CN105001109A - N<alpha>-acyl lysine surfactant, preparation method and application thereof - Google Patents
N<alpha>-acyl lysine surfactant, preparation method and application thereof Download PDFInfo
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- CN105001109A CN105001109A CN201510359028.9A CN201510359028A CN105001109A CN 105001109 A CN105001109 A CN 105001109A CN 201510359028 A CN201510359028 A CN 201510359028A CN 105001109 A CN105001109 A CN 105001109A
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- acyl
- active agent
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- JJUHWJQHBPFMJW-CZQLGGELSA-N CCCCCCCC/C=C/CCCCCCCC(N[C@@H](CCCCN)C(O)=O)=O Chemical compound CCCCCCCC/C=C/CCCCCCCC(N[C@@H](CCCCN)C(O)=O)=O JJUHWJQHBPFMJW-CZQLGGELSA-N 0.000 description 1
- VWYVABSAUVXYNS-QFIPXVFZSA-N CCCCCCCCCCCCCCCCCC(N[C@@H](CCCCN)C(O)=O)=O Chemical compound CCCCCCCCCCCCCCCCCC(N[C@@H](CCCCN)C(O)=O)=O VWYVABSAUVXYNS-QFIPXVFZSA-N 0.000 description 1
Abstract
The invention discloses a preparation method of an N<alpha>-acyl lysine surfactant. The method includes: taking lysine as the basis to carry out cyclization to obtain alpha-amino-epsilon-caprolactam, reacting alpha-amino-epsilon-caprolactam with acyl chloride to obtain N<alpha>-acyl amino caprolactam, conducting ring opening under alkaline conditions to obtain the N<alpha>-acyl lysine surfactant. Compared with the prior art, the N<alpha>-acyl lysine surfactant provided by the invention has the advantages of simple synthesis, low critical micelle concentration, good surface activity, high thermal stability, green and no toxicity, and easy biodegradation, can be widely used in pharmaceutics, cosmetics, biomedicine and other industries, and has broad market prospects.
Description
Technical field
The invention belongs to surfactant field, be specifically related to a kind of N
α-acyl-lysine class tensio-active agent and preparation method thereof and application.
Background technology
Tensio-active agent refers to and just significantly can reduce solution surface tension when adding a small amount of and the material changing interface state, generally has hydrophilic and oleophylic structure.The constructional feature of tensio-active agent makes it to have wetting, infiltration, solubilising, emulsification, dispersion, and washing, foaming, steady bubble, the functional performance such as soft, antistatic, have important effect in the industrial production, have the title of " industrial monosodium glutamate ".
Tensio-active agent is of many uses, and demand is huge.Market analysis was by 2019, and global surface promoting agent ultimate production will reach 2,000 ten thousand tons, and sales volume will reach 40,000,000,000 dollars.Tensio-active agent is various in style, but traditional petroleum base tensio-active agent is while extensive application, and the waste water of undecomposed complete tensio-active agent can enter soil, causes body eutrophication, thus works the mischief to waterplant, animal.The life-time service of petroleum base tensio-active agent also can produce irritation effect to skin, make cutaneous ageing, easy in accumulated in creatures after entering human body, be difficult to degraded, even can change the activity of human enzymes's preparation, dissolve gastrointestinal mucosal fat, change its perviousness, thus affect the absorption of nutritive substance, harm is produced to HUMAN HEALTH.
Tensio-active agent based on biomass is subject to extensive concern in recent years because of its good biodegradability and hypotoxicity.Amino acid surfactant has good wettability, whipability, stability in hard water, antibacterial corrosion stability, the ability such as antistatic, be that a class is quite gentle, pungency is less, the tensio-active agent of hypotoxicity, water-soluble good, readily biodegradable, oneself is widely used in the industries such as personal care clean-out system, makeup, food, beverage, health care, floatable minerals and agricultural chemicals allotment at present.
Methionin is amino containing α, ε is amino and the peculiar structures shape of carboxyl its can synthesize the tensio-active agent of various different structure.N is synthesized by mantoquita protection method as far back as people such as chestnut former rattan three youths in 1969
ε-lauroyl Methionin, but cumbersome.In order to process simplification, people's 1Bs such as Sohroeder in 1971 and lauric acid mixture direct heating dewater and carry out acidylate, Tong chi grand in 1976 dewaters with 1B lauroleate and synthesizes N in dimethylbenzene medium
ε-lauroyl Methionin, but generate a large amount of N
αn
ε-lauroyl lysine.At present in order to obtain single product, in laboratory study, obtain N mainly with amido protecting method
α-lauroyl lysine, cost height is more difficult is generalized to industrial application.The Methionin based surfactants of development of new structure, seeking the few simple and easy to do synthetic method of synthesis step is a direction from now on.Patent US7977450 B2 makees solvent by Methionin cyclization with alcohol, obtained aminocaproic lactam (ACL).Aminocaproic lactam acidylate, obtain N
α-acyl group class aminocaproic lactam, finally obtains N by open loop under its alkaline condition
α-acyl group class Methionin.The method is simple and easy to do, and productive rate is high, N
α-acyl group class lysine surfaces is better active, wide market.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of N
αthe preparation method of-acyl-lysine class tensio-active agent, loaded down with trivial details with the preparation method solving prior art existence, the problems such as productive rate is not high.
