CN102658058B - 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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- CN102658058B CN102658058B CN201210107960.9A CN201210107960A CN102658058B CN 102658058 B CN102658058 B CN 102658058B CN 201210107960 A CN201210107960 A CN 201210107960A CN 102658058 B CN102658058 B CN 102658058B
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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 of method of being prepared cationic surfactant TSQA by Tea Saponin modification, belong to modified active agent technical field.
Background technology
Tea Saponin is a kind of oleanane type triterpene five rings saponins mixture, by triterpenoid saponin, glycogen, three parts of organic acid, formed, and under normal condition, be milky or faint yellow solid powder.Tea Saponin is a kind of natural non-ionic surface active agent, has good emulsification, dispersion, foaming, the performance such as wetting, is widely used in the industries such as daily use chemicals, medicine, agricultural chemicals.Tea Saponin structure is as follows:
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 most people.Yet the research of Tea Saponin all lays particular emphasis in extraction, application, few people attempt Tea Saponin to carry out modification.
Summary of the invention
The object of this invention is to provide a kind of method of being prepared cationic surfactant TSQA by Tea Saponin modification, prepare a kind of biological degradability and be better than traditional cationic surfactant.
According to technical scheme of the present invention,
A method of being prepared cationic surfactant TSQA by Tea Saponin modification, Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction equation is as follows:
By acid number content in assaying reaction liquid, follow the tracks of reaction process, when reactant liquor acid number drops to 7～10mg/g, reaction finishes.Now reaction conversion ratio reaches more than 60%.
Quaterisation equation is as follows:
By tertiary amine mass percent in assaying reaction liquid, follow the tracks of reaction process, when reactant liquor tertiary amine mass percent drops to 0～5%, reaction finishes.Now reaction conversion ratio reaches more than 90%.
A method of being prepared cationic surfactant TSQA by Tea Saponin modification, step is as follows:
(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 high boiling solvent, dissolve Tea Saponin: high boiling solvent mol ratio is 1: 8～12; Stirring is warming up to 90～110 ℃, until raw material dissolves completely; According to Tea Saponin: N, N-dimethyl-1,3-propane diamine mol ratio 1: 1.5～2 is got reactant, slowly by N, N-dimethyl-1,3-propane diamine adds in reactant liquor, stirs and is warming up to 120～130 ℃, logical N
2protection, reacts 6～8h; 0.01～0.03MPa, 90～130 ℃ of decompression distillation, remove unnecessary N, N-dimethyl-1,3-propane diamine; In reactant liquor, add precipitating reagent, until precipitate completely, tertiary amine is recrystallized to obtain;
(2) quaterisation:
It is in 50% 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-1,2-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 with absolute ethyl alcohol, filter; Get gained filtrate through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L; Eluent neutralizes with alkali, filters 100 ℃ of concentrated product cationic surfactant TSQA that obtain of filtrate.
The described Tea Saponin content that has extracted purifying is more than 80%.
Described high boiling solvent is triethylene glycol or ethylene glycol.
Described precipitating reagent is acetone, calcium oxide or barium hydroxide.
In described, be NaOH or KOH with the alkali of eluent.
Tool of the present invention has the following advantages: the performances such as cationic surfactant TSQA prepared by the present invention has better sterilization, antistatic, its excitant is little, has good compatibility with other surfactants.TSQA product is green surfactant, and biological degradability is better than traditional cationic surfactant.
Accompanying drawing explanation
The cationic surfactant TSQA infrared spectrum curve of Fig. 1 embodiment 1 preparation.
The infrared spectrum curve of the raw material Tea Saponin using in Fig. 2 embodiment.
The specific embodiment
Technical solution of the present invention is not limited to following the lifted specific embodiment, also comprises any combination between each specific embodiment.
Embodiment 1: in the present embodiment, the preparation method of the cationic surfactant being obtained by Tea Saponin modification (TSQA) is as follows:
(1) Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction: add the Tea Saponin (content is more than 80%) that has extracted purifying in reaction vessel, dissolve with triethylene glycol, its mol ratio is n (Tea Saponin): n (solvent)=1: 8, stirs and is warming up to 100 ℃.Until completely dissolved, according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 2, slowly add N, N-dimethyl-1,3-propane diamine, stirs and is warming up to 120 ℃, logical N
2protection, reaction 6h, measures acid number and tertiary amine value, stops reaction when acid number and tertiary amine value no longer changed with the reaction time.Decompression distillation, removes unnecessary N, N-dimethyl-1,3-propane diamine.In the solution obtaining, add acetone, tertiary amine is recrystallized to obtain.
(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-1,2-propane diols)=1: 2, add 3-chlorine-1,2-propylene glycol, sustained response 6h, measure at set intervals tertiary amine value, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, obtains 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.Filtrate is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with NaOH, filters the concentrated product TSQA-1 that obtains of filtrate.
Product qualitative analysis:
(1) mixed indicator development process: the product TSQA-1 that takes a morsel adds suitable quantity of water to dissolve in tool plug test tube, then adds 5ml mixed indicator and 5mL chloroform, fully layering after concussion, lower floor's chloroform is aobvious blue.Illustrate that product exists cationic surfactant.
