CN103012469B - The preparation method of high alkyl phosphate used for cosmetic - Google Patents
The preparation method of high alkyl phosphate used for cosmetic Download PDFInfo
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- CN103012469B CN103012469B CN201210594236.3A CN201210594236A CN103012469B CN 103012469 B CN103012469 B CN 103012469B CN 201210594236 A CN201210594236 A CN 201210594236A CN 103012469 B CN103012469 B CN 103012469B
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Abstract
The invention discloses a kind of preparation method of alkyl phosphate, the method is that add solvent as water entrainer to remove the water in reaction system, to improve the transformation efficiency of reaction, the structural formula of this alcohol is CH with phosphorylating agent and alcohol for raw material
3(CH
2)
ncH
2oH, wherein n=18 or 20, add corresponding alcohol and solvent in phosphorylating agent, and the mol ratio of alcohol and phosphorylating agent is 1:1.1 ~ 2.0, and after having added of alcohol, controlling temperature of reaction is 110 ~ 130 DEG C, react 4 hours, and in reaction process, one leads directly to N
2protection, the preparation of head product alkyl phosphate completes; Above-mentioned head product is carried out washing process, then leaves standstill, after layering, separate upper strata product, upper strata product is first carried out simple distillation, then add water repeatedly carry out azeotropic distillation thoroughly desolvation, complete the preparation of alkyl phosphate finally by cryodrying.The mixture of alkyl phosphate prepared by the present invention and its correspondent alcohol has good emulsifying property, water resisting property, preferably dispersive ability, can well be applied in makeup.
Description
Technical field
The invention belongs to the preparation method field of alkyl phosphate, especially a kind of C
20-C
22the preparation method of alkyl phosphate.
Background technology
Alkyl phosphate is that a class applies wider anion surfactant, is made up of monoalkyl phosphoric acid esters (MAP), bisalkyl phosphate (DAP), trialkyl phosphates (TAP).Monoalkyl phosphoric acid esters, bisalkyl phosphate belong to ionogenic surfactant, monoalkyl phosphoric acid esters due to its wetting ability strong, and it is water-soluble, convergency and static resistance effect better, there is certain rust inhibition, and the anion surfactant such as alkylsulfonate and alkyl-sulphate is less than to the pungency of skin; Bisalkyl phosphate has good smoothness, effectively can reduce the frictional coefficient of treated object, is mainly used as smooth agent; Trialkyl phosphates belongs to nonionogenic tenside, is commonly used for the softening agent and fire retardant etc. of macromolecular material.
Because alkyl phosphate has so many application, in the market the demand of phosphoric acid ester is also got more and more, the research and development of domestic phosphoric acid ester are started late, be generally to 16 carbon below phosphoric acid ester research more, and for more than 18 carbon alkyl phosphate research less, alkyl phosphate major parts more than 18 carbon relies on external import, but external price virtual height.From range of product, quality and quantity all with outer state-owned larger gap, because phosphoric acid ester has very important special performance, make the exploitation in this field have very large prospect, therefore, the alkyl phosphate for research long-chain has realistic meaning and economic worth.
Summary of the invention
For solving problems of the prior art, the present invention proposes a kind of C used for cosmetic
20-C
22the preparation method of even number alkyl phosphate.
A kind of C
20~ C
22the preparation method of even number alkyl phosphate, described preparation method is that the structural formula of described alcohol is CH with phosphorylating agent and alcohol for raw material
3(CH
2)
ncH
2oH, wherein n=18 or 20, comprise the following steps:
A, in the flask that phosphoric acid is housed, add solvent benzol, connect water trap, prolong switching on power, regulate temperature to be 90 DEG C, treat to occur layering in water trap, release the water of lower floor, the preparation of phosphorylating agent completes;
B, in phosphorylating agent described in step a, add corresponding alcohol and add a certain amount of solvent; the mol ratio of described alcohol and phosphorylating agent is 1:1.1 ~ 2.0, and after having added of alcohol, controlling temperature of reaction is 110 DEG C ~ 130 DEG C; reaction 4h, a straight-through N in reaction process
2protection, the preparation of head product alkyl phosphate completes;
C, the head product in above-mentioned steps b carried out washing process, then leave standstill, upper strata product is separated after layering, upper strata product is first carried out simple distillation and remove most of solvent, and then repeatedly add water and carry out the thorough desolvation of azeotropic distillation, last cryodrying, the preparation of alkyl phosphate completes.
Described alkyl phosphate is C
20~ C
22even number alkyl phosphate, the carbonatoms of alkyl phosphate is corresponding with the carbonatoms of alcohol.
In described step a, the volume ratio of solvent benzol and phosphoric acid is 4:1.
