KR850000076B1 - Phosphoric acid triesters - Google Patents

Abstract

Epichlorohydrin was reacted with phosphoric acid to give halogen- containing epibiphosphate, which was reacted with tertiary amine. This gave surface-active cationic triester phosphate (I) where R1,R2 and R3 each have a formula (II) or (III), in which R4,R5 and R6 are 1-22C alkyl, alkenyl or a polyoxyalkyl ether gp., provided that at least one of the R4,R5 and R6 gps. contains at least 6C, or R5 and R6 together form a heterocyclic gp. with the bonded N atom. R7 is 2-12C alkylene in mono- or polyoxyalkylene, opt. substd. by an alkyl, OH or hydroxyalkyl gp. contg. up to 10C. R8 is H or alkyl; n is an integer 1-10 and X is an anion. I is used in hair-care compsns., e.g. as conditioners to facilitate combing-out, and in shampoos.

Description

Process for preparing phosphoric acid triester

The present invention relates to a process for the production of novel cationic triesters of phosphoric acid.

These compounds are useful for the preparation of hair dressing agents, and have bacteriostatic and bactericidal properties.

The present invention relates to the production of novel phosphorus derivatives. More specifically, the present invention relates to the preparation of novel cation triesters of phosphoric acid having the following general formula (I).

In the general formula (I), R ₁ , R ₂ and R ₃ may be the same as or different from each other and may be represented by the following general formulas (II) and (III).

Wherein R ₄ , R ₅ and R ₆ are the same or different from each other and are alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxy alkylated ethers containing 1 to about 22 carbon atoms, provided that R ₄ At least one of R ₅ and R ₆ has at least 8 carbon atoms.

And R ₅ and R ₆ attached with nitrogen may also form heterocyclic structures of morpholine, thiomorpholine, indole and constant velocity; R ₇ is alkylene or mono or polyoxy alkylene of 2 to 12 carbon atoms which may be substituted with alkyl, alkoxy, hydroxy or hydroxy alkyl groups of up to about 10 carbon atoms; R ₈ is hydrogen, alkyl up to 7 carbon atoms, hydroxyalkyl, alkenyl or cycloalkyl, or polyoxy alkylated hydroxy alkyl up to 10 carbon atoms; n is an integer from about 1 to 10, and X is an anion such as Cl ⁻ , Br ⁻ constant velocity.

The novel compounds of the present invention can be prepared by several methods including the following methods.

Method A: Reaction of hydroxyl group containing quaternary ammonium compound with phosphorus oxychloride.

A suitable tertiary amine of formula (IV) or (V) is then quaternized using a compound having the formula XR ₇ -OH with a suitable solvent, reactor and reaction conditions.

In the general formula, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and n are the same as defined above, and X is a halogen such as Cl, Br or I.

More specifically, the quaternization reaction is embedded in glass or glass equipped with a heater, high stirrer, thermometer and reflux condenser using a solvent such as lower alkanol, water or mixtures thereof to ensure good mixing and temperature control. It proceeds in a reactor.

The reaction temperature may be in the range of about 70 ° C to 120 ° C, but is generally determined by the reflux temperature of the reaction mixture. The progress of the reaction can be monitored by the silver titration of halogen ions generated during the quaternization reaction.

These reactions can be represented by the following expression.

To separate the quaternary ammonium compound, a portion of the solvent is organic and acetone is added while the reaction mixture is maintained at 40-50 ° C. Cooling it forms a crystal precipitate which is separated by suction filtration and vacuum drying. The second stage of this reaction can be represented by the following scheme.

or

The reaction between the hydroxyl group-containing quaternary ammonium compound and phosphorus oxychloride is usually carried out by dispersing the quaternary ammonium compound in a low boiling point low polar solvent such as methylene chloride, and gradually adding the required phosphorus oxychloride at room temperature.

Or once phosphorus oxychloride is added, the temperature is raised to the boiling point of the reaction mixture and the mixture is refluxed for 18 hours. The solvent is distilled off and the phosphate triester is purified by recrystallization in hot acetone.

