in a closed container to prevent free amine from escaping when the amine is volatile.
  • the pre-mixture (mono or di-alkylamine and corresponding mono- or di-alkylammonium salt, preferably formed via hydrohalide introduction) is preferably in aqueous solution, most preferably both the amine and hydrohalide are in aqueous solution.
  • the pre-mixture is substantially free of alcohol solvent. “Substantially free” means concentrations less than 0.1%, preferably less than 0.01%, or more preferably, less than 0.001%.
  • epihalohydrin is suitably used, but epichlorohydrin is the preferred epihalohydrin because it is readily available and chloride ion is considered more environmentally acceptable than other halides.
  • the amine is a monoalkylamine
  • at least about two equivalents of epihalohydrin are reacted with the pre-mixture.
  • two equivalents of epihalohydrin will provide an ammonium halide of formula (I) in which y is 2, and one R is hydrogen.
  • Three or more equivalents of epihalohydrin will provide an ammonium halide of formula (I) in which y is 1 and R is alkyl.
  • the amine is a dialkylamine
  • at least about two equivalents of epihalohydrin are reacted with the pre- mixture so that the amine is completely reacted with the epihalohydrin to form the desired product.
  • the epihalohydrin to amine plus hydrohalide mole ratio is at least 2.05 : 1 , more preferably about 3:1.
  • impurities as used herein means reaction by-products and/or starting materials other than water or solvent. More preferably, no more than about 15 wt. percent of impurities are present.
  • the invention provides bis(3-chloro-2-hydroxypropyl)dimethylammonium chloride present in an amount of at least 90 wt. percent. In other embodiments, the bis(3- chloro-2-hydroxypropyl)dimethylammonium chloride is present in an amount of at least 95 wt. percent. In still other embodiments, the bis(3-chloro-2- hydroxypropyl)dimethylammonium chloride is present in an amount of at least 97.5 wt. percent.
  • Measuring the concentrations of quaternary compounds is within the skill in the art, for instance, by liquid chromatography of an aqueous solution of alkylammonium halide product.
  • Such liquid, preferably paired-ion chromatography is suitably conducted on a system such as the Waters Liquid Chromatograph System commercially available from Millipore, Waters, Chromatography Division.
  • a system such as the Waters Liquid Chromatograph System commercially available from Millipore, Waters, Chromatography Division.
  • Such a system has a pump, sample injection system, radial column compression system, and a refractive index detector. Suitable columns include, for instance, C-18 reverse-phase columns.
  • a paired-ion chromatography reagent such as that prepared from 3.98 g (grams) of 1-octane sulfonic acid, 143 g sodium perchlorate, 132 g methanol and 1750 g high purity water, filtered through e.g. 0.45 micron paper and degassed 15 minutes under vacuum is suitably used as chromatographic solvent, and a solution such as 5 percent methanol in water (similarly filtered and degassed) is suitably used to flush the column prior to periods of inactivity.
  • solution concentrations are optionally optimized for some liquid chromatography columns. Determining chromatograph parameters is within the skill in the art, but for the suggested system, suitable combinations include a pump flow rate of 0.8 mL/min.
  • the chromatograph system is preferably used with an integrator, such as that commercially available from Hewlett-Packard and designated as Model 3393.
  • the system is preferably purged with the paired-ion chromatography reagent at least until a flat baseline is obtained. Then a weighed sample is introduced into the system, e.g. using a syringe and sample injection valve. Peaks areas are obtained using the system and an integrator. This procedure is within the skill in the art.
  • epihalohydrin is added to the pre-mixture.
  • the epihalohydrin, aqueous free amine, and amine hydrohalide are added simultaneously to form the desired product.
  • the temperature is advantageously sufficient to result in a desired reaction rate, conveniently to have the reaction proceed with minimal build-up of reactants and a slow exotherm, but slow enough to avoid appreciable diquaternary compound and dihaloalcohol by-product formation.
  • appreciable is meant less than 1 weight percent diquaternary compound based upon the weight of the desired product plus diquaternary compound, and less than 10 weight percent dihaloalcohol by-product based upon the weight of the desired product plus dihaloalcohol.
