CN102614808A - Organic silicon double-ion surfactant and preparation method thereof - Google Patents
Organic silicon double-ion surfactant and preparation method thereof Download PDFInfo
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- CN102614808A CN102614808A CN2012100590404A CN201210059040A CN102614808A CN 102614808 A CN102614808 A CN 102614808A CN 2012100590404 A CN2012100590404 A CN 2012100590404A CN 201210059040 A CN201210059040 A CN 201210059040A CN 102614808 A CN102614808 A CN 102614808A
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Abstract
The invention discloses an organic silicon double-ion surfactant and a preparation method thereof. The structural formula of the organic silicon double-ion surfactant is as follows. Ammonia ethyl ammonia propyl methyl dimethoxy silane, hexamethyldisiloxane, glycidyl ether and acid anhydride serve as raw materials of the organic silicon double-ion surfactant. A synthetic method comprises three steps: synthesizing the ammonia ethyl ammonia propyl trisiloxane, performing alkylation for ring opening of the glycidyl ether, and performing amidation. The synthetic process conditions of the organic silicon double-ion surfactant are that the molar ratio of the oxethyl-modified ammonia ethyl ammonia propyl trisiloxane to the acid anhydride is 1:4, the reaction temperature is 50 to 60 DEG C, the reaction time is 1 to 2 hours, and absolute ethyl alcohol serves as a solvent.
Description
Technical field:
The present invention relates to a kind of organosilicone gemini surfactant, the invention still further relates to a kind of preparation method of this Gemini surface active agent.
Background technology:
The research of organic silicon surfactant is existing for many years, and as far back as nineteen sixty-eight, W.G.Reid has at first synthesized cation silicon surface active agent (Me
3SiO)
2Si (Me)-(CH
2)
3OCH
2CH (OH) CH
2N
+Me
zRCl
-(R=H, Me).But the research of organosilicone gemini surfactant report seldom.2004; Han Fu etc. utilize primary amine groups and the maltonic acid-delta-lactone in the trisiloxanes of diamine base to carry out amidatioon; Secondary amine and low methoxypolyethylene glycol glycidol ether, diglycidyl ether carry out alkylation and have prepared novel sugared amide groups trisiloxanes Gemini surface active agent; This achievement in research be published in chemical journal (2004,62:733-737) with Journal of Surfactants and Detergents (2004,7:175-180) on the magazine and thesis for the doctorate in (Wuhan University; 2004,4).
Shandong light industry Academy Li Junying in 2009 etc. are with (RO)
2CH
3Si (CH
2) Cl and (CH
3)
2ONR
1N (CH
3)
2For raw material has synthesized organosilicon bi-quaternary ammonium salt surfactant, application Chinese patent (2009100515380.5).
At present, both at home and abroad the research of organosilicone gemini surfactant is reported seldom, because the property that the organosilicone gemini surfactant is had is attracting a lot of researchers constantly to carry out more researchs.We have synthesized a kind of organosilicone gemini surfactant that does not appear in the newspapers, and the synthetic kind that increases the organosilicone gemini surfactant of this product provides reference for the research of this aspect simultaneously.
Summary of the invention
The objective of the invention is for a kind of preparation organosilicone gemini surfactant and preparation method thereof is provided.This surfactant has surface-active preferably, preferably solubilising property, emulsibility and submissive performance.This preparation method's raw material is easy to get, and reaction condition is gentle, control, the product easy separation of being easy to easy and simple to handle.
What the present invention synthesized is to serve as second (third) the acid amides dimerization trisiloxane surfactant of connection base with the low carbon chain glycidol ether.Its structural formula is:
The concrete synthetic method of organic silicon surfactant comprises following three steps:
(1) aminoethyl aminopropyl trisiloxanes is synthetic
In the dry there-necked flask of the 50mL that has agitator, thermometer; Add aminoethyl aminopropyl methyl dimethoxysilane and HMDO mixture; The mol ratio of aminoethyl aminopropyl methyl dimethoxysilane and HMDO is 1: 5; Make catalyst (hydroxide flake potassium need be crushed into powder vacuum drying) with potassium hydroxide; The addition of catalyst is 0.45% of a reactant gross mass, and the air with in the nitrogen purge there-necked flask heats to 100 ℃ of back flow reaction 4h with oil bath.Reaction finishes, and reclaims unreacted HMDO, places separatory funnel to the light yellow transparent liquid that obtains, and using deionized water cyclic washing to aqueous pH values is 8.Remove moisture remaining in the residue and obtain weak yellow liquid aminoethyl aminopropyl trisiloxanes.