Other manufacturing methods that have proven to be effective include the following methods.

Method B: Reaction of tertiary amine with phosphate ester halide.

The manufacturing process of an initial stage and a phosphate ester intermediate can be shown by the following diagram.

Wherein X is a halogen functional group and Y is an alkylene of up to 12 carbon atoms in which the alkylene chain may be optionally substituted with lower alkyl, alkoxy, hydroxy or hydroxyalkyl of up to 10 carbon atoms each of which is optionally 3 Up to two oxygen atoms may be incorporated. The next step, ie the reaction of the phosphate ester with the tertiary amine, is shown as follows.

In general, the reaction is carried out in a super reactor equipped with a high stirrer, an addition funnel (FUNNEL), a reflux condenser and an external heating and cooling device.

를 반응기에 장입하고, 이를 강렬히 교반하면서 1부의 농축인산을 적가(滴加)한다.3 parts substituted oxirane,

Is charged to the reactor, and 1 part of concentrated phosphoric acid is added dropwise with vigorous stirring.

The phosphoric acid addition rate is adjusted to maintain the reaction temperature at 65 to 95 ° C, preferably 85 to 90 ° C. Halogen-containing epibiphosphate intermediates are formed. Three parts of a suitable tertiary amine are added in small amounts while maintaining the reaction temperature at 90-100 ° C. After completion of the amine addition, the reaction mixture is partially taken and "silver titrated" and the reaction mixture is heated to 100-120 ° C until the end of the reaction is confirmed.

After cooling, the reaction mixture is dissolved in hot ethanol / acetone. The methanol formed by acetone / acetone solution is cooled down and the dried precipitate is dried to give the desired product.

The novel phosphate triester compounds of the present invention are cationic surfactants that can be readily absorbed into hair fibers or other negatively charged surfaces to reduce mutual electrostatic action.

When R ₄ , R ₅ or R ₆ has 16 or more carbon atom skeletons, the use of such a compound in the hair can eliminate the curling of the hair and provide good wet and dry combing conditions.

Conventional cationic quaternary ammonium salts were not readily mixed with a large number of surfactants. Surprisingly, however, the compounds of the present invention include anionic surfactants of sodium lauryl sulfate or sodium lauryl ether sulfate; Amphoteric surfactants such as betaines, sulleines, and phosphobetaines; And a wide range of surfactants such as nonionic surfactants such as ethoxylated sorbitan esters. This unexpected mixing makes it easy to add the compound of the present invention to a conventional shampoo and cream liquid composition.

The compound of the present invention can be used in about 0.1% to about 20% by weight depending on the composition using the same.

When using an amount of 20% or more by weight, the obtained composition is not soft and irritant when used as a cream or shampoo. Furthermore, when R ₄ , R ₅ , or R ₆ of Formula (II) or R ₄ of Formula (III) of the phosphate triester compound of the present invention are 8 to 14 carbon atom chains, these compounds are excellent bacteria. It exhibits growth inhibition and bactericidal properties. Compounds having such characteristics can be used in an amount of about 0.1% to about 5.0% by weight of the total composition, and when used in an amount of about 0.1% or less, the required properties cannot be obtained. It will not be able and irritating.

The following examples are intended to illustrate the invention and are not intended to limit the invention thereto.

Example 1

46.53 g of epichlorohydrin is charged into a 500 ml glass reactor equipped with a high stirrer, a water-cooled condenser, an addition funnel, a thermometer and a heating mesh. Then, while vigorously stirring, 19.0 g of 85.5% phosphoric acid is added at an addition rate capable of maintaining a temperature of 80 to 85 ° C through a dropping funnel.

When the exothermic reaction stops, the reactor is heated to maintain the reaction mixture at 80 ° C. for 1 hour. 148 g of octadecyl dimethylamine are then added to the reactor and the mixture is stirred at 102 ° C. for 20 hours.

