CN102614808B - 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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- CN102614808B CN102614808B CN2012100590404A CN201210059040A CN102614808B CN 102614808 B CN102614808 B CN 102614808B CN 2012100590404 A CN2012100590404 A CN 2012100590404A CN 201210059040 A CN201210059040 A CN 201210059040A CN 102614808 B CN102614808 B CN 102614808B
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- trisiloxane
- aminoethyl aminopropyl
- glycidyl ether
- necked flask
- surfactant
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Abstract
The invention discloses an acetamide trisiloxane surfactant preparation method with carbon chain glycidyl ether as linker. The structural formula of the organic silicon double-ion surfactant is as follows, n=2, m=0. 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 preparation method of organosilicone gemini tensio-active agent.
Background technology:
The research of organic silicon surfactant is existing for many years, and as far back as nineteen sixty-eight, at first W.G.Reid has synthesized positively charged ion Silicon surfactant (Me
3SiO)
2Si (Me)-(CH
2)
3OCH
2CH (OH) CH
2N
+Me
ZRCl
-(R=H, Me).But the research of organosilicone gemini tensio-active agent 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 amidation, secondary amine and low methoxypolyethylene glycol glycidyl ether, diglycidylether carry out alkylation and have prepared novel sugared amide group trisiloxanes Gemini surface active agent, this achievement in research is published in chemical journal (2004,62:733-737) with Journal of Surfactants and Detergents (2004,7:175-180) reach (Wuhan University in Ph D dissertation on the magazine, 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 the organosilicon Bis-quaternary Ammonium Salt Surfactant, application Chinese patent (2009100515380.5).
At present, both at home and abroad the research of organosilicone gemini tensio-active agent is reported seldom,, due to the property that the organosilicone gemini tensio-active agent has, attracted a lot of researchers constantly to carry out more researchs.We have synthesized a kind of organosilicone gemini tensio-active agent that has no report, the synthetic kind that increases the organosilicone gemini tensio-active agent of this product, and the research for this aspect simultaneously provides reference.
Summary of the invention
The objective of the invention is in order to provide take the low carbon chain glycidyl ether as connecting the preparation method of basic ethanamide dimerization trisiloxane surfactant.This tensio-active agent has surfactivity preferably, preferably lyotropy, emulsifying property and submissive performance.This preparation method's raw material is easy to get, and reaction conditions is gentle, and easy and simple to handle being easy to controlled, and product easily separates.
Synthesized of the present invention be take the low carbon chain glycidyl ether as connecting second (third) the acid amides dimerization trisiloxane surfactant of base.Its structural formula is:
The concrete synthetic method of organic silicon surfactant comprises following three steps:
(1) the aminoethyl aminopropyl trisiloxane is synthetic
In the dry there-necked flask of the 50mL with agitator, thermometer, add aminoethyl aminopropyl methyl dimethoxysilane and hexamethyldisiloxane mixture, the mol ratio of aminoethyl aminopropyl methyl dimethoxysilane and hexamethyldisiloxane is 1:5, make catalyzer (hydroxide flake potassium need to be crushed into powder vacuum-drying) with potassium hydroxide, the add-on of catalyzer is 0.45% of reactant total mass,, with the air in the nitrogen purge there-necked flask, with oil bath, heat to 100 ℃ of back flow reaction 4h.Reaction finishes, and reclaims unreacted hexamethyldisiloxane, and the light yellow transparent liquid that obtains is placed in separating funnel, with deionized water repetitive scrubbing to aqueous pH values, is 8.Remove moisture remaining in residuum and obtain weak yellow liquid aminoethyl aminopropyl trisiloxane.
(2) oxyethyl group modification aminoethyl aminopropyl trisiloxane is synthetic
In the dry there-necked flask of the 50mL with agitator, thermometer, add aminoethyl aminopropyl trisiloxane and Virahol, stirring is warmed up to 40 ℃, slowly drip ethylene glycol diglycidylether and the aqueous isopropanol that (1.5h dropwises) prepares in advance in there-necked flask, the mol ratio of the amount of aminoethyl aminopropyl trisiloxane and glycidyl ether is 2:1.After dropwising, be warmed up to 50-60 ℃ of reaction 2.5-3h.Reaction finishes to remove Virahol, and remaining mixture is placed in the separating funnel deionized water wash, removes unreacted glycidyl ether.Obtain faint yellow oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid.
(3) organic silicon surfactant is synthetic
Oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid and anhydrous ethanol solvent are mixed to join in dry 50mL there-necked flask; stirring is warmed up to 30-40 ℃; carry out acylation reaction to slowly dripping diacetyl oxide and the ethanolic soln that (1h dropwises) prepare in advance in there-necked flask, the mol ratio of the amount of oxyethyl group modification aminoethyl aminopropyl trisiloxane and diacetyl oxide is 1:4.After dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h.Reaction finishes except desolventizing.Residuum is 50 ℃ of dry 3h in air dry oven, obtain the brown color thick liquid, and connecting base is low carbon chain diglycidylether ethanamide dimerization trisiloxane surfactant.
