CN104788487A - Hydrolysis resistant Si-C-Si type cation organosilicon surfactant - Google Patents
Hydrolysis resistant Si-C-Si type cation organosilicon surfactant Download PDFInfo
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Abstract
The invention discloses a hydrolysis resistant Si-C-Si type cation organosilicon surfactant. The hydrolysis resistant Si-C-Si type cation organosilicon surfactant is prepared by performing reaction on the chloropropy carbosilane, N-methylimidazole, N-methylpyrrolidine, N, N-dimethylethanolamine, trimethylamine, triethylamine or pyridine. The prepared surfactant has good surface activity and a certain germicidal activity and can be used in the fields such as pesticide adjuvants, drug sustained release, functional nano-materials and textile processing aids.
Description
Technical field
A kind of hydrolysis Si-C-Si of the present invention type cationic silicones tensio-active agent, the preparation method of this tensio-active agent be specifically related to, belongs to the synthesis technical field of organic silicon surfactant.
Background technology
Organic silicon surfactant is hydrophobic chain link with silica/carbon alkane, connects the tensio-active agent that a class of one or more hydrophilic radical composition is new and effective.Not only there is the surfactivity more excellent than alkanes tensio-active agent and " surpass and sprawl " property, and the performance that the high-low temperature resistant, weather-resistant, nontoxic physiological inertia etc. that possess organosilicon material are excellent.Such organic silicon surfactant with the performance of its excellence be widely used in polyurethane foam, agricultural chemicals, textile auxiliary agent, day used additives, the field such as oil field chemical.To further develop along with organosilicon material and to the deep exploitation of organosilicon derived product, the kind of organic silicon surfactant also will constantly increase, and Application Areas also can constantly expand, and this is all developing direction and the study hotspot of tensio-active agent.
At present, organic silicon surfactant is mainly hydrophobic chain with Si-O-Si, although embody the advantages such as the excellent surfactivity of organic silicon surfactant, also there is the shortcoming of facile hydrolysis, especially has obvious bottleneck at agricultural agent.Because surfactivity can be caused to reduce after hydrolysis, often need in field now with the current when therefore using, not only bring trouble to user, and be difficult in a lot of pesticide preparation formula add, make its development in agricultural agent receive serious restriction.In organic silica tensio-active agent, the hydrolysis of Si-O-Si key is subject to the impact of many factors, and topmost influence factor is pH value and time.Under neutral (pH value is 6 ~ 8) condition, the permanent stability of organo-siloxane tensio-active agent are better; Be place in the solution of 5 ~ 6 or 8 ~ 9 to spend the night in pH value, its surfactivity can not significantly decline; Then must use immediately under acid or alkaline conditions; Under extreme pH value condition, during as sprayed certain plants growth regulator, solution can hydrolysis rapidly.
Although reported hydrolysis type organic silicon surfactant at present, if the silicon-carbon alkane nonionogenic tenside in US0269467A1 patent is in 3 ~ 10 scopes in pH value, place and be hydrolyzed hardly for 30 weeks, when pH value is 2 or 12, still have 72% (massfraction) not to be hydrolyzed, show higher resistance to hydrolysis; In US 0167269A1, multiple carbosilane surfactant is in 4 ~ 11 scopes in pH value, it is sprawled diameter and remains unchanged for 2 months, demonstrate good resistance to hydrolysis, in water, add this type of carbosilane surfactant that massfraction is 0.1%, its surface tension is 22 ~ 23 mN/m.But be substantially all non-ionic silicone surfactant, and adopt Si―H addition reaction method to introduce the hydrophilic radicals such as polyethers at hydrophobic segment, because Si―H addition reaction exists α and β addition reaction, so synthesized product out exists isomers, thus have impact on the activity of tensio-active agent.Adopt trimethyl silicane lithium methide to prepare chloropropyl silicon-carbon alkane before applicant and prepare Si-C-Si type organic silicon surfactant again, but employ trimethyl silicane lithium methide reagent costly in this method, see Tan, J. L.; Feng, S. Y., Colloid Polym. Sci., 2013,29 (6): 1487-1494, be not too applicable to suitability for industrialized production.
The organic silicon surfactant new variety of exploitation efficient stable, particularly synthesis has the organic silicon surfactant of resistant to hydrolysis performance, improve the stability of auxiliary agent to acid, alkali aqueous solution, broadened application scope, studies its application performance in every field very necessary.The present invention is directly by grignard reaction, and chloropropyl silicon-carbon alkane and reactive tertiary amine containing chloropropyl silicon-carbon alkane, then are prepared a kind of Si-C-Si type cationic silicones tensio-active agent of high surface hydrolysis by synthesis.