Described solvent benzol can also adopt toluene, C3-Fluoroalcohol, dimethylbenzene or ethylene dichloride.
The volume ratio of described toluene and phosphoric acid is 3:1, and described dimethylbenzene is 2:1 with the volume ratio of phosphoric acid, and C3-Fluoroalcohol is 4:1 with the volume ratio of phosphoric acid, and ethylene dichloride is 3:1 with the volume ratio of phosphoric acid.
In described step b, alcohol starts to add when oil bath starting temperature reaches 70 DEG C ~ 80 DEG C, and the joining day should control within 40 ~ 60min; Amount and the phosphoric acid volume ratio of adding solvent in described step c are 2 ~ 4:1.
In described step c, washing temperature is 70 DEG C, washing twice, and regulate pH to be 5 ~ 6, washing time is 1 ~ 2h.
The present invention adopts phosphorylating agent and higher alcohols (C
20~ C
22alcohol) prepare the mixture of corresponding alkyl phosphate and higher alcohols.In the preparation process of phosphorylating agent, by adding solvent benzol in phosphoric acid, the water in phosphoric acid better can be removed; In desolvation, first remove wherein most solvent by simple distillation, and then carry out azeotropic distillation to ensure thorough desolvation by repeatedly adding water, the alkyl phosphate prepared and the mixture of alcohol corresponding thereof, there are good emulsifying property, water resisting property, preferably dispersive ability, can well be applied in makeup.
Embodiment
The invention provides the preparation method of high alkyl phosphate, high alkyl phosphate is C
20~ C
22even number alkyl phosphate, in order to make object of the present invention, technical scheme and advantage clearer, clear and definite, below with reference to specific embodiment, the present invention is described in more detail.
Embodiment one:
Embodiment 1:
The preparation method of eicosyl phosphoric acid ester, with phosphorylating agent and eicosanol (carbonatoms is the alcohol of 20), for raw material, this preparation method comprises the following steps:
The preparation of phosphorylating agent: measure the phosphatase 11 0ml of 85%, add in there-necked flask, add 40ml solvent benzol; Then connect water trap, prolong, condensing reflux, open electric stirring, regulate oil bath temperature to 90 DEG C.After there is layering in water trap, release the water of lower floor, after approximately receiving 2ml, the preparation of phosphorylating agent completes.In phosphoric acid, add solvent benzol, because benzene can form azeotropic with water, be conducive to the water better removed in phosphoric acid.
Be 1:1.1 according to the mol ratio of eicosanol and phosphorylating agent, take 47.25g eicosanol and 10ml phosphorylating agent, when oil bath starting temperature reaches 70 DEG C, eicosanol starts slowly to join in phosphorylating agent, the joining day of eicosanol controls within 40 ~ 60min, adds excessive velocities and is unfavorable for that sufficient reacting carries out; During adding alcohol, add 20ml benzene, better except the water generated in dereaction, transformation efficiency can be improved, a straight-through N in reaction process
2protection, after having added of eicosanol, controlling temperature of reaction is 110 ~ 130 DEG C, and react 4 hours, the preparation of head product alkyl phosphate completes.
Head product alkyl phosphate is carried out washing process, washing temperature is 70 DEG C, wash twice, pH is regulated to be 5 ~ 6, washing time is 1 ~ 2h, wash rear leaving standstill, upper strata product is separated after layering, upper strata product is carried out simple distillation to remove a large amount of solvent benzols, and then add 5ml water and carry out azeotropic distillation, add water azeotropic distillation 3 times afterwards more repeatedly, after solvent thoroughly removes, take out product and carry out cryodrying, finally obtained product, product passes through mass spectrum, infrared, high performance liquid chromatography carries out analysis and obtains dibasic acid esters: 37.32%, monoesters: 13.43%, phosphoric acid: 0.99%, eicosanol: 48%.
The above-mentioned solvent benzol adopted when preparing phosphorylating agent and during adding alcohol the solvent benzol that supplements, also can replace with toluene, C3-Fluoroalcohol, dimethylbenzene or ethylene dichloride.
Embodiment 2:
Difference from Example 1 is: the mol ratio of eicosanol and phosphorylating agent is 1:1.5, and finally obtained product is carried out analysis obtained dibasic acid esters by mass spectrum, infrared, high performance liquid chromatography: 36.92%, monoesters: 13.87%, phosphoric acid: 0.98%, eicosanol: 46%.
Embodiment 3:
Difference from Example 1 is: the mol ratio of eicosanol and phosphorylating agent is 1:1.8, and finally obtained product is carried out analysis obtained dibasic acid esters by mass spectrum, infrared, high performance liquid chromatography: 36.12%, monoesters: 13.89%, phosphoric acid: 0.98%, eicosanol: 46%.
