CN102658058A - Method for preparing cationic surfactant TSQA by tea saponin modification - Google Patents
Method for preparing cationic surfactant TSQA by tea saponin modification Download PDFInfo
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- CN102658058A CN102658058A CN2012101079609A CN201210107960A CN102658058A CN 102658058 A CN102658058 A CN 102658058A CN 2012101079609 A CN2012101079609 A CN 2012101079609A CN 201210107960 A CN201210107960 A CN 201210107960A CN 102658058 A CN102658058 A CN 102658058A
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Abstract
A method for preparing a cationic surfactant TSQA by tea saponin modification belongs to the technical field of modified activators. According to the invention, the cationic surfactant TSQA is prepared by steps of reaction between tea saponin and N,N-dimethyl-1,3-propane diamine, quaternization and product purification. The prepared cationic surfactant TSQA has better sterilization performance and antistatic performance, has little irritation, and has good compatibility with other surfactants. The TSQA product is a green surfactant and has better biodegradability than a traditional cationic surfactant.
Description
Technical field
The present invention relates to a kind ofly prepare the method for cationic surfactant TSQA, belong to modified active agent technical field by the Tea Saponin modification.
Background technology
Tea Saponin is a kind of oleanane type triterpene five rings saponins mixture, is made up of triterpenoid saponin, glycogen, three parts of organic acid, under the normal condition, is milky or faint yellow solid powder.Tea Saponin is a kind of natural non-ionic surface active agent, has good emulsification, dispersion, foaming, performance such as wetting, is widely used in industries such as daily use chemicals, medicine, agricultural chemicals.The Tea Saponin structure is following:
Constantly perfect along with the extraction and purification process of Tea Saponin, the using value of Tea Saponin is also paid close attention to by majority.Yet the research of Tea Saponin all lays particular emphasis in extraction, the application, and few people attempt Tea Saponin is carried out modification.
Summary of the invention
The purpose of this invention is to provide and a kind ofly prepare the method for cationic surfactant TSQA, prepare a kind of biological degradability and be superior to traditional cationic surfactant by the Tea Saponin modification.
According to technical scheme of the present invention,
A kind ofly prepare the method for cationic surfactant TSQA by the Tea Saponin modification, Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction equation is following:
Follow the tracks of reaction process through acid number content in the assaying reaction liquid, when the reactant liquor acid number dropped to 7～10mg/g, reaction finished.This moment, reaction conversion ratio reached more than 60%.
The quaterisation equation is following:
Follow the tracks of reaction process through tertiary amine mass percent in the assaying reaction liquid, when reactant liquor tertiary amine mass percent dropped to 0～5%, reaction finished.This moment, reaction conversion ratio reached more than 90%.
A kind ofly prepare the method for cationic surfactant TSQA by the Tea Saponin modification, step is following:
(1) Tea Saponin and N, N-dimethyl-1, the reaction of 3-propane diamine:
In reaction vessel, add the Tea Saponin that has extracted purifying, with the high boiling solvent dissolving, Tea Saponin: the high boiling solvent mol ratio is 1: 8～12; Stirring is warming up to 90～110 ℃, dissolves fully until raw material; According to Tea Saponin: N, N-dimethyl-1,3-propane diamine mol ratio 1: 1.5～2 is got reactant, and slowly with N, N-dimethyl-1,3-propane diamine add in the reactant liquor, stir and are warming up to 120～130 ℃, logical N
2Protection, reaction 6～8h; 0.01 unnecessary N is removed in～0.03MPa, 90～130 ℃ of decompression distillation, N-dimethyl-1,3-propane diamine; In reactant liquor, add precipitating reagent, until fully the deposition till, be recrystallized tertiary amine;
(2) quaterisation:
It is in 50% the isopropanol water solution that the tertiary amine that step (1) is obtained is dissolved in mass concentration; Under 80～90 ℃ of conditions, according to Tea Saponin: 3-chloro-1,2-propane diols mol ratio 1: 1.5～2 slowly adds 3-chloro-1; The 2-propane diols; Stirring reaction 4～6h, excessive solvent is removed in 0.01～0.03MPa, 90～130 ℃ of decompression distillation, obtains thick product;
(3) product is purified:
Get the thick product of step (2) gained and be diluted to 0.05～0.1mol/L, filter with absolute ethyl alcohol; Get gained filtrating through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L; Eluent neutralizes with alkali, filters, and filtrates 100 ℃ to concentrate to obtain product cationic surfactant TSQA.