Summary of the invention
The object of the invention is to provide a kind of a kind of method preparing hydrolysis Si-C-Si type cationic silicones tensio-active agent efficiently.
The structural formula of a kind of hydrolysis Si-C-Si of the present invention type cationic silicones tensio-active agent is:
Preparation process is as follows:
Step 1: grignard reaction
N
2under protection, first chloromethyl silane is prepared into grignard reagent; Afterwards at N
2under protection, chloropropyl organoalkoxysilane or chloropropyl chlorosilane are added in the four-hole boiling flask that anhydrous tetrahydro furan or anhydrous diethyl ether are housed, drip chloromethyl silane grignard reagent, synthesis chloropropyl silicon-carbon alkane;
Step 2: quaterisation
The product chloropropyl silicon-carbon alkane of step 1 is loaded in there-necked flask, adds tertiary amine, solvent, at N
2under protection, system after 15 ~ 36 hours of reacting at 70 ~ 85 DEG C is down to room temperature; Be separated with n-hexane extraction, remove the solid that obtains after normal hexane afterwards in 0.1 MPa, 40 DEG C of dryings 1 day, after cooling Si-C-Si type cationic silicones tensio-active agent.
Described chloromethyl silane can be chloromethyl trimethyl silane, chloromethyl vinyl base dimethylsilane, chloromethyl ethyldimethylsilane, chloromethyl phenyl dimethylsilane, chloromethyl dimethylamine base silane or chloromethyl butyldimethylsilane.
Described tertiary amine can be N-Methylimidazole, N-crassitude, pyridine, Trimethylamine 99, triethylamine or N, N-dimethylethanolamine.
Described chloropropyl organoalkoxysilane can be chloropropyl dimethoxy (diethoxy) methyl-monosilane, r-chloropropyl trimethoxyl (triethoxy) silane or chloropropyl dimethyl methoxyl group (oxyethyl group) methyl-monosilane.
Described chloropropyl chlorosilane can be chloropropyl dichloro methyl silane, chloropropyl trichloro-silane or chloropropyl dimethylchlorosilane.
Described chloropropyl silicon-carbon alkane and tertiary amine mol ratio are 1:2 ~ 4.
Described solvent can be Virahol, butanols, acetonitrile or dimethyl formamide.
beneficial effect
Si-C-Si type cationic silicones tensio-active agent γ prepared by the present invention
cMCbe less than 24 mN/m, there is high surface, and there is not isomers to its surface-active impact, and there is excellent hydrolysis resistance, can be used for the fields such as inert ingredient, medicament slow release, functional nanomaterials, textile process auxiliary agent, and there is certain bactericidal properties.Compare Si-O-Si type organic silicon surfactant, Si-C-Si type organic silicon surfactant has Si-CH
2-Si key and there is excellent hydrolytic resistance, and Si-CH
2-Si key has hydrophobicity, and makes Si-C-Si type organic silicon surfactant have less CMC value.
Preparation method of the present invention is feasible, easy handling, is applicable to suitability for industrialized production application.
Embodiment
below in conjunction with embodiment, the present invention will be further described, but be not limited thereto.
embodiment 1
N
2under protection, in 250 ml four-hole boiling flasks, 8.6 g chloropropyl dichlorosilanes are joined in 50 ml anhydrous tetrahydro furans, is cooled to 0 DEG C, drip the trimethyl silicon based methylmagnesium-chloride of 8 g, naturally rise to room temperature, continue stirring 4 hours.After completion of the reaction, use anhydrous methanol termination reaction, filtering separation, then extract separatory, concentrate to obtain chloropropyl three silicon-carbon alkane.
In the 100ml there-necked flask of assembling prolong, add 5.0 g chloropropyl three silicon-carbon alkane, 4.0 g N-Methylimidazoles, 10ml Virahol, N
2in 85 DEG C of reactions 36 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 30 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml anhydrous methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by anhydrous methanol-ethyl acetate redissolve-precipitation 5 times.Product is in 0.1 MPa, and 40 DEG C of dryings obtained Si-C-Si type organic silicon surfactant after 1 day, and productive rate is 90%.Hermetically drying is preserved.γ
cMCbe 22.3 mN/m.When pH value is 2 or 12,88% (massfraction) is still had not to be hydrolyzed.
embodiment 2
N
2under protection, in 250 ml four-hole boiling flasks, 8.6 g chloropropyl dichlorosilanes are joined in 50 ml anhydrous tetrahydro furans, is cooled to 0 DEG C, drip the silica-based magnesium chloride grignard reagent of 12 g pheiiyldimetliyl, naturally rise to room temperature, continue stirring 5 hours.After completion of the reaction, use anhydrous methanol termination reaction, filtering separation, then extract separatory, concentrate to obtain chloropropyl three silicon-carbon alkane.
