CN102030806A - Tea saponin high-grade fatty ester as well as preparation method and application thereof - Google Patents
Tea saponin high-grade fatty ester as well as preparation method and application thereof Download PDFInfo
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- CN102030806A CN102030806A CN 201010515905 CN201010515905A CN102030806A CN 102030806 A CN102030806 A CN 102030806A CN 201010515905 CN201010515905 CN 201010515905 CN 201010515905 A CN201010515905 A CN 201010515905A CN 102030806 A CN102030806 A CN 102030806A
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Abstract
The invention discloses a tea saponin high-grade fatty ester as well as a preparation method and an application thereof. The tea saponin high-grade fatty ester has the structure disclosed in the formula I and is prepared by the following method: in the presence of a catalyst, mixing tea saponin with high-grade fatty ester to react, and separating the catalyst to obtain the tea saponin high-grade fatty ester disclosed in the formula I. The tea saponin high-grade fatty ester is made of natural raw materials, is nontoxic and is easy to degrade. The tea saponin high-grade fatty ester has simple preparation technology and easily-controlled reaction conditions and can be used for industrial production. What is more important is that the tea saponin high-grade fatty ester has stronger foaming power and foam stabilization performance at high temperature and in oil when the fatty ester serves as a surfactant. The tea saponin high-grade fatty ester overcomes the defect that the existing tea saponin has poor foaming power and foam stabilization performance in high-temperature oily environments.
Description
Technical field
The present invention relates to the tensio-active agent field, be specifically related to senior fatty ester of a kind of theasaponin and preparation method thereof, with and as the application of lipophilic nonionic bio-surfactant in pesticide emulsion, oil production, oil type cosmetics of everyday use.
Background technology
Tensio-active agent have dispersion, infiltration, solubilising, emulsification, wetting, bubble, performance such as lubricated, sterilization, be widely used in fields such as food, medicine, agricultural chemicals, weaving, chemical industry, tamanori, ore dressing, oil field chemical, papermaking, leather, sensitive materials, articles for washing, makeup, its kind and consumption increase day by day.But for a long time, people use artificial synthetic tensio-active agent always, and a large amount of uses of synthetic surfactant have caused environmental pollution and safety issue.Bio-surfactant nontoxic, easy degraded more and more is subject to people's attention.
Many natural compoundss have surfactivity, and as saponins compound, but than synthetic surfactant, its surfactivity is still on the low side.
Modern study shows that long its intermolecular force of cohesion of foaming agent of hydrophobic group chain can make liquid film elasticity and intensity increase, thereby the foam height that produces is higher.Side chain or hydrophilic group chain are in the tensio-active agent at middle part, and it is bigger to reduce capillary ability, and whipability is better.In the time of in the middle of hydrophilic group is being shifted to by straight chain one end, its foaming height generally is to increase.This shows, change the natural surface active agent structure, help the raising of its surfactivity ability.
Theasaponin is to be present in a kind of main pentacyclic triterpene compound in tea seed or the tea seed, forms by sapogenin, sugared body and organic acid three parts, and be that a class has surface-active compound, it has the advantages that foaming power is strong, foam is little, dispersion force is strong.Yet find in the practical application that foaming power and foam stability can be relatively poor in high temperature and heavy wool environment for theasaponin.
Summary of the invention
The shortcoming that primary and foremost purpose of the present invention is to overcome prior art provides a kind of senior fatty ester of the active theasaponin of superior refractory surfaces that has with not enough.
Another object of the present invention is to provide the preparation method of the senior fatty ester of above-mentioned saponin(e.
A further object of the present invention is to provide the application of the senior fatty ester of above-mentioned saponin(e.
Purpose of the present invention is achieved through the following technical solutions:
The senior fatty ester of a kind of theasaponin has suc as formula the structure shown in the I:
(formula I)
Wherein, R is C
12～C
18Saturated or unsaturated alkane.
The preparation method of the senior fatty ester of above-mentioned theasaponin may further comprise the steps being characterised in that:
Under the situation that catalyzer exists, theasaponin is mixed, reacts with high fatty alcohol, obtain suc as formula the senior fatty ester of the theasaponin shown in the I behind the separating catalyst.
Described catalyzer is N, the mixture of N-dicyclohexylcarbodiimide (DCC) and 4-dimethylamino pyridine (DMAP), and wherein, the DCC consumption is 1～1.5 times of molar mass of theasaponin, the DMAP consumption is 5～10% of a theasaponin quality.
Described high fatty alcohol is meant C
12～C
18Saturated or unsaturated fatty alcohol, molar masss such as its add-on and theasaponin.