(2) ethyoxyl modification aminoethyl aminopropyl trisiloxanes is synthetic
In the dry there-necked flask of the 50mL that has agitator, thermometer; Add aminoethyl aminopropyl trisiloxanes and isopropyl alcohol; Stirring is warmed up to 40 ℃; In there-necked flask, slowly drip ethylene glycol diglycidylether and the aqueous isopropanol that (1.5h dropwises) prepares in advance, the mol ratio of the amount of aminoethyl aminopropyl trisiloxanes and glycidol ether is 2: 1.After dropwising, be warmed up to 50-60 ℃ of reaction 2.5-3h.Reaction finishes to remove isopropyl alcohol, places separatory funnel to spend deionised water remaining mixture, removes unreacted glycidol ether.Obtain faint yellow ethyoxyl modification aminoethyl aminopropyl trisiloxanes liquid.
(3) organic silicon surfactant is synthetic
Ethyoxyl modification aminoethyl aminopropyl trisiloxanes liquid and anhydrous ethanol solvent are mixed to join in the dry 50mL there-necked flask; Stirring is warmed up to 30-40 ℃; In there-necked flask, slowly drip acetic anhydride and the ethanolic solution that (1h dropwises) prepare in advance and carry out acylation reaction, the mol ratio of the amount of ethyoxyl modification aminoethyl aminopropyl trisiloxanes and acetic anhydride is 1: 4.After dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h.Reaction finishes to remove desolvates.Residue is 50 ℃ of dry 3h in air dry oven, get pale brown look thick liquid, and connecting base is low carbon chain diglycidyl ether acetamide dimerization trisiloxane surfactant.
Below be the synthetic reaction process (is example with the acetic anhydride) of organic silicon surfactant of the present invention:
(1) aminoethyl aminopropyl trisiloxanes is synthetic
(2) ethylene glycol diglycidylether open loop, alkylated reaction
(3) amidation process
Compared with prior art, the present invention has following beneficial effect:
(1) surfactant of the present invention is to serve as second (third) the acid amides dimerization trisiloxane surfactant that connects base with the low carbon chain diglycidyl ether, and the Gemini surface active agent that has this structure does not at present see that as yet bibliographical information is arranged.
(2) this product good water solubility, have organosilyl introducing to increase the compliance of product again, can be used as aspects application such as emulsifying agent, blowing agent, textile finishing softening agent.
(3) synthetic method of the present invention is simple, has that aminoethyl aminopropyl trisiloxanes is synthetic, glycidol ether alkylation and acid anhydrides amidation process constitute.Reaction condition is gentle, and easy and simple to handle being easy to controlled, and post processing is simple, and product is easy to separate and purifies.
Description of drawings
Accompanying drawing 1 is the infrared spectrogram of target product organic silicon surfactant of the present invention
The specific embodiment is following:
Synthetic (with n=2, acetic anhydride is that amidation reagent is an example) of embodiment 1 organic silicon surfactant
(1) aminoethyl aminopropyl trisiloxanes is synthetic
In the dry there-necked flask of the 50mL that has agitator, thermometer; Add 4.12g (0.02mol) aminoethyl aminopropyl methyl dimethoxysilane and 16.22g (0.10mol) HMDO mixture; The mol ratio of aminoethyl aminopropyl methyl dimethoxysilane and HMDO is 1: 5; Make catalyst (hydroxide flake potassium need be crushed into powder vacuum drying) with potassium hydroxide; The addition of catalyst is 0.45% of a reactant gross mass, and the air with in the nitrogen purge there-necked flask heats to 100 ℃ of back flow reaction 4h with oil bath.Reaction finishes, and reclaims unreacted HMDO, places separatory funnel to the light yellow transparent liquid that obtains, and using deionized water cyclic washing to aqueous pH values is 8.Remove moisture remaining in the residue and obtain weak yellow liquid aminoethyl aminopropyl trisiloxanes.