  • the temperature of addition is preferably from about 0 0 C to about 25 0 C, more preferably from about 5 0 C to about 20 0 C, most preferably from about 10 0 C to about 15 0 C.
  • the epihalohydrin is preferably added to the pre-mixture over a period of time rather than all at once to avoid an exotherm which is difficult to control and leads to high levels of aqueous and organic by-products. Conveniently, it is added over a period of from about 1 to about 4 hours.
  • the process is continuous and comprises adding the epihalohydrin and pre-mixture in a continuous fashion.
  • the continuous process advantageously has a short residence time in a mixer with a longer residence time in a reactor.
  • a batch process advantageously has the epihalohydrin added slowly to the pre-mixture with continual mixing during and after the addition.
  • the epihalohydrin, amine, and amine hydrohalide mixture are preferably digested for a period of time sufficient to permit the product to form.
  • digest time refers to the time after addition of epihalohydrin is complete during which additional reaction takes.
  • the digest time is preferably about 1-20 hours at about 10-50 0 C. More preferably, the reaction is digested for 1-15 hours at about 10 0 C and then about 1-3 hours at about 50 0 C. Even more preferably, the reaction is digested for about 1 hour at about 10 0 C and then about 1 hour at about 50 0 C. Following the digest time, the pH is lowered to about 1 to about 3.
  • hydrochloric acid is used to lower the pH and stop the reaction.
  • Some by-products are unavoidably produced and are optionally reacted suitably before, after, or when possible during the process of the invention.
  • epoxy by-product can optionally be hydrochlorinated with hydrochloric acid.
  • the epihalohydrin is removed by any means within the skill in the art such as by organic solvent extraction or steam distillation.
  • Other by-products such as l,3-dichloro-2-propanol, are also removed. Removal is suitably performed by any method within the skill in the art, but preferably by solvent extraction, such as with methylene chloride.
  • solvent extraction such as with methylene chloride.
  • the reaction solution is extracted six times with a 2:1 weight ratio of a halogenated solvent, such as methylene chloride.
  • Methylene chloride can then be removed by methods known in the art, such as sparging with nitrogen.
  • the product preferably comprises no more than about 20 wt. percent, preferably no more than about 15 wt. percent, even more preferably no more than 10 wt. percent, of impurities.
  • Example 1 253.24 mL of 40 wt % aqueous dimethylamine (2.00 mol) was added to a 1 L jacketed round bottom flask equipped with a condenser, addition funnel, and pH probe. The pH was decreased to 9 using 195.73 g (1.99 mol) concentrated HCl. 470.34 mL of epichlorohydrin (6.00 mol) was added to the dimethylamine hydrochloride solution over a two hour period at a temperature between 15-20 0 C. The reaction solution was stirred for an additional 16 hours at 15 0 C.
  • HPLC chromatograms show a doublet peak for both the chlorohydrin and epoxide forms of the product due to the molecule having two chiral carbon atoms.
  • HPLC analysis showed a purity of 91.7 %, with 8.3 % impurities.
  • the solution was extracted with methylene chloride using a 2:1 weight ratio seven times to remove the l,3-dichloro-2-propanol that was generated from the excess epichlorohydrin. The solution was then sparged with nitrogen to remove the residual methylene chloride from the solution. HPLC analysis showed a purity of 97.4%.
  • the present invention includes reacting a mono or di alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin.
  • the combination of mono or di alkylamine hydrohalide salt and its corresponding free amine yields a much purer product, as shown in Examples 1 and 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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Abstract

Alkylammonium halides of the formula are described wherein the alkylammonium halide is prepared by reacting an alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin.

Description

PROCESS FOR PREPARING QUATERNARY ALKYLAMMONIUM HALIDES
Field
The present invention relates to high purity quaternary alkylammonium halides and methods for preparing the same.
Background Quaternary alkylammonium compounds have a variety of commercial applications, including in the textile industry and the personal care industry. In many of these applications, it is desirable to provide the quaternary alkylammonium compound in a high purity form. Conventional compositions either possess undesirable amounts of impurities or require concentration or purification steps that increase production costs. Consequently, processes for preparing compositions having higher concentrations of the quaternary alkylammonium halide and reduced levels of impurities are much needed and would be very useful.