Completion of the reaction is confirmed by the thermotitration of the generated chlorine ions. After cooling to about 40 ° C., the reaction mixture is diluted with 200 ml ethanol, transferred to a 2 liter beaker and 1000 ml acetone are added. Tannin color precipitates are formed which are separated by suction filtration and recrystallized in an ethanol / acetone mixture to give tannin powder. The quantitative analysis of the warm titration and saponification of chlorine ions showed that the purity of this material was 98.6%.

This product contains the phosphate triester of the following general formula.

Example 2

Using the first reactor of Example 1, 93.52 g of epichlorohydrin was reacted with 238 g of 85.5% phosphoric acid at 85 to 90 ° C. for 2 hours. 213.2 g of dodecyldimethylamine is then added over 3 hours while maintaining the temperature between 85 and 90 ° C. After further heating for 72 hours at 100 ± 5 ℃, the temperature titration for chlorine ions was found that the reaction proceeded more than 90%. The reaction product was separated by the method of Example 1 to obtain a tamtannin free flowing powder and the quantitative analysis showed a purity of 99.0%.

The product contains the phosphate triester of the following general formula.

Example 3

Using the apparatus of Example 1, 19.0 g of concentrated phosphoric acid is added dropwise to 46.53 g of epichlorohydrin while maintaining the reaction temperature between 85 and 90 ° C. 176.5 g of a 50/50 melt mixture of icosyldimethylamine and docosyldimethylamine are added over 2 hours while maintaining the temperature at 100 ° C. The temperature of the reaction mixture was raised to 140 ° C. for 90 minutes after further maintaining 12 hours at 100 ° C. After cooling, the desired product is crystallized in hot ethanol, separated by suction filtration and dried. Warm titration indicates 94.6% activity. The structure was the same as that of Example 2 except that the C ₁₂ H ₂₅ substituent was replaced with a mixture of C ₂₀ H ₄₁ and C ₁₂ H ₄₅ in a 1: 1 ratio.

Example 4

140.28 g of epichlorohydrin is reacted with 57 g of 85.5% phosphoric acid using a 2 liter super reactor equipped with a high stirrer and a reflux condenser, and the reaction is performed at 85 to 90 ° C for at least 2 hours.

548.6 g of 3-oleomiamipropyl dimethylamine is added to the reaction and the temperature is raised to 95-100 ° C. After 22 hours, on titration shows that the reaction is nearing completion. The reaction is then cooled.

After crystallization in ethanol / acetone, suction filtration and vacuum drying yield an off-white powder.

This product contains phosphate triesters of the general formula:

Example 5

112.2 g of epichlorohydrin is reacted with 45.6 g of 85.5% phosphoric acid using the reaction vessel and conditions of Example 3. 458.4 g of stear amido ethyl diethyl amine are added to the reaction mixture which is kept at 95 ° C. for 20 hours. Completion of the reaction was confirmed by thermal titration, and the product contained phosphate triester of the following general formula.

Example 6

297 g of octadecyldimethylamine and 80 g of ethylenechlorohydrin are dissolved in anhydrous ethanol to make the total amount to 1500 ml. The mixture is then heated in a two liter round bottom flask equipped with a reflux condenser. After 6 days, chlorine titration indicated that the reaction was 91% complete, thereby terminating the reaction.

The desired stearyl dimethyl-2-hydroxyethyl ammonium chloride is isolated by precipitation with acetone.

After recrystallization in an ethanol / acetone mixture, filtration and vacuum drying yielded a white powder, which was 98.9% pure by chlorine titration. 228.7 g of this stearyl dimethyl-2-hydroxy ethylammonium chloride are charged to three liters of two round bottom flasks equipped with a high stirrer, an addition funnel and a reflux condenser.

1200 ml of methylene chloride are added and the quaternary ammonium compound is dispersed by vigorous stirring.

30.70 g of phosphoryl chloride POCl ₃ is added dropwise over 1 hour. The reaction mixture is then refluxed for 18 hours, methylene chloride is distilled off and recrystallized in hot acetone to purify the triester.