(2) ethyoxyl modification aminoethyl aminopropyl trisiloxanes is synthetic
In the dry there-necked flask of the 50mL that has agitator, thermometer; Add 1.50g (4.66mmol) aminoethyl aminopropyl trisiloxanes and 10mL isopropyl alcohol; Stirring is warmed up to 40 ℃; In there-necked flask, slowly drip ethylene glycol diglycidylether 0.406g (2.33mmol) and the 10mL aqueous isopropanol that (1.5h dropwises) prepares in advance, the mol ratio of the amount of aminoethyl aminopropyl trisiloxanes and glycidol ether is 2: 1.After dropwising, be warmed up to 50-60 ℃ of reaction 2.5-3h.Reaction finishes to remove isopropyl alcohol, places separatory funnel to spend deionised water (30mL * 3) remaining mixture, removes unreacted glycidol ether.Obtain faint yellow ethyoxyl modification aminoethyl aminopropyl trisiloxanes liquid.
(3) organic silicon surfactant is synthetic
3.27g (4.00mmol) ethyoxyl modification aminoethyl aminopropyl trisiloxanes liquid and 10mL anhydrous ethanol solvent are mixed to join in the dry 50mL there-necked flask; Stirring is warmed up to 30-40 ℃; In there-necked flask, slowly drip acetic anhydride 1.63g (16.0mmol) and the 10mL ethanolic solution that (1h dropwises) prepare in advance and carry out acylation reaction, the mol ratio of the amount of ethyoxyl modification aminoethyl aminopropyl trisiloxanes and acetic anhydride is 1: 4.After dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h.Reaction finishes to remove desolvates.Residue is 50 ℃ of dry 3h in air dry oven, get pale brown look thick liquid, and connecting base is low carbon chain diglycidyl ether acetamide dimerization trisiloxane surfactant.
Connect base and be propionamide dimerization trisiloxane surfactant synthetic the same of low carbon chain diglycidyl ether.
The infrared spectrum of embodiment 2 organic silicon surfactants
The target product that uses acetic anhydride to obtain is example, adopts coating method, with the Fourier infrared spectrum analyzer product is done infrared analysis, sees accompanying drawing 1.
3300cm
-1, 3081cm
-1Be N-H stretching vibration in the amide groups and deformation vibration absworption peak, 2957cm
-1The place is-CH
3,-CH
2-symmetry and antisymmetric stretching vibration peak, at 1632cm
-1For-the N-C=O stretching vibration peak, 1555cm
-1Be N-H flexural vibrations peaks, 1423cm
-1The place is-CH
2-the scissoring vibration peak, 1369cm
-1Be the C-N vibration peak, 1258cm
-1Be Si-CH
3In-CH
3Antisymmetry sex change vibration absorption peak, 1046cm
-1Be the stretching vibration absworption peak of Si-O-Si key and ehter bond C-O-C, 843cm
-1Be Si-C stretching vibration absworption peak.
Claims (3)
1. organosilicone gemini surfactant and preparation method thereof is characterized in that this surfactant has following structural formula:
It is second (third) the acid amides dimerization trisiloxane surfactant of low carbon chain glycidol ether that this organosilicone gemini surfactant connects base.
2. organosilicone gemini surfactant structure formula according to claim 1, it is characterized in that: concrete synthetic method comprises three steps: the first step is the synthetic of aminoethyl aminopropyl trisiloxanes; Second step was that alkylated reaction is carried out in the glycidol ether open loop; The 3rd step was carried out amidation process with acid anhydrides.
