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
  • C07C213/10—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/82—Purification; Separation; Stabilisation; Use of additives
  • C07C209/84—Purification
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/82—Purification; Separation; Stabilisation; Use of additives
  • C07C209/86—Separation
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/03—Monoamines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/03—Monoamines
  • C07C211/08—Monoamines containing alkyl groups having a different number of carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/09—Diamines
  • C07C211/10—Diaminoethanes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
  • C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C211/14—Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines

Definitions

• This invention relates to a process for refining amines. More precisely, it relates to a process comprising refining aliphatic amines by treating them with herohydride compounds, and thereby preventing colorization of amine salts, quaternary ammonium salts or aminebetaine derived from the refined amines.
• Long-chain alkyl amines are widely used as cationic surfactants and as ampholytic surfactants such as amine salts, quaternary ammonium salts, or alkyl betaine, or they are converted to known useful long-chain alkylamine oxides.
• the products are undesirably colored yellow or pale red. Colorization is marked when the surfactants are derived from long-chain alkyl amines obtained from ethylene low polymers or derived from alkylamine mixtures containing said long-chain alkylamines as a constituent, and the commercial value of the products are reduced greatly.
• the present invention provides an improved process for refining aliphatic amines by treating said amines with hydrogenated boron compounds.
• the invention is a method of refining aliphatic hydrocarbon amines having at least one alkyl group of 9 to 22 carbon atoms attached to the amino nitrogen, said amines being derived from polymerized ethylene by known methods and having a tendency to form colored amine salts, which comprises suppressing said tendency "by reacting said aliphatic amine with 0.01 to 5% by weight based on the amine of a borohydride compound selected from the group consisting of an alkali metal borohydride, amine borohydrides, quaternary ammonium borohydrides and mixtures thereof, and recovering refined aliphatic amine from the reaction mixture.
• the amine material to which the refining process of the invention can be applied are generally aliphatic primary, secondary and tertiary amines, and mixtures of such amines.
• the amines have the formulas RNH RRNH and RRR"N, wherein R is alkyl havingifrom 9 the amine material is a mixture of primary, secondary or tertiary amines in which R has various values within the range of carbon atom number for R set forth above.
• the amine material can be a mixture of primary and/or secondary and/or tertiary amines.
• amine materials with which the process of the invention is particularly effective there are enumerated amine materials derived from ethylene low polymers such as a-olefins and Ziegler alcohols or amine mixtures containing said amines as a constituent. These amine materials derived from ethylene low polymers have the tendency of forming undesired color substances when converted to aminesalts, quaternary ammonium salts and/or betaines, apparently owing to a minor amount of impurities therein. Examples of such amines and their preparation are described in (l) M. T. Atwood, .IAOCS. 40, 64 (1963); (2) T. Clarke et al., .IAOCS. 41, 78 (1964); (3) Onyx Corp. U.S. Pat. No. 3,471,562 (Oct. 7, 1969); and (4) Sun Chemical Corp. U.S. Pat. No. 3,401,203 (Sept. 10, 1968).
• boron hydride there can be employed an alkali metal salt of boron hydride such as sodium borohydride, potassium borohydride and lithium borohydride, an amine salt of boron hydride, a quaternaryammonium salt of boron hydride and mixtures thereof.
• the boron hydrides can be added in the form of dry powder or in alkaline aqueous solution.
• the amount of boron hydride to be added is dependent on the kind of amine to be treated, the process by which it was manufactured, and its properties.
• the amount of boron hydride used should be kept as low as possible in order to minimize expense, but the use of an excess amount of boron hydride does not cause any adverse effect.
• the boron hydride compound is added in an amount from about 0.01 to about 5% by weight, based on the weight of the starting amine material, preferably from 0.05 to 2% by weight.
• the alkali is preferably water-soluble and is added in an amount up to 50%, preferably in the range of 0.1 to 10%, based on the weight of the starting amine materials.
• the alkali it is preferred to use sodium hydroxide, potassium hydroxide and sodium carbonate. The amount thereof to be added is not critical.
• the boron hydride compound is effective even if no alkali at all is added.