The said Tea Saponin content that has extracted purifying is more than 80%.
Said high boiling solvent is triethylene glycol or ethylene glycol.
Said precipitating reagent is acetone, calcium oxide or barium hydroxide.
Alkali with eluent in said is NaOH or KOH.
The present invention has following advantage: performances such as the cationic surfactant TSQA of the present invention's preparation has better sterilization, and is antistatic, its excitant is little, with other surfactants good compatibility is arranged.The TSQA product is a green surfactant, and biological degradability is superior to traditional cationic surfactant.
Description of drawings
The cationic surfactant TSQA infrared spectrum curve of Fig. 1 embodiment 1 preparation.
The infrared spectrum curve of employed raw material Tea Saponin among Fig. 2 embodiment.
The specific embodiment
Technical scheme of the present invention is not limited to the following specific embodiment of lifting, and also comprises the combination in any between each specific embodiment.
Embodiment 1: in this embodiment, the preparation method of the cationic surfactant (TSQA) that is obtained by the Tea Saponin modification is following:
(1) Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction: in reaction vessel, add the Tea Saponin (content is more than 80%) that has extracted purifying, with the triethylene glycol dissolving, its mol ratio is n (Tea Saponin): n (solvent)=1: 8, stirs and is warming up to 100 ℃.After treating to dissolve fully,, slowly add N according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 2, N-dimethyl-1, the 3-propane diamine stirs and is warming up to 120 ℃, logical N
2Protection, reaction 6h measures acid number and tertiary amine value, when acid number and tertiary amine value no longer changed with the reaction time, stops to react.Unnecessary N is removed in decompression distillation, N-dimethyl-1,3-propane diamine.In the solution that obtains, add acetone, be recrystallized tertiary amine.
(2) synthetic quaternary ammonium salt: the tertiary amine that step (1) is obtained is dissolved in isopropyl alcohol (50%) solution, under 80 ℃ of conditions, according to mol ratio n (Tea Saponin): n (3-chloro-1; The 2-propane diols)=1: 2; Add 3-chloro-1,2-propane diols, sustained response 6h; Measure tertiary amine value at set intervals, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, gets thick product.
(3) product is purified: the thick product that step (2) is obtained is diluted to 0.05mol/L with absolute ethyl alcohol, filters.Filtrating is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with NaOH, filters, and filtrating concentrating obtains product TSQA-1.
The product qualitative analysis:
(1) mixed indicator development process: the product TSQA-1 that takes a morsel adds the suitable quantity of water dissolving in tool plug test tube, adds 5ml mixed indicator and 5mL chloroform again, fully concussion back layering, and it is blue that lower floor's chloroform shows.Explain that there is cationic surfactant in product.
(2) infrared spectrum: the product TSQA-1 that takes a morsel is infrared analysis (cm
-1, pressed disc method): 3411cm
-1The place broad peak be-CONH-in N-H stretching vibration absworption peak and-OH in O-H stretching vibration absworption peak; 2953cm
-1The place is C-H stretching vibration absworption peak; 1646cm
-1The place is the C=O characteristic absorption peak of acid amides; 1389cm
-1Place's absworption peak is C-H flexural vibrations absworption peaks; 1266cm
-1The place is the flexural vibrations absworption peak of C-O-H; 1200～1000cm
-1Be C-N stretching vibration absworption peak; 731cm
-1The place is the OOP vibration of N-H.Contrast the infrared absorption peak of raw material Tea Saponin, can find the C=O characteristic absorption peak (1716cm of raw material-COOH
-1The place) disappears.The carboxyl that can judge Tea Saponin reacts.In conjunction with above indicator development process, can judge synthetic target product.