Summary The invention provides alkylammonium halides of the formula (I):
[(R)y-N-[CH2-CH(OH)-CH2-Z]4-y]+ X~
(I) wherein y is 1 or 2; Z is halogen; X" is halide; and R at each occurrence is independently H or C1-C18 alkyl, provided that at least one R is C1-C18 alkyl, and wherein the alkylammonium halide is prepared by reacting an alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin. Detailed Description
The present invention concerns methods of producing alkylammonium halides of the formula (I): [(R)y-N-[CH2-CH(OH)-CH2-Z]4-y]+ X"
(I) wherein y is 1 or 2, Z is halogen, X" is halide, and R at each occurrence is independently H or C1-C18 alkyl, provided that at least one R is C1-C18 alkyl.
The term "alkyl" as used herein is intended to include hydrocarbon-containing groups having 1 to 18 carbon atoms including linear alkyl groups, substituted alkyl groups, branched alkyl groups, and cyclic alkyl groups. Preferred alkyl groups are linear or branched.
Preferred alkylammonium halides of formula (I) include those wherein y is 2.
Preferred alkylammonium halides of formula (I) include those wherein Z is chloro. Preferred alkylammonium halides of formula (I) include those wherein R is Ci-Ci2 alkyl. More preferably, R is Ci-C6 alkyl, even more preferably C1-C3 alkyl. A particularly preferred R group is methyl. While the R group at each occurrence may be the same or different, it is preferred that, when more than one R groups are present, all the R groups are the same. While some embodiments include any combination of alkyl groups as the R groups, in particular embodiments each R group (when more than one is present ) is the same alkyl group, for example, providing a dimethylammonium-, diethylammonium-, or di- n-propylammonium compound. A preffered quaternary alkylammonium compound is bis(3-chloro-2-hydroxypropyl)dialkylammonium chloride.
Preferred alkylammonium halides of formula (I) include those wherein X is chloride.
An especially preferred alkylammonium halide of formula (I) is bis(3-chloro-2- hy droxypropy l)dimethy lammonium chloride .
In one embodiment, the present invention provides methods of making the alkylammonium halide of formula (I) wherein the alkylammonium halide of formula (I) is prepared by reacting an alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin.
It should be understood that the alkylamine is a mono -alkylamine or a di- alkylamine. The process is suitable for any mono- or di-alkylamine and the corresponding hydrohalide, such as methylamine, dimethylamine, n-propyl-amine, di-n-propylamine, n- butylamine, di-n-butylamine, n-hexylamine, di-n-hexylamine, and other primary and secondary amines having linear, branched, or cyclic hydrocarbon groups each independently containing from 1 to 18 carbon atoms. More preferably, the process is suitable for dimethylamine and its hydrohalides, particularly its hydrochloride.
The mono- and di-alkylamines and their salts are commercially available, or are formed in reactions within the skill in the art such as the reaction of the corresponding free mono- or di-alkylamine with an acid, preferably a hydrohalic acid, to form the amine hydrohalide salt. Alternatively, one could start with the salt and add free amine (or a strong base to form the free amine from the salt). Any means within the skill in the art for forming mixtures of the free amine and its salt in the preferred pH ranges is suitable.
The pH of the combined alkylamine hydrohalide salt and its corresponding free amine is below about 10, preferably below about 9, and more preferably below about 8. In one embodiment, sufficient amine is admixed with or otherwise present with the amine salt, preferably hydrohalide, to reach an initial pH (before addition of epihalohydrin) of from about 7 to about 10, preferably from 7 to 9, more preferably from 7-8.
In a preferred embodiment, the corresponding free mono- or di-alkylamine is treated with an acid, more preferably with hydrochloric acid to lower the pH and form the salt. While the hydrohalide is preferred, any acid would sufficiently neutralize the base to be useful in the practice of the invention.
In one embodiment, the alkylamine hydrohalide salt and its corresponding free amine are combined before addition of the epihalohydrin to form a pre -mixture. In one embodiment, the pre-mixture is admixed just prior to reaction with epihalohydrin. Alternatively, the pre-mixture is prepared in advance or obtained commercially. If the pre- mixture is stored, it is advantageous to store the pre-mixture in a closed container to prevent free amine from escaping when the amine is volatile.