• the preferred mode of performance of this invention consists of treating the starting amine material with boron hydride compound in an amount of from about 0.01 to about 5% by weight, based on the weight of the amine, in the presence of an alkali.
• a specific preferred process according to this invention comprises placing the starting amine material, boron hydride compound and an aqueous solution of caustic alkali in a reactor, and agitating the mixture for several (about 2 to about 10) hours at about 50 to C. It will be understood, however, that the treating temperature and the treating time are not critical.
• the present invention is carried out usually in a homogeneous or non-homogeneous phase of amine and water, but if necessary, alcohol such as methanol, ethano] or isopropanol can be added.
• the presence of inorganic salts in the starting amine material does not inhibit the desired effect of the boron hydride compound. Therefore, it is possible to employ as a starting amine material, a tertiary amine produced by reaction of an alkyl halide and a primary or secondary amine in the presence of an excess of alkali, followed by treatment of the resultant tertiary amine in place as it is, not isolated, with the boron hydride compound. This is an effective and simple process.
• the amine treated according to the process of this invention When the amine treated according to the process of this invention is isolated and converted to an amine salt, quaternary ammonium salt or amine betaine, by a known process, there is obtained a practically colorless product. Thus the colorization that occurs when an untreated product is similarly converted, is avoided by treating the amine material by the process of this invention.
• the amine material treated according to the process of this invention and the above-described compounds obtained from that amine material are quite similar to the corresponding products obtained from untreated amine material in the features, of chemical analysis, physical properties and chemical activity, but they are remarkably free of colorization.
• the treated and untreated tertiary amines were each i.
• EXAMPLE 2 The same conditions as in Example 1 were employed except that the amount of sodium borohydride was re- I quizd to 100 mg.
• the lauryl dimethylamine hydrochloride obtained by a conventional process as in Example l was, colorless and had a percent transmission of 93.6%. (The percent transmission was determined by the method used in Example 1. This applies also in the following examples.)
• EXAMPLE 3 The same conditions as in Example 1 were employed except that there was used 550mg. of potassium borohydride instead of sodium borohydride.
• the hydrochloride obtained by a conventional process as in Example 1 was colorless and had a percent transmission of 93.8%.
• lauryl benzyl dimethylammonium chorides were prepared by a conventional process.
• the chloride derived from the amine treated with sodium borohydride was colorless
• lauryl dimethylamine was prepared in the presence of an excess of caustic soda by a conventional process. 112 mg. of sodium borohydride were added to 152 grams of the unrefined crude amine reaction product, and the mixture was treated at 50 C for2 hours. Then, a 25% aqueous solution of lauryl dimethylamine hydrochloride was prepared by a conventional process as in Example 1. 1t was colorless andthe percent transmission thereof was 94.0%.
• a method for refining aliphatic hydrocarbon amines having at least one alkyl group of 9 to 22 carbon atoms attached to the amino nitrogen, said amines being derived from polymerized ethylene and containing impurities which form coloring substances when the amines are converted to amine salts which comprises the steps of: reacting said amine with A. from 0.01 to 5 percent by weight, based on said amine, of a borohydride substance selected from the group consisting of alkali metal borohydrides,
• said amine is selected from the group consisting of compounds of the formulas RNl-l, RRNH and RR'R"H and mixtures thereof, wherein R is alkyl having 9 to 22 carbon atoms, and wherein R and R" are alkyls having 1 to 22 carbon atoms.
• R is alkyl having 10 to 18 carbon atoms and R and R are alkyls having 1 to 6 carbon atoms.
• R is lauryl and R and R" are methyl or ethyl.
• said borohydride substance is selected from the group consisting of sodium borohydride, potassium borohydride and lithium borohydride.
• said alkali is selected from the group consisting of sodium hydroxide, potassium hydroxide and sodium carbonate, and the amount of said alkali is from 0.1 to 10 percent by weight, based on said amine.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=11741322

Family Applications (1)

Country Status (3)

Cited By (12)

Citations (4)

• 1973
  • 1973-01-24 JP JP1011673A patent/JPS5522465B2/ja not_active Expired
• 1974
  • 1974-01-21 US US435086A patent/US3922306A/en not_active Expired - Lifetime
  • 1974-01-23 ES ES422539A patent/ES422539A1/es not_active Expired

Patent Citations (4)

Also Published As

Similar Documents