Embodiment 2: in this embodiment, the preparation method of the cationic surfactant that is obtained by the Tea Saponin modification is following:
(1) Tea Saponin and N, N-dimethyl-1, the reaction of 3-propane diamine.In reaction vessel, add the Tea Saponin (content is more than 80%) extracted purifying, with the triethylene glycol dissolving, its mol ratio is n (Tea Saponin): n (solvent)=1: 10, stirs and is warming up to 100 ℃.After treating to dissolve fully,, slowly add N according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 1.7, N-dimethyl-1, the 3-propane diamine stirs and is warming up to 125 ℃, logical N
2Protection, reaction 7h measures acid number and tertiary amine value, when acid number and tertiary amine value no longer changed with the reaction time, stops to react.Unnecessary N is removed in decompression distillation, N-dimethyl-1,3-propane diamine.In the solution that obtains, add acetone, be recrystallized tertiary amine.
(2) synthetic quaternary ammonium salt: the tertiary amine that step (1) is obtained is dissolved in isopropyl alcohol (50%) solution, under 85 ℃ of conditions, according to mol ratio n (Tea Saponin): n (3-chloro-1; The 2-propane diols)=1: 1.5; Add 3-chloro-1,2-propane diols, sustained response 5h; Measure tertiary amine value at set intervals, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, gets thick product.
(3) product is purified: the thick product that step (2) is obtained is diluted to 0.1mol/L with absolute ethyl alcohol, filters.Filtrating is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with KOH, filters, and filtrating concentrating obtains product TSQA-2.
Embodiment 3: in this embodiment, the preparation method of the cationic surfactant that is obtained by the Tea Saponin modification is following:
(1) Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction: in reaction vessel, add the Tea Saponin (content is more than 80%) that has extracted purifying, with the diethylene glycol (DEG) dissolving, its mol ratio is n (Tea Saponin): n (solvent)=1: 12.Stirring is warming up to 100 ℃.After treating to dissolve fully,, slowly add N according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 1.5, N-dimethyl-1, the 3-propane diamine stirs and is warming up to 130 ℃, logical N
2Protection, reaction 8h measures acid number and tertiary amine value, when acid number and tertiary amine value no longer changed with the reaction time, stops to react.Unnecessary N is removed in decompression distillation, N-dimethyl-1,3-propane diamine.In the solution that obtains, add acetone, be recrystallized tertiary amine.
(2) synthetic quaternary ammonium salt: the tertiary amine that step (1) is obtained is dissolved in isopropyl alcohol (50%) solution, under 90 ℃ of conditions, according to mol ratio n (Tea Saponin): n (3-chloro-1; The 2-propane diols)=1: 1.5; Add 3-chloro-1,2-propane diols, sustained response 4h; Measure tertiary amine value at set intervals, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, gets thick product.
(3) product is purified.The thick product that step (2) is obtained is diluted to 0.07mol/L with absolute ethyl alcohol, filters.Filtrating is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with NaOH, filters, and filtrating concentrating obtains product TSQA-3.
Claims (5)
1. one kind prepares the method for cationic surfactant TSQA by the Tea Saponin modification, it is characterized in that step is following:
(1) Tea Saponin and N, N-dimethyl-1, the reaction of 3-propane diamine:
In reaction vessel, add the Tea Saponin that has extracted purifying, with the high boiling solvent dissolving, tea Zao Su ︰ high boiling solvent mol ratio is 1:8～12; Stirring is warming up to 90 ~ 110 ℃, dissolves fully until raw material; According to Tea Saponin: N, N-dimethyl-1, reactant is got in 3-propane diamine mol ratio 1:1.5～2, and slowly with N, N-dimethyl-1,3-propane diamine add in the reactant liquor, stir and are warming up to 120～130 ℃, logical N
2Protection, reaction 6～8h; 0.01 unnecessary N is removed in～0.03MPa, 90～130 ℃ of decompression distillation, N-dimethyl-1,3-propane diamine; In reactant liquor, add precipitating reagent, until fully the deposition till, be recrystallized tertiary amine;
(2) quaterisation:
It is in 50% the isopropanol water solution that the tertiary amine that step (1) is obtained is dissolved in mass concentration; Under 80～90 ℃ of conditions, according to Tea Saponin: 3-chloro-1,2-propane diols mol ratio 1:1.5～2 slowly add 3-chloro-1; The 2-propane diols; Stirring reaction 4～6h, excessive solvent is removed in 0.01～0.03MPa, 90～130 ℃ of decompression distillation, obtains thick product;
(3) product is purified:
Get the thick product of step (2) gained and be diluted to 0.05～0.1mol/L, filter with absolute ethyl alcohol; Get gained filtrating through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L; Eluent neutralizes with alkali, filters, and filtrates 100 ℃ to concentrate to obtain product cationic surfactant TSQA.