In a preferred embodiment, the pre-mixture (mono or di-alkylamine and corresponding mono- or di-alkylammonium salt, preferably formed via hydrohalide introduction) is preferably in aqueous solution, most preferably both the amine and hydrohalide are in aqueous solution. In one embodiment, the pre-mixture is substantially free of alcohol solvent. "Substantially free" means concentrations less than 0.1%, preferably less than 0.01%, or more preferably, less than 0.001%.
Any epihalohydrin is suitably used, but epichlorohydrin is the preferred epihalohydrin because it is readily available and chloride ion is considered more environmentally acceptable than other halides. When the amine is a monoalkylamine, at least about two equivalents of epihalohydrin are reacted with the pre-mixture. In particular, two equivalents of epihalohydrin will provide an ammonium halide of formula (I) in which y is 2, and one R is hydrogen. Three or more equivalents of epihalohydrin will provide an ammonium halide of formula (I) in which y is 1 and R is alkyl. When the amine is a dialkylamine, at least about two equivalents of epihalohydrin are reacted with the pre- mixture so that the amine is completely reacted with the epihalohydrin to form the desired product. Preferably, the epihalohydrin to amine plus hydrohalide mole ratio is at least 2.05 : 1 , more preferably about 3:1. Surprisingly, it has been found that the process, without additional steps, affords compounds with no more than about 20 wt. percent of impurities after extraction. The term "impurities" as used herein means reaction by-products and/or starting materials other than water or solvent. More preferably, no more than about 15 wt. percent of impurities are present. Even more preferably, no more than about 10 wt. percent of impurities are present. Other preferred embodiments have lower concentrations of impurity, such as 7.5 wt. percent, 5 wt. percent, 4 wt. percent, 3 wt. percent, 2 wt. percent, or 1 wt. percent. In one embodiment, the invention provides bis(3-chloro-2-hydroxypropyl)dimethylammonium chloride present in an amount of at least 90 wt. percent. In other embodiments, the bis(3- chloro-2-hydroxypropyl)dimethylammonium chloride is present in an amount of at least 95 wt. percent. In still other embodiments, the bis(3-chloro-2- hydroxypropyl)dimethylammonium chloride is present in an amount of at least 97.5 wt. percent.
Measuring the concentrations of quaternary compounds is within the skill in the art, for instance, by liquid chromatography of an aqueous solution of alkylammonium halide product. Such liquid, preferably paired-ion chromatography is suitably conducted on a system such as the Waters Liquid Chromatograph System commercially available from Millipore, Waters, Chromatography Division. Such a system has a pump, sample injection system, radial column compression system, and a refractive index detector. Suitable columns include, for instance, C-18 reverse-phase columns. A paired-ion chromatography reagent such as that prepared from 3.98 g (grams) of 1-octane sulfonic acid, 143 g sodium perchlorate, 132 g methanol and 1750 g high purity water, filtered through e.g. 0.45 micron paper and degassed 15 minutes under vacuum is suitably used as chromatographic solvent, and a solution such as 5 percent methanol in water (similarly filtered and degassed) is suitably used to flush the column prior to periods of inactivity. These solution concentrations are optionally optimized for some liquid chromatography columns. Determining chromatograph parameters is within the skill in the art, but for the suggested system, suitable combinations include a pump flow rate of 0.8 mL/min. and using a detector having an internal temperature of 400C. The chromatograph system is preferably used with an integrator, such as that commercially available from Hewlett-Packard and designated as Model 3393. The system is preferably purged with the paired-ion chromatography reagent at least until a flat baseline is obtained. Then a weighed sample is introduced into the system, e.g. using a syringe and sample injection valve. Peaks areas are obtained using the system and an integrator. This procedure is within the skill in the art. Advantageously, epihalohydrin is added to the pre-mixture. Alternatively, the epihalohydrin, aqueous free amine, and amine hydrohalide are added simultaneously to form the desired product. When the epihalohydrin is added, the temperature is advantageously sufficient to result in a desired reaction rate, conveniently to have the reaction proceed with minimal build-up of reactants and a slow exotherm, but slow enough to avoid appreciable diquaternary compound and dihaloalcohol by-product formation. By appreciable is meant less than 1 weight percent diquaternary compound based upon the weight of the desired product plus diquaternary compound, and less than 10 weight percent dihaloalcohol by-product based upon the weight of the desired product plus dihaloalcohol. The temperature of addition is preferably from about 0 0C to about 25 0C, more preferably from about 5 0C to about 20 0C, most preferably from about 10 0C to about 15 0C.