3. according to the preparation method of the said organosilicone gemini surfactant of claim 2, it is characterized in that: the 3rd step adopted the low-molecular-weight acid anhydrides as acylating reagent, and absolute ethyl alcohol is as solvent, and concrete operations are following:
Ethyoxyl modification aminoethyl aminopropyl trisiloxanes liquid and anhydrous ethanol solvent are mixed to join in the dry 50mL there-necked flask; Stirring is warmed up to 30-40 ℃; In there-necked flask, slowly drip acetic anhydride and the ethanolic solution that (1h dropwises) prepare in advance and carry out acylation reaction, the mol ratio of the amount of ethyoxyl modification aminoethyl aminopropyl trisiloxanes and acetic anhydride is 1: 4.After dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h.Reaction finishes to remove desolvates.Residue is 50 ℃ of dry 3h in air dry oven, get pale brown look thick liquid, and connecting base is low carbon chain diglycidyl ether acetamide dimerization trisiloxane surfactant.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406068A (en) * | 2013-08-21 | 2013-11-27 | 齐齐哈尔大学 | Organosilicon gemini surfactant containing amido bonds and preparation method thereof |
| CN103908926A (en) * | 2014-03-18 | 2014-07-09 | 五邑大学 | A dimeric polyoxyethylene ether trisiloxane surfactant and a preparing method thereof |
| CN105289409A (en) * | 2015-10-08 | 2016-02-03 | 陕西科技大学 | Quaternary ammonium salt organic silicon gemini 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 |
| WO2021126668A1 (en) * | 2019-12-19 | 2021-06-24 | Advansix Resins & Chemicals Llc | Surfactants for agricultural products |
| US11427760B2 (en) | 2020-02-05 | 2022-08-30 | Advansix Resins & Chemicals Llc | Surfactants for electronics |
| US11525105B2 (en) | 2019-12-20 | 2022-12-13 | Advansix Resins & Chemicals Llc | Surfactants for cleaning products |
| US11542428B2 (en) | 2019-12-31 | 2023-01-03 | Advansix Resins & Chemicals Llc | Surfactants for oil and gas production |
| US11571377B2 (en) | 2019-12-19 | 2023-02-07 | Advansix Resins & Chemicals Llc | Surfactants for use in personal care and cosmetic products |
| US11633481B2 (en) | 2019-12-20 | 2023-04-25 | Advansix Resins & Chemicals Llc | Surfactants for use in healthcare products |
| US11952394B2 (en) | 2019-08-22 | 2024-04-09 | Advansix Resins & Chemicals Llc | Siloxane derivatives of amino acids having surface-active properties |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103406068A (en) * | 2013-08-21 | 2013-11-27 | 齐齐哈尔大学 | Organosilicon gemini surfactant containing amido bonds and preparation method thereof |
| CN103908926A (en) * | 2014-03-18 | 2014-07-09 | 五邑大学 | A dimeric polyoxyethylene ether trisiloxane surfactant and a preparing method thereof |
| CN105289409A (en) * | 2015-10-08 | 2016-02-03 | 陕西科技大学 | Quaternary ammonium salt organic silicon gemini surfactant and preparation method thereof |
| CN105289409B (en) * | 2015-10-08 | 2017-04-26 | 陕西科技大学 | Quaternary ammonium salt organic silicon gemini 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 |
| US11952394B2 (en) | 2019-08-22 | 2024-04-09 | Advansix Resins & Chemicals Llc | Siloxane derivatives of amino acids having surface-active properties |
| AU2020407386B2 (en) * | 2019-12-19 | 2024-01-04 | Advansix Resins & Chemicals Llc | Surfactants for agricultural products |
| CN115087349A (en) * | 2019-12-19 | 2022-09-20 | 艾德凡斯化学公司 | Surfactants for agricultural products |
| US11571377B2 (en) | 2019-12-19 | 2023-02-07 | Advansix Resins & Chemicals Llc | Surfactants for use in personal care and cosmetic products |
| US11905304B2 (en) | 2019-12-19 | 2024-02-20 | Advansix Resins & Chemicals Llc | Surfactants for agricultural products |
| WO2021126668A1 (en) * | 2019-12-19 | 2021-06-24 | Advansix Resins & Chemicals Llc | Surfactants for agricultural products |
| US11525105B2 (en) | 2019-12-20 | 2022-12-13 | Advansix Resins & Chemicals Llc | Surfactants for cleaning products |
| US11633481B2 (en) | 2019-12-20 | 2023-04-25 | Advansix Resins & Chemicals Llc | Surfactants for use in healthcare products |
| US11542428B2 (en) | 2019-12-31 | 2023-01-03 | Advansix Resins & Chemicals Llc | Surfactants for oil and gas production |
| US11891568B2 (en) | 2019-12-31 | 2024-02-06 | Advansix Resins & Chemicals Llc | Surfactants for oil and gas production |
| US11427760B2 (en) | 2020-02-05 | 2022-08-30 | Advansix Resins & Chemicals Llc | Surfactants for electronics |
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