2. prepared the method for cationic surfactant TSQA according to claim 1 by the Tea Saponin modification, it is characterized in that: the said Tea Saponin content that has extracted purifying is more than 80%.
3. prepared the method for cationic surfactant TSQA according to claim 1 by the Tea Saponin modification, it is characterized in that: said high boiling solvent is triethylene glycol or ethylene glycol.
4. prepared the method for cationic surfactant TSQA according to claim 1 by the Tea Saponin modification, it is characterized in that: said precipitating reagent is acetone, calcium oxide or barium hydroxide.
5. prepared the method for cationic surfactant TSQA according to claim 1 by the Tea Saponin modification, it is characterized in that: the alkali with eluent in said is NaOH or KOH.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107047936A (en) * | 2016-12-12 | 2017-08-18 | 安徽天泽饲料有限责任公司 | A kind of egg duck feed of green and healthy |
| CN107047967A (en) * | 2016-12-12 | 2017-08-18 | 安徽天泽饲料有限责任公司 | It is a kind of to improve the feed of duck's egg quality |
| CN109320701A (en) * | 2018-08-30 | 2019-02-12 | 奚正华 | A kind of preparation method of the degradable fruits and vegetables antibiotic preservative bag based on polydactyl acid |
| CN113186042A (en) * | 2021-04-19 | 2021-07-30 | 安徽达尔美生物科技有限公司 | Kitchen detergent and preparation method thereof |
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| US4406833A (en) * | 1982-06-04 | 1983-09-27 | Fats And Proteins Research Foundation, Inc. | Surfactants derived from fatty acid esters and proteinaceous material |
| CN87102063A (en) * | 1987-07-21 | 1988-06-15 | 阳运涛 | A kind of preparation method of non-ionic surface active agent |
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2012
- 2012-04-13 CN CN201210107960.9A patent/CN102658058B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4406833A (en) * | 1982-06-04 | 1983-09-27 | Fats And Proteins Research Foundation, Inc. | Surfactants derived from fatty acid esters and proteinaceous material |
| CN87102063A (en) * | 1987-07-21 | 1988-06-15 | 阳运涛 | A kind of preparation method of non-ionic surface active agent |
Non-Patent Citations (1)
| Title |
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| 冯章明等: "茶皂素改性有机硅季铵盐的合成及应用", 《精细化工中间体》, vol. 34, no. 5, 31 October 2004 (2004-10-31), pages 54 - 56 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107047936A (en) * | 2016-12-12 | 2017-08-18 | 安徽天泽饲料有限责任公司 | A kind of egg duck feed of green and healthy |
| CN107047967A (en) * | 2016-12-12 | 2017-08-18 | 安徽天泽饲料有限责任公司 | It is a kind of to improve the feed of duck's egg quality |
| 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 |
| CN109320701A (en) * | 2018-08-30 | 2019-02-12 | 奚正华 | A kind of preparation method of the degradable fruits and vegetables antibiotic preservative bag based on polydactyl acid |
| CN113186042A (en) * | 2021-04-19 | 2021-07-30 | 安徽达尔美生物科技有限公司 | Kitchen detergent and preparation method thereof |
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