The epihalohydrin is preferably added to the pre-mixture over a period of time rather than all at once to avoid an exotherm which is difficult to control and leads to high levels of aqueous and organic by-products. Conveniently, it is added over a period of from about 1 to about 4 hours. Alternatively, the process is continuous and comprises adding the epihalohydrin and pre-mixture in a continuous fashion. The continuous process advantageously has a short residence time in a mixer with a longer residence time in a reactor. A batch process advantageously has the epihalohydrin added slowly to the pre-mixture with continual mixing during and after the addition. Following addition of the epihalohydrin, the epihalohydrin, amine, and amine hydrohalide mixture are preferably digested for a period of time sufficient to permit the product to form. As used herein, "digest time" refers to the time after addition of epihalohydrin is complete during which additional reaction takes. The digest time is preferably about 1-20 hours at about 10-50 0C. More preferably, the reaction is digested for 1-15 hours at about 10 0C and then about 1-3 hours at about 50 0C. Even more preferably, the reaction is digested for about 1 hour at about 10 0C and then about 1 hour at about 50 0C. Following the digest time, the pH is lowered to about 1 to about 3. Preferably, hydrochloric acid is used to lower the pH and stop the reaction. Some by-products are unavoidably produced and are optionally reacted suitably before, after, or when possible during the process of the invention. For instance, epoxy by-product can optionally be hydrochlorinated with hydrochloric acid.
After the digest time is completed, the epihalohydrin is removed by any means within the skill in the art such as by organic solvent extraction or steam distillation. Other by-products, such as l,3-dichloro-2-propanol, are also removed. Removal is suitably performed by any method within the skill in the art, but preferably by solvent extraction, such as with methylene chloride. For instance, in a preferred embodiment, the reaction solution is extracted six times with a 2:1 weight ratio of a halogenated solvent, such as methylene chloride. Methylene chloride can then be removed by methods known in the art, such as sparging with nitrogen.
Following removal of the methylene chloride, and without further purification, the product preferably comprises no more than about 20 wt. percent, preferably no more than about 15 wt. percent, even more preferably no more than 10 wt. percent, of impurities.
The following examples are presented to illustrate the invention and are not to be interpreted as limiting it. All percentages, parts and ratios are by weight unless otherwise stated.
Examples
Example 1 253.24 mL of 40 wt % aqueous dimethylamine (2.00 mol) was added to a 1 L jacketed round bottom flask equipped with a condenser, addition funnel, and pH probe. The pH was decreased to 9 using 195.73 g (1.99 mol) concentrated HCl. 470.34 mL of epichlorohydrin (6.00 mol) was added to the dimethylamine hydrochloride solution over a two hour period at a temperature between 15-20 0C. The reaction solution was stirred for an additional 16 hours at 15 0C. the solution was extracted with methylene chloride using a 2:1 weight ratio six times to remove the l,3-dichloro-2-propanol that was generated from the excess epichlorohydrin. The solution was then sparged with nitrogen to remove the residual methylene chloride from the solution. 13C NMR spectra and HPLC analysis showed the presence of the epoxide form of the desired product. The reaction solution was brought to pH 2 and the temperature increased to 70 0C for one hour to hydrochlorinate the residual epoxide. 13C NMR spectra and HPLC analysis after the hydrochorination showed very small amounts of the epoxide form. The HPLC chromatograms show a doublet peak for both the chlorohydrin and epoxide forms of the product due to the molecule having two chiral carbon atoms. HPLC analysis showed a purity of 91.7 %, with 8.3 % impurities.