The temperature of reaction of described theasaponin and high fatty alcohol is 20～30 ℃, and the reaction times is 8～16h; Preferred 10～12h of reaction times.
The application of the senior fatty ester of above-mentioned theasaponin is characterized in that: the senior fatty ester of described theasaponin is directly used in water-in-oil emulsifier, missible oil type farm chemical emulgent, oil field foam flooding, oil type cosmetics of everyday use etc. as lipophilic nonionic bio-surfactant.
The present invention carries out structure of modification to theasaponin, in the theasaponin molecular structure, increased a hydrophobic group chain, make it to possess have hydrophilic radical to be in the middle part, two ends are distributed with the surfactant structure of hydrophobic grouping, have improved its foam stability energy in high temperature and heavy wool environment.
The present invention has following advantage and effect with respect to prior art:
(1) the senior fatty ester of theasaponin of the present invention, as tensio-active agent, foaming power in high temperature and oil and foam stability can be stronger.
(2) the senior fatty ester tensio-active agent of theasaponin of the present invention is nontoxic from natural matter, easily degraded.
(3) preparation technology of the present invention is simple, and easily-controlled reaction conditions can be used for suitability for industrialized production.
Embodiment
The present invention is described in further detail below in conjunction with embodiment, but embodiments of the present invention are not limited thereto.
Embodiment 1
With theasaponin solid 100g, join in the pyridine of 300mL, stir and make it dissolving.Add lauryl alcohol 15.3g by the theasaponin equimolar amount, add DCC (17g), DMAP (5g), 20 ℃ of following stirring reaction 8h.The pressure reducing and steaming pyridine.Add the dissolving of 500mL toluene, the elimination insolubles adds saturated aqueous common salt 500mL, washs 3 times.Obtain product 53g behind the reclaim under reduced pressure toluene.
Structural analysis to product shows that MS:m/z 1385; Elementary compositionly be: C61.54%, H8.44%, O30.02%, its molecular formula is C
71H
116O
26,
1H-NMR and
13C-NMR shows has increased by 1 methyl and 11 mesomethylene carbon chain structures, and other is identical with theasaponin.Its structure is as follows:
Embodiment 2
With theasaponin solid 100g, join in the pyridine of 300mL, stir and make it dissolving.Add 14 carbon dienol 17.2g by the theasaponin equimolar amount, add DCC (20g), DMAP (7g), 24 ℃ of following stirring reaction 10h.The pressure reducing and steaming pyridine.Add the dissolving of 500mL toluene, the elimination insolubles adds saturated aqueous common salt 500mL, washs 3 times.Obtain product 56g behind the reclaim under reduced pressure toluene.
Structural analysis to product shows that MS:m/z 1409; Elementary compositionly be: C62.20%, H8.29%, O29.51%, its molecular formula is C
73H
116O
26,
1H-NMR and
13C-NMR shows has increased by 1 methyl, 9 methylene radical carbochains and 4 unsaturated carbon atom structures, and other is identical with theasaponin.Its structure is as follows:
Embodiment 3
With theasaponin solid 100g, join in the pyridine of 300mL, stir and make it dissolving.Add palmityl alcohol 20g by the theasaponin equimolar amount, add DCC (22g), DMAP (8g), 27 ℃ of following stirring reaction 12h.The pressure reducing and steaming pyridine.Add the dissolving of 500mL toluene, the elimination insolubles adds saturated aqueous common salt 500mL, washs 3 times.Obtain product 62g behind the reclaim under reduced pressure toluene.
Structural analysis to product shows that MS:m/z 1441; Elementary compositionly be: C62.48%, H8.67%, O28.85%, its molecular formula is C
75H
124O
26,
1H-NMR and
13C-NMR shows has increased by 1 methyl and 15 mesomethylene carbon chain structures, and other is identical with theasaponin.Its structure is as follows:
Embodiment 4
With theasaponin solid 100g, join in the pyridine of 300mL, stir and make it dissolving.Add 18 carbon dienol 22g by the theasaponin equimolar amount, add DCC (26g), DMAP (10g), 30 ℃ of following stirring reaction 16h.The pressure reducing and steaming pyridine.Add the dissolving of 500mL toluene, the elimination insolubles adds saturated aqueous common salt 500mL, washs 3 times.Obtain product 66g behind the reclaim under reduced pressure toluene.