This product contains the phosphate triester of the following general formula.

Example 7

213.14 g of dodecyl dimethylamine is dissolved in 1200 ml of anhydrous ethanol and 80 g of ethylenechlorohydrin is added to reflux the reaction mixture for 72 hours. Precipitate with acetone, recrystallize in ethanol / acetone, filter and vacuum dry to give dodecyl dimethyl-2-hydroxy ethyl ammonium chloride in 84% yield.

175.9 g of the aforementioned dodecyl dimethyl-2-hydroxy ethyl ammonium chloride is reacted with 30.70 g of inoxychloride using the apparatus and reaction conditions described in Example 5.

This product contains the phosphate triester of the following general formula.

Example 8

305.6 g of stearamido ethyldiethylamine are dissolved in 2000 ml of anhydrous ethanol. The reaction mixture, which was added by adding 64 g of ethylene chlorohydrin, was refluxed for 120 hours. Approximately 3/4 of methanol is removed by flash evaporation and acetone is added saturated at the boiling point. The reaction mixture is then cooled to room temperature. The white precipitate formed was isolated and dried in vacuo to prove that stear amido is ethyldiethyl-2-hydroxy ethylammonium chloride.

277.2 g of the aforementioned steamiamido ethyldiethyl-2-hydroxy ethylammonium chloride was reacted with 30.7 g of inoxychloride using the apparatus and reaction conditions described in Example 5.

This product contains the phosphate triester of the following general formula.

Example 9

Hairdressing products are manufactured as follows:

Of the following general formula

(Where R is a C ₁₁ -C ₁₃ mixture in a 1: 1 ratio)

When the solution obtained by mixing 150 parts by weight of 30% active solution of phosphobetaine with 200 parts of distilled water at room temperature and subsequently adding 77 parts of 26% active solution of the cationic triphosphate ester of Example 1 by weight Mix until.

This is subsequently prepared by the method described in US Pat. No. 2,970,161, followed by the following general formula

(Where R is a C ₁₁ -C ₁₃ mixture in a 1: 1 ratio)

150 parts by weight of the 30% active solution of the amphoteric substance represented by.

The resulting mixture is then heated at 70 ° C. for 20 minutes by adding 200 parts of 72% polyoxyethylene (80) sorbitan monococoate followed by 12 g of 6000 distearate polyethylene glycol.

The solution is cooled to 35 ° C. and the pH is adjusted to 7.0 ± 1 with 15% HCl solution.

Preservatives and fragrances are added and sufficient demineralized water is added to make the total amount 1000 g.

This finished product was clear with a viscosity of 1225 cps at 25 ° C. measured using a Brookfield viscometer with 12 RPM and # 2 spindle.

The product showed excellent foaming and cleaning properties, and as it was confirmed through the half head studies of the beauty salon, it showed an excellent effect of hair grooming.

These studies separate each study subject's hair into two parts, use the shampoo composition using the compound of the present invention on one of the hairs, and the shampoo product without the compound of the present invention on the other hairs. The results were graded and progressed.

Example 10

The following hair cleansers or skin cleansers were prepared by the method outlined in Example 9.

The pH of the solution was adjusted to 5.5 with water HCl.

Example 11

Detergent, softener, and income system were prepared as follows.

The pH of the solution was adjusted to 7.0 ± 1 with 15% HCl. The composition of Example 11 was compared with two commercial compositions using the following method to test its cleaning power. A comparative cleaning power of the test compositions was evaluated using a standard contaminated wool fabric (Test Fabrics Inc). The cleaning behavior was simulated using Terg-O-Tometer model 7243. The contrasted conditions are as follows.

The test fabric was woolly woven and 10 yards rolls. Contaminated mixtures, primarily of lemp black, oil and shapan solvents, were contaminated with printing rolls and only half of the 8-inch-wide woven fabrics. This test fabric was cut into 4 × 8 pieces so that half of each piece was contaminated and the other half was not contaminated.