Example 2
84 mL of 40 wt % aqueous dimethylamine (0.67 mol) was added to a 1 L jacketed round bottom flask equipped with a condenser, addition funnel, and pH probe. The pH was decreased to 7.29 using 63.51 g (0.64 mol) concentrated HCl. 157 mL of epichlorohydrin (2.00 mol) was added to the dimethylamine hydrochloride solution over a 1.25 hour period at a temperature between 10-15 0C. The reaction solution was stirred for an additional 1 hour at 15 0C. The temperature was increased to 40 0C and maintained for 1.5 hours. The reaction solution was brought to pH 2 using concentrated hydrochloric acid and the temperature increased to 70 0C for one hour. The solution was extracted with methylene chloride using a 2:1 weight ratio seven times to remove the l,3-dichloro-2-propanol that was generated from the excess epichlorohydrin. The solution was then sparged with nitrogen to remove the residual methylene chloride from the solution. HPLC analysis showed a purity of 97.4%.
Example 3 (Comparative)
8.2 g of dimethylamine hydrochloride were added to 70 mL of ethanol. 20.4 g of epichlorohydrin (2.20:1.00 mole ratio of epi:amine hydrochloride) was slowly added to the dimethylamine hydrochloride/ethanol solution. No free amine was present per this comparative example.
The reaction was allowed to proceed at room temperature for 36 hours whereupon the solvent and residual epichlorohydrin were evaporated from the reaction solution. The resulting viscous liquid was analyzed by 13C NMR and High Performance Liquid Chromatography (procedure described above). The purity of the resulting product was as follows: Table 1
Figure imgf000009_0001
Using the hydrochloride salt alone under these conditions formed a high amount of dichloropropanol.
In contrast, the present invention includes reacting a mono or di alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin. The combination of mono or di alkylamine hydrohalide salt and its corresponding free amine yields a much purer product, as shown in Examples 1 and 2.
The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.

Claims

Claims:
1. A process for making an alkylammonium halide of the formula (I):
[(R)y-N-[CH2-CH(OH)-CH2-Z]4-y]+ X-
(I) wherein y is 1 or 2;
Z is halogen; X- is halide; and
R, at each occurrence, is independently H or Ci -Ci 8 alkyl, provided that at least one
Figure imgf000010_0001
the process comprising: reacting a mono or di alkylamine hydrohalide salt and its corresponding free amine with at least two equivalents of an epihalohydrin.
2. The process of claim 1, further comprising combining the alkylamine hydrohalide salt and its corresponding free amine previous to combination with the epihalohydrin.
3. The process of claim 2, further comprising combining the alkylamine hydrohalide salt and its corresponding free amine in a proportion to achieve a pH less than about 10 in the resulting pre-mixture.
4. The process of claim 2, further comprising combining the alkylamine hydrohalide salt and its corresponding free amine in a proportion to achieve a pH less than about 9 in the resulting pre-mixture.
5. The process of claim 2, further comprising combining the alkylamine hydrohalide salt and its corresponding free amine in a proportion to achieve a pH less than about 8 in the resulting pre-mixture.
6. The process of claim 3, 4, or 5, wherein the pre-mixture is substantially free of alcohol solvent.
7. The process of claim 1 , wherein y is 2.
8. The process of claim 1 , wherein R is unsubstituted C 1 -C3 alkyl.
9. The process of claim 1, wherein the alkylamine is a dialkylamine.
10. The process of claim 1 , wherein the alkylammonium halide of formula (I) is bis(3- chloro-2-hydroxypropyl)dimethylammonium chloride.
11. The process of claim 1 , wherein the epihalohydrin is epicholorhydrin.
12. The process of claim 1, wherein the epihalohydrin to amine plus hydrohalide mole ratio is at least 2.05 : 1.
13. The process of claim 1, wherein the epihalohydrin to amine plus hydrohalide mole ratio is about 3:1.
14. The process of claim 1, further comprising extracting alkylammonium halide of the formula (I) with a halogenated solvent.
15. The process of claim 14, wherein the product of the process comprises no more than about 20 wt. percent of impurities.
16. The process of claim 14, wherein the product of the process comprises no more than about 15 wt. percent of impurities.
17. The process of claim 14, wherein the product of the process comprises no more than about 10 wt. percent, of impurities.