Structural analysis to product shows that MS:m/z 1465; Elementary compositionly be: C63.09%, H8.53%, O28.38%, its molecular formula is C
77H
124O
26,
1H-NMR and
13C-NMR shows has increased by 1 methyl, 13 methylene radical carbochains and 4 unsaturated carbon atom structures, and other is identical with theasaponin.Its structure is as follows:
(formula V)
Embodiment 5
Employing standard GB/T 22237-2008 " the capillary mensuration of tensio-active agent " and Waring Blender foaming power assay method are as follows to the The performance test results of the senior fatty ester of theasaponin that embodiment 1-4 prepares:
Surface tension :≤30 milli ox/rice,
Foam volume (0.5% concentration, base fluid 100mL, 120 ℃): 〉=400mL,
Half foam life period (0.5% concentration, 120 ℃) :≤12500s.
The senior fatty ester of above presentation of results theasaponin of the present invention has superior refractory surfaces activity.
Embodiment 6
The senior fatty ester of theasaponin is as missible oil type inert ingredient.It is as follows to fill a prescription:
Deltamethrin 25g, the senior fatty ester 10g of theasaponin adds dimethylbenzene and is diluted to 1000g, stirs the system breast.This emulsion is not stratified, do not separate out good stability.The prevention effect that is used for cotton, fruit tree, vegetables pest is good.
Embodiment 7
The senior fatty ester of theasaponin is as the oil field foam flooding.The application experiment condition:
The parallel two-tube model, A pipe Φ 25 * 600mm, voidage 32%, rate of permeation 990 * 10
-3μ m
2B pipe Φ 25 * 600mm, voidage 36%, rate of permeation 3800 * 10
-3μ m
2Simulated oil viscosity 10.8mPa.s, rate of displacement 0.4mL/min, concentrations of foam 0.3%, foam vapour-liquid ratio 1: 1.
Effect: can improve tar productivity 20%.
Embodiment 8
The senior fatty ester of theasaponin is as protective skin cream.It is as follows to fill a prescription:
Mono-glycerides 2g, stearyl alcohol 3g, white oil 3g, tea oil 1g, the senior fatty ester 5g of theasaponin, glycerine 5g adds water to 1000mL.Heating system breast, be cooled to room temperature after, it is an amount of to add essence, sanitas, pigment, mixes.This protective skin cream good stability, not stratified, and have moist, whiten, anti-inflammatory, effect such as antipruritic.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
1. senior fatty ester of theasaponin, it is characterized in that: the senior fatty ester of described theasaponin has suc as formula the structure shown in the I:
(formula I)
Wherein, described R is C
12～C
18Saturated or unsaturated alkane.
2. the preparation method of the senior fatty ester of the described theasaponin of claim 1 may further comprise the steps being characterised in that:
Under the situation that catalyzer exists, theasaponin is mixed, reacts with high fatty alcohol, obtain suc as formula the senior fatty ester of the theasaponin shown in the I behind the separating catalyst.
3. the preparation method of the senior fatty ester of theasaponin according to claim 2, be characterised in that: described catalyzer is N, the mixture of N-dicyclohexylcarbodiimide and 4-dimethylamino pyridine, wherein, N, N-dicyclohexylcarbodiimide consumption is 1～1.5 times of molar mass of theasaponin, and 4-dimethylamino pyridine consumption is 5～10% of a theasaponin quality.
4. the preparation method of the senior fatty ester of theasaponin according to claim 2 is being characterised in that: described high fatty alcohol is meant C
12～C
18Saturated or unsaturated fatty alcohol, molar masss such as its add-on and theasaponin.
5. the preparation method of the senior fatty ester of theasaponin according to claim 2 is being characterised in that: the temperature of reaction of described theasaponin and high fatty alcohol is 20～30 ℃, and the reaction times is 8～16h.
6. the application of the senior fatty ester of the described theasaponin of claim 1 is characterized in that: the senior fatty ester of described theasaponin is directly used in missible oil type inert ingredient, oil field foam flooding, oil type cosmetics of everyday use as lipophilic nonionic bio-surfactant.