An initial color value (whiteness) of the contaminated and non-contaminated portions of each piece was obtained using a Gardner color difference measuring instrument. Three aforementioned three pieces, along with three 4 × 8 inch cotton blender pieces, were placed in a Terg-O-Tometer beaker in which 1000 ml of a 10% aqueous solution of the above test composition was infiltrated. The above solution was stirred for 2 minutes in advance and equilibrated at 105 ° F. The sample was stirred for 5 minutes, taken out and put back into a stirred beaker with 1000 ml of compressed, clean 105 ° F. tap water.

After stirring for 5 minutes, the pieces were taken out, compressed, and stretched to dryness. Once dried, they were again evaluated using a color difference meter to measure the degree of decontamination and adhesion of non-contaminated woven fabrics. Comparative wash effectiveness is expressed as the difference between the initial and final white measurements measured with ΔR. Commercial compositions were compared with the compositions of Example 11 to yield the following results.

Example 12

Injection cream wash was prepared having the following composition.

This composition showed excellent wet hair combing ability and hairdressing properties.

Example 13

In order to clarify the antimicrobial properties of the compounds of the present invention, the following standard minimum concentration tests were conducted to determine the lowest effective concentrations of the compounds that would inhibit the growth of various test organisms. First, 200 mg of each of the compounds of Examples 2 and 7 were added to 100 ml of distilled water to a concentration of 2.00 mg / ml. Ten serial fold dilutions were performed to achieve a final concentration of 0.0038 mg / ml.

Thus, the concentration range was 0.0038 mg / ml to 2.00 mg / ml. Separately 1000 ml of standard antibiotic 3 was inoculated into each test organism in 1 ml of 24-hour fermentation broth culture. The resulting solution was dispersed in a 13 mm × 100 mm test tube at 4 ° C. in 2 ml portions. Two test tubes were prepared for each test microorganism. 0.4 ml of the concentrate of each compound to be tested was then placed in each test tube. These were shaken and kept at 35 ° C. for 18 hours. The end point of activity was measured using a loop expressed in Trypticasesoy Agar to determine the final tube (concentration) at which growth occurred, and then the highest concentration was viewed as the minimum stop concentration.

The results are shown in the first table below.

[Table 1]

When these results were compared with the control bacterium growth inhibitory agent and / or bactericidal cetylpyridinium chloride, it was found that the compound of the present invention exhibited bacteriostatic and bactericidal properties at a relatively low concentration and was an excellent antimicrobial agent.

While the invention has been described and described in terms of specific embodiments thereof, it will be readily apparent to those skilled in the art that various changes, modifications, omissions, and substitutions can be made without departing from the scope of the invention. Therefore, the present invention should be limited only by the following claims.

Claims (1)

Reacting epichlorohydrin with phosphoric acid to form a halogen-containing epibiphosphate, and reacting the epibiphosphate intermediate with a tertiary amine.

In Formula (I), R ₁ , R _2, and R ₃ may be represented by the same or different following Formulas (II) and (III).

Provided that R ₄ , R ₅ and R ₆ are alkyl, alkenyl, hydroxyalkyl, arylalkyl or polyoxyalkylated ethers containing from 1 to about 22 carbon atoms which are the same or different from each other, wherein R ₄ , R ₅ And at least one of R ₆ must have at least 8 carbon atoms; In addition, R ₅ and R ₆ attached with nitrogen may form a heterocyclic structure of morpholine, thiomorpholine, indole and the like; R ₇ is an alkylene or mono- or di-polyoxyalkylene of about 2 to 12 carbon atoms which may be substituted with an alkyl, alkoxy, hydroxy or hydroxyalkyl group of up to about 10 carbon atoms; R ₈ is hydrogen, alkyl up to 7 carbon atoms, hydroxyalkyl, alkenyl or cycloalkyl, or polyoxyalkylated hydroxyalkyl up to 10 carbon atoms; n is an integer from about 1 to 10, and X is an anion such as Cl ⁻ , Br ⁻ constant velocity.