18. The process of claim 14, wherein wherein the product of the process comprises no more than about 4 wt. percent of impurities.
PCT/US2007/075775 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides WO2008022062A1 (en)

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AT07814019T ATE501112T1 (en) 2006-08-15 2007-08-13 METHOD FOR PRODUCING QUATERNARY ALKYLAMMONIUM HALIDES
MX2009001633A MX2009001633A (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides.
US12/377,488 US8217201B2 (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkammonium halides
BRPI0714492A BRPI0714492B1 (en) 2006-08-15 2007-08-13 process for preparing an alkylammonium halide
EP07814019A EP2054371B1 (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides
AU2007286075A AU2007286075A1 (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides
DE602007013063T DE602007013063D1 (en) 2006-08-15 2007-08-13 PROCESS FOR PREPARING QUATERNAR ALKYLAMMONIUM HALIDE
CA002660131A CA2660131A1 (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides
JP2009524752A JP5221538B2 (en) 2006-08-15 2007-08-13 Production method of quaternary alkylammonium halides
PL07814019T PL2054371T3 (en) 2006-08-15 2007-08-13 Process for preparing quaternary alkylammonium halides

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1507406A (en) * 1975-04-14 1978-04-12 Buckman Labor Inc Cationic polyamines
GB2090877A (en) * 1981-01-10 1982-07-21 Sandoz Ltd Improvements in or relating to organic compounds

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4054542A (en) * 1975-04-14 1977-10-18 Buckman Laboratories, Inc. Amine-epichlorohydrin polymeric compositions
DE3136628A1 (en) * 1981-09-15 1983-03-31 Henkel KGaA, 4000 Düsseldorf "METHOD FOR PRODUCING QUARTERA AMMONIUM COMPOUNDS"
US4764306A (en) * 1984-12-03 1988-08-16 Ppg Industries, Inc. Process for the manufacture of bis-quaternary ammonium compounds
US4812263A (en) * 1986-08-22 1989-03-14 Ppg Industries, Inc. Bis-quaternary ammonium compounds
US5463127A (en) * 1995-01-17 1995-10-31 The Dow Chemical Company Process for preparation of halohydroxypropyl-trialkylammonium halides
US7214806B2 (en) * 2004-03-05 2007-05-08 Sachem, Inc. Synthetic multiple quaternary ammonium salts

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1507406A (en) * 1975-04-14 1978-04-12 Buckman Labor Inc Cationic polyamines
GB2090877A (en) * 1981-01-10 1982-07-21 Sandoz Ltd Improvements in or relating to organic compounds

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CHLEBICKI J ET AL: "PREPARATION, SURFACE-ACTIVE PROPERTIES, AND ANTIMICROBIAL ACTIVETIES OF BIS-QUATERNARY AMMONIUM SALTS FROM AMINES AND EPICHLOROHYDRIN", JOURNAL OF SURFACTANTS AND DETERGENTS, AOCS PRESS, CHAMPAIGN, IL, US, vol. 8, no. 3, July 2005 (2005-07-01), pages 227 - 232, XP001233095, ISSN: 0024-4201 *
J. B. MCKELVEY ET AL: "Reaction of epichlorohydrin with cyclohexylamine", JOURNAL OF ORGANIC CHEMISTRY., vol. 24, 1959, USAMERICAN CHEMICAL SOCIETY, WASHINGTON, DC., pages 614 - 616, XP002461494 *
T.-S. KIM ET AL: "Preparation and properties of multiple ammonium salts quaternized by epichlorohydrin", LANGMUIR., vol. 12, no. 26, 1996, USAMERICAN CHEMICAL SOCIETY, NEW YORK, NY., pages 6304 - 6308, XP002461493 *
WEGRZYNSKA H ET AL: "PREPARATION, SURFACE-ACTIVE AND ANTIELECTROSTATIC PROPERTIES OF MULTIPLE QUARTERNARY AMMONIUM SALTS", JOURNAL OF SURFACTANTS AND DETERGENTS, AOCS PRESS, CHAMPAIGN, IL, US, vol. 9, no. 3, 2006, pages 221 - 226, XP001245893, ISSN: 0024-4201 *

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