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
| CN103804460A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin myristinate surfactant and product thereof |
| CN103804463A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin octanoate surfactant and product thereof |
| CN103804462A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin laurate surfactant and product thereof |
| CN103819527A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin decylate surfactant and product thereof |
| CN103819526A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin stearate surfactant and product thereof |
| CN103819528A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin palmitate surfactant and product |
| CN104531120A (en) * | 2014-12-01 | 2015-04-22 | 程叶红 | Environment-friendly salt-resistant high-temperature-resistant oil displacement agent containing biological surfactant and used in petrochemical industry |
| CN106693830A (en) * | 2017-01-09 | 2017-05-24 | 青田中科植物科技有限公司 | Preparation method of benzyloxymethyl ether type modified tea saponin surfactant and product |
| CN106726781A (en) * | 2017-01-13 | 2017-05-31 | 华南理工大学 | A kind of camellia mildy wash and preparation method thereof |
| CN106880520A (en) * | 2017-01-13 | 2017-06-23 | 华南理工大学 | A kind of tea oil elite hair conditioner and preparation method thereof |
| CN111534384A (en) * | 2020-05-21 | 2020-08-14 | 上海毅诺生物科技有限公司 | Multipurpose cleaning agent containing tea saponin citrate modified surfactant and preparation method thereof |
| CN112126281A (en) * | 2020-10-10 | 2020-12-25 | 福建师范大学泉港石化研究院 | Preparation method of modified tea saponin and application of modified tea saponin as carbon black color paste wetting agent |
| CN114805467A (en) * | 2022-04-29 | 2022-07-29 | 西北大学 | Tea saponin gemini surfactant with strong foaming capacity under acidic and high-fat oil stains |
| CN115448974A (en) * | 2022-10-25 | 2022-12-09 | 杨江淼 | Surfactant and application thereof in daily chemical products |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731608A (en) * | 2012-06-29 | 2012-10-17 | 浙江大学 | Preparation method of tea saponin ester succinate surfactant and product thereof |
| CN103804462B (en) * | 2014-02-17 | 2016-01-06 | 浙江大学 | The preparation method of tea saponin laurate tensio-active agent and product |
| CN103819527A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin decylate surfactant and product thereof |
| CN103819526B (en) * | 2014-02-17 | 2016-01-06 | 浙江大学 | The preparation method of tea saponin stearate tensio-active agent and product |
| CN103819528B (en) * | 2014-02-17 | 2016-04-20 | 浙江大学 | The preparation method of tea saponin cetylate tensio-active agent and product |
| CN103804463B (en) * | 2014-02-17 | 2016-01-06 | 浙江大学 | The preparation method of tea saponin octanoate tensio-active agent and product |
| CN103819528A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin palmitate surfactant and product |
| CN103804463A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin octanoate surfactant and product thereof |
| CN103819527B (en) * | 2014-02-17 | 2016-01-06 | 浙江大学 | The preparation method of tea saponin decylate tensio-active agent and product |
| CN103804460B (en) * | 2014-02-17 | 2016-01-06 | 浙江大学 | The preparation method of tea saponin tetradecanoic acid ester surfactant and product |
| CN103804460A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin myristinate surfactant and product thereof |
| CN103804462A (en) * | 2014-02-17 | 2014-05-21 | 浙江大学 | Preparation method of tea saponin laurate surfactant and product thereof |
| CN103819526A (en) * | 2014-02-17 | 2014-05-28 | 浙江大学 | Preparation method of tea saponin stearate surfactant and product thereof |
| CN104531120A (en) * | 2014-12-01 | 2015-04-22 | 程叶红 | Environment-friendly salt-resistant high-temperature-resistant oil displacement agent containing biological surfactant and used in petrochemical industry |
| CN104531120B (en) * | 2014-12-01 | 2017-06-30 | 程叶红 | Environment-friendly type salt tolerant high temperature resistance oil displacement agent of the petrochemical industry containing biological surfactant |
| CN106693830A (en) * | 2017-01-09 | 2017-05-24 | 青田中科植物科技有限公司 | Preparation method of benzyloxymethyl ether type modified tea saponin surfactant and product |
| CN106726781A (en) * | 2017-01-13 | 2017-05-31 | 华南理工大学 | A kind of camellia mildy wash and preparation method thereof |
| CN106880520A (en) * | 2017-01-13 | 2017-06-23 | 华南理工大学 | A kind of tea oil elite hair conditioner and preparation method thereof |
| CN111534384A (en) * | 2020-05-21 | 2020-08-14 | 上海毅诺生物科技有限公司 | Multipurpose cleaning agent containing tea saponin citrate modified surfactant and preparation method thereof |
| CN112126281A (en) * | 2020-10-10 | 2020-12-25 | 福建师范大学泉港石化研究院 | Preparation method of modified tea saponin and application of modified tea saponin as carbon black color paste wetting agent |
| CN114805467A (en) * | 2022-04-29 | 2022-07-29 | 西北大学 | Tea saponin gemini surfactant with strong foaming capacity under acidic and high-fat oil stains |
| CN115448974A (en) * | 2022-10-25 | 2022-12-09 | 杨江淼 | Surfactant and application thereof in daily chemical products |
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Application publication date: 20110427 |