(2) infrared spectrum: the product TSQA-1 that takes a morsel is infrared analysis (cm
-1, pressed disc method): 3411cm
-1place's broad peak be-CONH-in O-H stretching vibration absworption peak in N-H stretching vibration absworption peak and-OH; 2953cm
-1place is C-H stretching vibration absworption peak; 1646cm
-1place is the C=O characteristic absorption peak of acid amides; 1389cm
-1place's absworption peak is C-H flexural vibrations absworption peaks; 1266cm
-1place is the flexural vibrations absworption peak of C-O-H; 1200～1000cm
-1for C-N stretching vibration absworption peak; 731cm
-1the OOP vibration that place is 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
-1place) disappear.The carboxyl that can judge Tea Saponin reacts.Indicator development process in conjunction with above, can judge synthetic target product.
Embodiment 2: in the present embodiment, the preparation method of the cationic surfactant being obtained by Tea Saponin modification is as follows:
(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%) that has extracted purifying, with triethylene glycol, dissolve, its mol ratio is n (Tea Saponin): n (solvent)=1: 10, stirs and is warming up to 100 ℃.Until completely dissolved, according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 1.7, slowly add N, N-dimethyl-1,3-propane diamine, stirs and is warming up to 125 ℃, logical N
2protection, reaction 7h, measures acid number and tertiary amine value, stops reaction when acid number and tertiary amine value no longer changed with the reaction time.Decompression distillation, removes unnecessary N, N-dimethyl-1,3-propane diamine.In the solution obtaining, add acetone, tertiary amine is recrystallized to obtain.
(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-1,2-propane diols)=1: 1.5, add 3-chlorine-1,2-propylene glycol, sustained response 5h, measure at set intervals tertiary amine value, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, obtains 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.Filtrate is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with KOH, filters the concentrated product TSQA-2 that obtains of filtrate.
Embodiment 3: in the present embodiment, the preparation method of the cationic surfactant being obtained by Tea Saponin modification is as follows:
(1) Tea Saponin and N, N-dimethyl-1,3-propane diamine reaction: add the Tea Saponin (content is more than 80%) that has extracted purifying in reaction vessel, dissolve with diethylene glycol (DEG), its mol ratio is n (Tea Saponin): n (solvent)=1: 12.Stirring is warming up to 100 ℃.Until completely dissolved, according to mol ratio n (Tea Saponin): n (N, N-dimethyl-1,3-propane diamine)=1: 1.5, slowly add N, N-dimethyl-1,3-propane diamine, stirs and is warming up to 130 ℃, logical N
2protection, reaction 8h, measures acid number and tertiary amine value, stops reaction when acid number and tertiary amine value no longer changed with the reaction time.Decompression distillation, removes unnecessary N, N-dimethyl-1,3-propane diamine.In the solution obtaining, add acetone, tertiary amine is recrystallized to obtain.
(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-1,2-propane diols)=1: 1.5, add 3-chlorine-1,2-propylene glycol, sustained response 4h, measure at set intervals tertiary amine value, when tertiary amine value no longer changes, stop reaction.Excessive solvent is removed in decompression distillation, obtains 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.Filtrate is through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L.Eluent neutralizes with NaOH, filters the concentrated product TSQA-3 that obtains of filtrate.
Claims (3)
1. by Tea Saponin modification, prepared a method of cationic surfactant TSQA, it is characterized in that step is as follows:
(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 high boiling solvent, dissolve, Cha Zao Su ︰ high boiling solvent mol ratio is 1 ︰ 8～12; Stirring is warming up to 90 ~ 110 ℃, until raw material dissolves completely; According to tea soap element ︰ N, N-dimethyl-1,3-propane diamine mol ratio 1 ︰ 1.5～2 gets reactant, slowly by N, N-dimethyl-1,3-propane diamine adds in reactant liquor, stirs and is warming up to 120～130 ℃, logical N
2protection, reacts 6～8h; 0.01～0.03MPa, 90～130 ℃ of decompression distillation, remove unnecessary N, N-dimethyl-1,3-propane diamine; In reactant liquor, add precipitating reagent, until precipitate completely, tertiary amine is recrystallized to obtain;
(2) quaterisation:
It is in 50% isopropanol water solution that the tertiary amine that step (1) is obtained is dissolved in mass concentration, under 80～90 ℃ of conditions, according to Cha Zao Su ︰ 3-chloro-1,2-propane diols mol ratio 1 ︰ 1.5～2 slowly adds 3-chloro-1,2-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 with absolute ethyl alcohol, filter; Get gained filtrate through cationic ion-exchange resin, and with the HCl eluant solution of 0.5mol/L; Eluent neutralizes with alkali, filters 100 ℃ of concentrated product cationic surfactant TSQA that obtain of filtrate;
Described high boiling solvent is triethylene glycol or ethylene glycol; Described precipitating reagent is acetone.
2. by Tea Saponin modification, prepared as claimed in claim 1 the method for cationic surfactant TSQA, it is characterized in that: the described Tea Saponin content that has extracted purifying is more than 80%.
3. by Tea Saponin modification, prepared as claimed in claim 1 the method for cationic surfactant TSQA, it is characterized in that: in described, be NaOH or KOH with the alkali of eluent.
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| 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 |
| CN106693830B (en) * | 2017-01-09 | 2018-11-27 | 青田中科植物科技有限公司 | The preparation method and product of the modified Surface Activity of Tea Saponin agent of benzyloxymethyl ether type |
| CN109320701B (en) * | 2018-08-30 | 2020-11-10 | 深圳市聚亿新材料科技股份有限公司 | Preparation method of degradable fruit and vegetable antibacterial freshness protection package based on modified polylactic 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 |
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 |
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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 (2)
| Title |
|---|
| 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》.2004,第34卷(第5期),第54-56页. |
| 茶皂素改性有机硅季铵盐的合成及应用;冯章明等;《精细化工中间体》;20041031;第34卷(第5期);第54-56页 * |
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