In the 100ml there-necked flask of assembling prolong, add 6.0 g containing phenyl-chloride propyl group three silicon-carbon alkane, 4.0 g N-Methylimidazoles, 10ml Virahol, N
2in 85 DEG C of reactions 36 hours under protection, after reaction terminates, naturally cool to room temperature.Be separated with normal hexane, remove normal hexane afterwards, obtain solid in 0.1 MPa, 40 DEG C of dryings 1 day, must contain phenyl Si-C-Si type organic silicon surfactant after cooling.Productive rate is 89%.Hermetically drying is preserved.γ
cMCbe 20.3 mN/m.When pH value is 2 or 12,92% (massfraction) is still had not to be hydrolyzed.
embodiment 3
N
2under protection, in 250 ml four-hole boiling flasks, 9.1 g chloropropylmethyldimethoxysilanes are joined in 50 ml anhydrous tetrahydro furans, drip the trimethyl silicon based magnesium chloride grignard reagent of 8 g, dropwise the micro-backflow of rear intensification, continue stirring 4 hours.After completion of the reaction, use anhydrous methanol termination reaction, filtering separation, then extract separatory, concentrate to obtain chloropropyl three silicon-carbon alkane.
In the 100ml there-necked flask of assembling prolong, add 5.0 g chloropropyl three silicon-carbon alkane, 4.0 g N-Methylimidazoles, 10ml Virahol, N
2in 85 DEG C of reactions 36 hours under protection, after reaction terminates, naturally cool to room temperature.Pour in 30 ml ethyl acetate the thick product that settles out into, pour out upper solution, then add 2 ml anhydrous methanols and dissolve thick product.Again the product of dissolving is joined in 30 ml ethyl acetate and again precipitate, by anhydrous methanol-ethyl acetate redissolve-precipitation 5 times.Product is in 0.1 MPa, and 40 DEG C of dryings obtained Si-C-Si type organic silicon surfactant after 1 day, and productive rate is 90%.Hermetically drying is preserved.γ
cMCbe 22.3 mN/m.When pH value is 2 or 12,88% (massfraction) is still had not to be hydrolyzed.
embodiment 4
N
2under protection, in 250 ml four-hole boiling flasks, 9.1 g chloropropylmethyldimethoxysilanes are joined in 50 ml anhydrous tetrahydro furans, drip the silica-based magnesium chloride grignard reagent of 12 g pheiiyldimetliyl, after dropwising, micro-back flow reaction that heats up 8 hours.After completion of the reaction, use anhydrous methanol termination reaction, filtering separation, then extract separatory, concentrate to obtain chloropropyl three silicon-carbon alkane.
In the 100ml there-necked flask of assembling prolong, add 6.0 g containing phenyl-chloride propyl group three silicon-carbon alkane, 4.0 g N-crassitudes, 10ml Virahol, N
2in 85 DEG C of reactions 30 hours under protection, after reaction terminates, naturally cool to room temperature.Be separated with normal hexane, remove normal hexane afterwards, obtain solid in 0.1 MPa, 40 DEG C of dryings 1 day, must contain phenyl Si-C-Si type pyrryl organic silicon surfactant after cooling.Productive rate is 91%.Hermetically drying is preserved.γ
cMCbe 20.7 mN/m.When pH value is 2 or 12,90% (massfraction) is still had not to be hydrolyzed.
embodiment 5
N
2under protection, in 250 ml four-hole boiling flasks, 11 g chloropropyl dichlorosilanes are joined in 50 ml anhydrous tetrahydro furans, is cooled to 0 DEG C, drip the trimethyl silicon based magnesium chloride grignard reagent of 8 g, micro-back flow reaction that heats up 6 hours.After completion of the reaction, use anhydrous methanol termination reaction, filtering separation, then extract separatory, concentrate to obtain chloropropyl three silicon-carbon alkane.
In the 100ml there-necked flask of assembling prolong, add 5.0 g chloropropyl four silicon-carbon alkane, 3.0 g pyridines, 10ml Virahol, N
2in 85 DEG C of reactions 32 hours under protection, after reaction terminates, naturally cool to room temperature.Be separated with normal hexane, remove normal hexane afterwards, obtain solid in 0.1 MPa, 40 DEG C of dryings 1 day, after cooling Si-C-Si type pyridyl organic silicon surfactant γ
cMCbe 21.5 mN/m.When pH value is 2 or 12,95% (massfraction) is still had not to be hydrolyzed.