The technical problem that the present invention also will solve is to provide the N that above-mentioned preparation method prepares
α-acyl-lysine class tensio-active agent.
The problem that the present invention finally will solve is to provide above-mentioned N
α-acyl-lysine class tensio-active agent is in the application of surfactant field.
For solving the problem, the technical solution used in the present invention is as follows:
A kind of N
αthe preparation method of-acyl-lysine class tensio-active agent, it comprises the steps:
(1), after Methionin cyclization being prepared alpha-amino group-ε-caprolactam, N is obtained with acyl chloride reaction
α-acyl amino hexanolactam;
(2) N will obtained in step (1)
α-acyl amino hexanolactam is dissolved in the aqueous solution of alcohol, to add after alkali open loop 10 ~ 48h at 70 ~ 100 DEG C;
(3) after solvent being removed in the mixed system underpressure distillation of gained in step (2), adjust pH to iso-electric point filtrate, separate out precipitation.
In step (1), the temperature of ring-closure reaction is 130 DEG C ~ 170 DEG C.
In step (1), described acyl chlorides is the full of carbon number 8 to 18 or unsaturated acyl chlorides; Wherein, the full or unsaturated acyl chlorides of the preferred carbon number 10 to 16 of described acyl chlorides; Wherein, the most preferably full or unsaturated acyl chlorides of 12 carbon and 14 carbon are full or unsaturated acyl chlorides.
In step (1), the mol ratio of alpha-amino group-ε-caprolactam and acyl chlorides is 1:1 ~ 1.5; Wherein, the temperature of alpha-amino group-ε-caprolactam and acyl chloride reaction is 0 ~ 40 DEG C, preferably 20 ~ 30 DEG C.
In step (2), described alcohol is the saturated alcohol that carbon number is greater than 3;
Wherein, the saturated alcohol of preferred carbon number 3 ~ 13; Further, the saturated alcohol of preferred carbon number 3 ~ 6;
Wherein, most preferably butanols and amylalcohol;
Wherein, in the aqueous solution of alcohol, the volume ratio of alcohol and water is 0.5 ~ 6:1.
In step (2), described alkali is NaOH or KOH; Wherein, alkali and N
αthe mol ratio of-acyl amino hexanolactam is 2 ~ 6:1.
In step (2), the temperature of ring-opening reaction is preferably 90 ~ 100 DEG C.
In step (3), the pressure of underpressure distillation is 10 ~ 100mbar, and temperature is 40 ~ 70 DEG C.
In step (3), the reagent regulating pH used is 1mol/L aqueous hydrochloric acid and 1mol/L aqueous sodium hydroxide solution.
In step (3), can the precipitation of precipitation be dissolved in acid or alkaline solution, through stirring, filter and after drying, obtaining the N of salt form
α-acyl-lysine class tensio-active agent;
Wherein,
Described acid solution is the aqueous hydrochloric acid of 1 ~ 5mol/L;
Described alkaline solution is 1 ~ 10mol/L aqueous sodium hydroxide solution;
In acid or alkaline solution, acid or the mol ratio of alkali and precipitation are 1:1.
The N that above-mentioned any one prepares
α-acyl-lysine class tensio-active agent is also within protection scope of the present invention.
Above-mentioned N
α-acyl-lysine class tensio-active agent in the application of surfactant field also within protection scope of the present invention.
Beneficial effect: compared with prior art, the present invention's cyclization based on Methionin obtains alpha-amino group-ε-caprolactam, and alpha-amino group-ε-caprolactam and acyl chloride reaction obtain N
α-acyl group class aminocaproic lactam, open loop under alkaline condition, obtains N
α-acyl-lysine class tensio-active agent.This Methionin class synthesis of surfactant is simple, and micelle-forming concentration is low, has good surfactivity, and thermostability is strong, green non-poisonous, is easy to biological degradation, can be widely used in the industries such as pharmaceutics, makeup, biological medicine and has wide market outlook.
Accompanying drawing explanation
Fig. 1 is N of the present invention
α-acyl-lysine class surfactant structure formula, wherein, R is the full of carbon number 7 ~ 17 or unsaturated carbon chains.