Embodiment 4:
As different from Example 1: the mol ratio of eicosanol and phosphorylating agent is 1:2.1, finally obtained product is carried out analysis obtained dibasic acid esters by mass spectrum, infrared, high performance liquid chromatography: 35.94%, monoesters: 14.97%, phosphoric acid: 0.98%, eicosanol: 45%.
Embodiment two:
Embodiment 1:
The preparation method of docosyl phosphoric acid ester, with phosphorylating agent and behenyl alcohol (carbonatoms is the alcohol of 22), for raw material, this preparation method comprises the following steps:
The preparation of phosphorylating agent: measure the phosphatase 11 0ml of 85%, add in there-necked flask, add 40ml solvent benzol; Then connect water trap, prolong, condensing reflux, open electric stirring, regulate oil bath temperature to 90 DEG C.After there is layering in water trap, release the water of lower floor, after approximately receiving 2ml, the preparation of phosphorylating agent completes.In phosphoric acid, add solvent benzol, because benzene can form azeotropic with water, be conducive to the water better removed in phosphoric acid;
Be 1:1.1 according to the mol ratio of behenyl alcohol and phosphorylating agent, take 51.69g behenyl alcohol and 10ml phosphorylating agent, oil bath starting temperature reaches 80 DEG C, behenyl alcohol starts slowly to join in phosphorylating agent, the joining day of behenyl alcohol controls within 40 ~ 60min, adds excessive velocities and is unfavorable for that sufficient reacting carries out; During adding alcohol, add 25ml benzene, better except the water generated in dereaction, transformation efficiency can be improved, a straight-through N in reaction process
2protection, after having added of behenyl alcohol, controlling temperature of reaction is 110 ~ 130 DEG C, and react 4 hours, the preparation of head product alkyl phosphate completes;
Head product alkyl phosphate is carried out washing process, washing temperature is 70 DEG C, wash twice, pH is regulated to be 5 ~ 6, washing time is 1 ~ 2h, wash rear leaving standstill, upper strata product is separated after layering, upper strata product is carried out simple distillation to remove a large amount of solvent benzols, and then add 5ml water and carry out azeotropic distillation, add water azeotropic distillation 3 times afterwards more repeatedly, after solvent thoroughly removes, take out product and carry out cryodrying, finally obtained product, product passes through mass spectrum, high performance liquid chromatography carries out analysis and records and consist of: dibasic acid esters: 37.45%, monoesters: 12.42%, phosphoric acid: 0.98%, behenyl alcohol: 48%.
The above-mentioned solvent benzol adopted when preparing phosphorylating agent and during adding alcohol the solvent benzol that supplements, also can replace with toluene, C3-Fluoroalcohol, dimethylbenzene or ethylene dichloride.
Embodiment 2:
Difference from Example 1 is: the mol ratio of behenyl alcohol and phosphorylating agent is 1:1.5, and finally obtained product is undertaken analyzing the composition recorded by mass spectrum, high performance liquid chromatography: dibasic acid esters: 36.59%, monoesters: 12.99%, phosphoric acid: 0.98%, behenyl alcohol: 47%.
Embodiment 3:
Difference from Example 1 is: the mol ratio of behenyl alcohol and phosphorylating agent is 1:1.8, and finally obtained product is undertaken analyzing the composition recorded by mass spectrum, high performance liquid chromatography: dibasic acid esters: 36.29%, monoesters: 13.42%, phosphoric acid: 0.98%, behenyl alcohol: 46%.
Embodiment 4:
Difference from Example 1 is: the mol ratio of behenyl alcohol and phosphorylating agent is 1:2.1, and finally obtained product carries out analyzing by mass spectrum, high performance liquid chromatography consisting of of recording: dibasic acid esters: 35.78%, monoesters: 14.97%, phosphoric acid: 0.99%, behenyl alcohol: 46%.
Should be understood that; the above-mentioned description for embodiment is comparatively detailed; therefore the restriction to scope of patent protection of the present invention can not be thought; those of ordinary skill in the art is under enlightenment of the present invention; do not departing under the ambit that the claims in the present invention protect; can also make the various deformation such as replacement, simple combination, request protection domain of the present invention should be as the criterion with claims.