Claims (7)
1. a hydrolysis Si-C-Si type cationic silicones tensio-active agent, is characterized in that the structural formula of described Si-C-Si type cationic silicones tensio-active agent is:
Preparation process is as follows:
Step 1: grignard reaction
N
2under protection, first chloromethyl silane is prepared into grignard reagent; Afterwards at N
2under protection, chloropropyl organoalkoxysilane or chloropropyl chlorosilane are added in the four-hole boiling flask that anhydrous tetrahydro furan or anhydrous diethyl ether are housed, drip chloromethyl silane grignard reagent, synthesis chloropropyl silicon-carbon alkane;
Step 2: quaterisation
The product chloropropyl silicon-carbon alkane of step 1 is loaded in there-necked flask, adds tertiary amine, solvent, at N
2under protection, system after 15 ~ 36 hours of reacting at 70 ~ 85 DEG C is down to room temperature; Be separated with n-hexane extraction, remove the solid that obtains after normal hexane afterwards in 0.1 MPa, 40 DEG C of dryings 1 day, after cooling Si-C-Si type cationic silicones tensio-active agent.
2. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described chloromethyl silane can be chloromethyl trimethyl silane, chloromethyl vinyl base dimethylsilane, chloromethyl ethyldimethylsilane, chloromethyl phenyl dimethylsilane, chloromethyl dimethylamine base silane or chloromethyl butyldimethylsilane.
3. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described tertiary amine can be N-Methylimidazole, N-crassitude, pyridine, Trimethylamine 99, triethylamine or N, N-dimethylethanolamine.
4. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described chloropropyl organoalkoxysilane can be chloropropyl dimethoxy (diethoxy) methyl-monosilane, r-chloropropyl trimethoxyl (triethoxy) silane or chloropropyl dimethyl methoxyl group (oxyethyl group) methyl-monosilane.
5. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described chloropropyl chlorosilane can be chloropropyl dichloro methyl silane, chloropropyl trichloro-silane or chloropropyl dimethylchlorosilane.
6. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described chloropropyl silicon-carbon alkane and tertiary amine mol ratio are 1:2 ~ 4.
7. a kind of hydrolysis Si-C-Si type cationic silicones tensio-active agent according to claim 1, is characterized in that described solvent can Virahol, butanols, acetonitrile or dimethyl formamide.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349274A (en) * | 2016-08-25 | 2017-01-25 | 浙江理工大学 | Organic silicon quaternary ammonium surfactant and preparation method thereof |
| CN106475005A (en) * | 2016-08-29 | 2017-03-08 | 浙江理工大学 | A kind of cation type organic silicon Gemini surface active agent and preparation method thereof |
| CN108102099A (en) * | 2017-11-28 | 2018-06-01 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| CN108905883A (en) * | 2018-06-15 | 2018-11-30 | 九江学院 | A kind of preparation method of Si-C-Si type anionic organic silicon surfactant |
| CN114806603A (en) * | 2022-05-26 | 2022-07-29 | 滁州学院 | Si-C novel organosilicon quaternary ammonium salt surfactant and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109054798B (en) * | 2018-07-13 | 2020-10-16 | 中国石油大学(华东) | Preparation method of high-temperature clay stabilizer for oil field |
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- 2015-05-11 CN CN201510233599.8A patent/CN104788487B/en active Active
Non-Patent Citations (1)
| Title |
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| 谭景林: "阳离子有机硅表面活性剂的制备及其聚集行为研究", 《中国博士论文全文数据库》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349274A (en) * | 2016-08-25 | 2017-01-25 | 浙江理工大学 | Organic silicon quaternary ammonium surfactant and preparation method thereof |
| CN106475005A (en) * | 2016-08-29 | 2017-03-08 | 浙江理工大学 | A kind of cation type organic silicon Gemini surface active agent and preparation method thereof |
| CN108102099A (en) * | 2017-11-28 | 2018-06-01 | 中国石油大学(华东) | A kind of preparation method of oil field high temperature clay stabilizer |
| CN108102099B (en) * | 2017-11-28 | 2020-10-16 | 中国石油大学(华东) | Preparation method of high-temperature clay stabilizer for oil field |
| CN108905883A (en) * | 2018-06-15 | 2018-11-30 | 九江学院 | A kind of preparation method of Si-C-Si type anionic organic silicon surfactant |
| CN114806603A (en) * | 2022-05-26 | 2022-07-29 | 滁州学院 | Si-C novel organosilicon quaternary ammonium salt surfactant and preparation method thereof |
| CN114806603B (en) * | 2022-05-26 | 2023-06-09 | 滁州学院 | Novel Si-C organosilicon quaternary ammonium salt surfactant and preparation method thereof |
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