Embodiment
According to following embodiment, the present invention may be better understood.But those skilled in the art will readily understand, the content described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
Embodiment 1:N
αthe preparation of-lauroyl lysine sodium.
Lauroyl aminocaproic lactam 15.5g (0.05mol), sodium hydroxide 4.0g (0.1mol), butanols 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 90 DEG C, 30h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-lauroyl lysine, mole 5M aqueous sodium hydroxide solution such as to add and stir 30min, drying obtains N
α-lauroyl lysine sodium 15.6g, productive rate 89%.ESI-MS m/z:(M+H)＝329.275。
Embodiment 2:N
αthe preparation of-lauroyl lysine hydrochloride.
Lauroyl aminocaproic lactam 15.5g (0.05mol), potassium hydroxide 5.6g (0.1mol), amylalcohol 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 90 DEG C, 28h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-lauroyl lysine, mole 2M hydrochloric acid such as to add and stir 30min, drying obtains N
α-lauroyl lysine hydrochloride 16.6g, productive rate 91%.ESI-MS m/z:(M+H)＝329.274。
Embodiment 3:N
αthe preparation of-lauroyl lysine.
Lauroyl aminocaproic lactam 15.5g (0.05mol), sodium hydroxide 6.0g (0.15mol), butanols 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 80 DEG C, 36h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-lauroyl lysine 15.6g, productive rate 95%.ESI-MS m/z:(M+H)＝329.275。
Embodiment 4:N
αthe preparation of-decoyl Sodium lysinate.
Decoyl aminocaproic lactam 12.7g (0.05mol), sodium hydroxide 4.0g (0.1mol), amylalcohol 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 90 DEG C, 18h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-decoyl Methionin, mole 4M aqueous sodium hydroxide solution such as to add and stir 30min, drying obtains N
α-decoyl Sodium lysinate 12.2g, productive rate 83%.ESI-MS m/z:(M+H)＝273.211。
Embodiment 5:N
αthe preparation of-caprinoyl Sodium lysinate.
Decanamido hexanolactam 14.1g (0.05mol), sodium hydroxide 4.0g (0.1mol), butanols 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 95 DEG C, 25h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-caprinoyl Methionin, mole 5M aqueous sodium hydroxide solution such as to add and stir 30min, drying obtains N
α-caprinoyl Sodium lysinate 14.2g, productive rate 88%.ESI-MS m/z:(M+H)＝300.245。
Embodiment 6:N
αthe preparation of-mnyristoyl Methionin.
Mnyristoyl aminocaproic lactam 16.9g (0.05mol), sodium hydroxide 8.0g (0.2mol), hexanol 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 100 DEG C, 34h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-mnyristoyl Methionin 15.9g, productive rate 89%.ESI-MS m/z:(M+H)＝357.301。
Embodiment 7:N
αthe preparation of-palmitoyllysines hydrochloride.
Palmitoylamino hexanolactam 18.3g (0.05mol), sodium hydroxide 8.0g (0.2mol), butanols 100ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 100 DEG C, 40h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-palmitoyllysines, mole 4M aqueous hydrochloric acid such as to add and stir 30min, drying obtains N
α-palmitoyllysines hydrochloride 18.9g, productive rate 90%.ESI-MS m/z:(M+H)＝385.343。
Embodiment 8:N
αthe preparation of-stearyl Methionin.
Stearyl aminocaproic lactam 19.7g (0.05mol), sodium hydroxide 10.0g (0.25mol), hexanol 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 100 DEG C, 48h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-stearyl Methionin 17.5g, productive rate 85%.ESI-MS m/z:(M+H)＝413.377。
Embodiment 9:N
αthe preparation of-oleoyl Methionin.
Oleoyl aminocaproic lactam 15.5g (0.05mol), sodium hydroxide 8.0g (0.2mol), butanols 50ml and water 100ml will be added in the there-necked flask of 1L, heated and stirred to 100 DEG C, 46h reacts end, solvent is removed in underpressure distillation, filtrate adjusts pH to iso-electric point with acid, separate out precipitation, obtain N
α-oleoyl Methionin 16.4g, productive rate 80%.ESI-MS m/z:(M+H)＝411.355。
Embodiment 10: above-described embodiment 1,2,4,5,7 surface tension, micelle-forming concentration (CMC), heat decomposition temperature are tested.