Claims (6)
1. a C
22the preparation method of even number alkyl phosphate, described preparation method is that the structural formula of described alcohol is CH with phosphorylating agent and alcohol for raw material
3(CH
2)
ncH
2oH, wherein n=20, is characterized in that comprising the following steps:
A, in the flask that phosphoric acid is housed, add solvent benzol, connect water trap, prolong switching on power, regulate temperature to be 90 DEG C, treat to occur layering in water trap, release the water of lower floor, the preparation of phosphorylating agent completes;
B, in phosphorylating agent described in step a, add corresponding alcohol and add a certain amount of solvent; the mol ratio of described alcohol and phosphorylating agent is 1:1.1 ~ 2.0, and after having added of alcohol, controlling temperature of reaction is 110 DEG C ~ 130 DEG C; reaction 4h, a straight-through N in reaction process
2protection, the preparation of head product alkyl phosphate completes;
C, the head product in above-mentioned steps b carried out washing process, then leave standstill, upper strata product is separated after layering, upper strata product is first carried out simple distillation and remove most of solvent, and then repeatedly add water and carry out the thorough desolvation of azeotropic distillation, last cryodrying, the preparation of alkyl phosphate completes;
Abovementioned alkyl phosphoric acid ester is C
22even number alkyl phosphate, the carbonatoms of alkyl phosphate is corresponding with the carbonatoms of alcohol.
2. a kind of C according to claim 1
22the preparation method of even number alkyl phosphate, is characterized in that: in described step a, the volume ratio of solvent benzol and phosphoric acid is 4:1.
3. a kind of C according to claim 1
22the preparation method of even number alkyl phosphate, is characterized in that: described solvent benzol adopts C3-Fluoroalcohol or ethylene dichloride to replace.
4. a kind of C according to claim 3
22the preparation method of even number alkyl phosphate, is characterized in that: the volume ratio of described C3-Fluoroalcohol and phosphoric acid is 4:1, and the volume ratio of ethylene dichloride and phosphoric acid is 3:1.
5. a kind of C according to claim 2
22the preparation method of even number alkyl phosphate, is characterized in that: in described step b, alcohol starts to add when oil bath starting temperature reaches 70 DEG C ~ 80 DEG C, and the joining day should control within 40 ~ 60min, and amount and the phosphoric acid volume ratio of adding solvent are 2 ~ 4:1.
6. a kind of C according to claim 5
22the preparation method of even number alkyl phosphate, is characterized in that: in described step c, washing temperature is 70 DEG C, washing twice, and regulate pH to be 5 ~ 6, washing time is 1 ~ 2h.
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|---|---|---|---|
| CN201210594236.3A CN103012469B (en) | 2012-12-29 | 2012-12-29 | The preparation method of high alkyl phosphate used for cosmetic |
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| CN103012469B true CN103012469B (en) | 2015-10-28 |
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| CN107266496B (en) * | 2017-05-10 | 2020-05-05 | 中国日用化学工业研究院 | Method for synthesizing high-selectivity alkyl phosphate monoester |
Citations (4)
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|---|---|---|---|---|
| US3146255A (en) * | 1962-09-12 | 1964-08-25 | Stauffer Chemical Co | Preparation of monoalkyl phosphates |
| CN100400027C (en) * | 2001-10-11 | 2008-07-09 | 化工产品开发公司(S.E.P.P.I.C.) | Emulsifying compositions based on fatty alcohol and alkylpolyglycosides |
| CN101450953A (en) * | 2008-12-30 | 2009-06-10 | 南京中狮化学品有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
| CN101838286A (en) * | 2010-04-29 | 2010-09-22 | 苏州元素集化学工业有限公司 | Method and equipment for preparing fatty alcohol (ether) phosphate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5838435B2 (en) * | 1978-11-06 | 1983-08-23 | 花王株式会社 | Method for producing phosphoric acid monoester |
-
2012
- 2012-12-29 CN CN201210594236.3A patent/CN103012469B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3146255A (en) * | 1962-09-12 | 1964-08-25 | Stauffer Chemical Co | Preparation of monoalkyl phosphates |
| CN100400027C (en) * | 2001-10-11 | 2008-07-09 | 化工产品开发公司(S.E.P.P.I.C.) | Emulsifying compositions based on fatty alcohol and alkylpolyglycosides |
| CN101450953A (en) * | 2008-12-30 | 2009-06-10 | 南京中狮化学品有限公司 | Method for preparing monoalkyl phosphoric acid esters and salt thereof |
| CN101838286A (en) * | 2010-04-29 | 2010-09-22 | 苏州元素集化学工业有限公司 | Method and equipment for preparing fatty alcohol (ether) phosphate |
Non-Patent Citations (3)
| Title |
|---|
| 共沸脱水法烷基磷酸酯的合成;何文猛 等;《西南工学院学报》;19971230;第12卷(第4期);第71页倒数第1-4行，第72页8-11行、第2.1节，第73页，第74页第2段，倒数第1段 * |
| 磷酸酯表面活性剂的基本合成方法进展;李正军;《西部皮革》;20061218(第12期);第26-30页 * |
| 长链烷基磷酸酯的合成研究;张雷 等;《延安大学学报（自然科学版）》;20090331;第28卷(第1期);第60-63页 * |
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