Get a certain amount of above-mentioned tensio-active agent, be configured to the solution of different concns with deionized water, by Kruss-K100 surface tension instrument determination surface tension at 25 DEG C, obtain micelle-forming concentration CMC.Above-mentioned tensio-active agent carries out thermogravimetric analysis further, and result is as following table.
| Embodiment is numbered | Lowest surface tension (mN/m) | CMC(mmol/L) | Heat decomposition temperature (DEG C) |
| 1 | 35.1 | 0.11 | 299 |
| 2 | 36.0 | 0.14 | 295 |
| 4 | 39.3 | 0.42 | 260 |
| 5 | 37.3 | 0.31 | 289 |
| 7 | 32.2 | 0.05 | 310 |
Embodiment 11: above-described embodiment 1,2,4,5,7 foaming powers and froth stability test
Prepare the above-mentioned surfactant soln 3mL that mass percentage is 10% respectively, be placed in 50mL tool plug graduated cylinder, adding distil water is diluted to 15mL, jumps a queue, concuss 10 times, immediate record lather volume (mL), again record lather volume after 10min, replication 3 times, averages, the above-mentioned tensio-active agent in surface has good foaming and steady bubble ability, and result is as following table.
| Foam cumulative volume/mL | 43 | 38 | 30 | 35 | 44 |
| Lather volume/mL after 10min | 35 | 29 | 18 | 23 | 31 |
Claims (10)
1. a N
αthe preparation method of-acyl-lysine class tensio-active agent, it is characterized in that, it comprises the steps:
(1), after Methionin cyclization being prepared alpha-amino group-ε-caprolactam, N is obtained with acyl chloride reaction
α-acyl amino hexanolactam;
(2) N will obtained in step (1)
α-acyl amino hexanolactam is dissolved in the aqueous solution of alcohol, to add after alkali open loop 10 ~ 48h at 70 ~ 100 DEG C;
(3) after solvent being removed in the mixed system underpressure distillation of gained in step (2), by filtrate adjust pH to iso-electric point, precipitation is separated out.
2. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (1), the temperature of ring-closure reaction is 130 DEG C ~ 170 DEG C.
3. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (1), described acyl chlorides is the saturated of carbon number 8 to 18 or unsaturated acyl chlorides.
4. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (1), the mol ratio of alpha-amino group-ε-caprolactam and acyl chlorides is 1:1 ~ 1.5; Wherein, the temperature of alpha-amino group-ε-caprolactam and acyl chloride reaction is 0 ~ 40 DEG C.
5. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (2), described alcohol is the saturated alcohol that carbon number is greater than 3; Wherein, in the aqueous solution of alcohol, the volume ratio of alcohol and water is 0.5 ~ 6:1.
6. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (2), described alkali is NaOH or KOH; Wherein, alkali and N
αthe mol ratio of-acyl amino hexanolactam is 2 ~ 6:1.
7. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (3), the pressure of underpressure distillation is 10 ~ 100mbar, and temperature is 40 ~ 70 DEG C, and the reagent regulating pH used is 1mol/L aqueous hydrochloric acid and 1mol/L aqueous sodium hydroxide solution.
8. N according to claim 1
αthe preparation method of-acyl-lysine class tensio-active agent, is characterized in that, in step (3), can be dissolved in acid or alkaline solution by the precipitation of precipitation, through stirring, filter and after drying, obtaining the N of salt form
α-acyl-lysine class tensio-active agent.
9. the N for preparing of claim 1 ~ 8 any one
α-acyl-lysine class tensio-active agent.
10. N according to claim 9
α-acyl-lysine class tensio-active agent is in the application of surfactant field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380420A (en) * | 2016-08-31 | 2017-02-08 | 中国药科大学 | N-alpha-acyllysine surfactant, and preparation method and application thereof |
| CN109761839A (en) * | 2019-03-04 | 2019-05-17 | 浙江华贝药业有限责任公司 | Compound N -2- alkanoyl-L-lysine synthetic method |
| CN112048048A (en) * | 2020-09-16 | 2020-12-08 | 南京工业大学 | Polyurethane foam material and preparation method thereof |
-
2015
- 2015-06-25 CN CN201510359028.9A patent/CN105001109A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380420A (en) * | 2016-08-31 | 2017-02-08 | 中国药科大学 | N-alpha-acyllysine surfactant, and preparation method and application thereof |
| CN106380420B (en) * | 2016-08-31 | 2018-08-17 | 中国药科大学 | A kind of NαAcyl-lysine class surfactant and the preparation method and application thereof |
| CN109761839A (en) * | 2019-03-04 | 2019-05-17 | 浙江华贝药业有限责任公司 | Compound N -2- alkanoyl-L-lysine synthetic method |
| CN112048048A (en) * | 2020-09-16 | 2020-12-08 | 南京工业大学 | Polyurethane foam material and preparation method thereof |
| CN112048048B (en) * | 2020-09-16 | 2021-10-15 | 南京工业大学 | Polyurethane foam material and preparation method thereof |
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