Below the synthetic reaction process (take diacetyl oxide as example) of organic silicon surfactant of the present invention:
(1) the aminoethyl aminopropyl trisiloxane is synthetic
(2) ethylene glycol diglycidylether open loop, alkylated reaction
(3) amidate action
Compared with prior art, the present invention has following beneficial effect:
(1) tensio-active agent of the present invention is that the Gemini surface active agent that has at present this structure there is not yet bibliographical information take the low carbon chain diglycidylether as connecting second (third) the acid amides dimerization trisiloxane surfactant of base.
(2) this product good water solubility, have organosilyl introducing to increase the kindliness of product again, can be used as the aspects such as emulsifying agent, whipping agent, textile finishing softening agent and apply.
(3) synthetic method of the present invention is simple, has that the aminoethyl aminopropyl trisiloxane is synthetic, glycidyl ether alkylation and acid anhydrides amidate action form.Reaction conditions is gentle, and easy and simple to handle being easy to controlled, and aftertreatment is simple, and product is easy to separating-purifying.
Description of drawings
Fig. 1 is the infrared spectrogram of target product of the present invention.
Embodiment is as follows:
Synthetic (with n=2, diacetyl oxide is that amidation reagent is example) of embodiment 1 organic silicon surfactant
(1) the aminoethyl aminopropyl trisiloxane is synthetic
In the dry there-necked flask of the 50mL with agitator, thermometer, add 4.12g (0.02mol) aminoethyl aminopropyl methyl dimethoxysilane and 16.22g (0.10mol) hexamethyldisiloxane mixture, the mol ratio of aminoethyl aminopropyl methyl dimethoxysilane and hexamethyldisiloxane is 1:5, make catalyzer (hydroxide flake potassium need to be crushed into powder vacuum-drying) with potassium hydroxide, the add-on of catalyzer is 0.45% of reactant total mass,, with the air in the nitrogen purge there-necked flask, with oil bath, heat to 100 ℃ of back flow reaction 4h.Reaction finishes, and reclaims unreacted hexamethyldisiloxane, and the light yellow transparent liquid that obtains is placed in separating funnel, with deionized water repetitive scrubbing to aqueous pH values, is 8.Remove moisture remaining in residuum and obtain weak yellow liquid aminoethyl aminopropyl trisiloxane.
(2) oxyethyl group modification aminoethyl aminopropyl trisiloxane is synthetic
In the dry there-necked flask of the 50mL with agitator, thermometer, add 1.50g (4.66mmol) aminoethyl aminopropyl trisiloxane and 10mL Virahol, stirring is warmed up to 40 ℃, slowly drip ethylene glycol diglycidylether 0.406g (2.33mmol) and the 10mL aqueous isopropanol that (1.5h dropwises) prepares in advance in there-necked flask, the mol ratio of the amount of aminoethyl aminopropyl trisiloxane and glycidyl ether is 2:1.After dropwising, be warmed up to 50-60 ℃ of reaction 2.5-3h.Reaction finishes to remove Virahol, and remaining mixture is placed in separating funnel with deionized water wash (30mL * 3), removes unreacted glycidyl ether.Obtain faint yellow oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid.
(3) organic silicon surfactant is synthetic
3.27g (4.00mmol) oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid and 10mL anhydrous ethanol solvent are mixed to join in dry 50mL there-necked flask; stirring is warmed up to 30-40 ℃; carry out acylation reaction to slowly dripping diacetyl oxide 1.63g (16.0mmol) and the 10mL ethanolic soln that (1h dropwises) prepare in advance in there-necked flask, the mol ratio of the amount of oxyethyl group modification aminoethyl aminopropyl trisiloxane and diacetyl oxide is 1:4.After dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h.Reaction finishes except desolventizing.Residuum is 50 ℃ of dry 3h in air dry oven, obtain the brown color thick liquid, and connecting base is low carbon chain diglycidylether ethanamide dimerization trisiloxane surfactant.
Connect base and be propionic acid amide dimerization trisiloxane surfactant synthetic the same of low carbon chain diglycidylether.
The infrared spectra of embodiment 2 organic silicon surfactants
Be example with the target product that acetic anhydride obtains, adopt coating method, with the Fourier infrared spectrum determinator, product is done infrared analysis, see accompanying drawing 1.
3300cm
-1, 3081cm
-1For N-H stretching vibration in amide group and formation vibration absorption peak, 2957cm
-1Place is-CH
3,-CH
2-symmetry and antisymmetric stretching vibration peak, at 1632cm
-1For-the N-C=O stretching vibration peak, 1555cm
-1N-H flexural vibration peaks, 1423cm
-1Place is-CH
2-the scissoring vibration peak, 1369cm
-1The C-N vibration peak, 1258cm
-1For Si-CH
3In-CH
3Unsymmetrically sex change vibration absorption peak, 1046cm
-1For the stretching vibration absorption peak of Si-O-Si key and ehter bond C-O-C, 843cm
-1For Si-C stretching vibration absorption peak.
Claims (1)
1. the preparation method take the low carbon chain glycidyl ether as the ethanamide dimerization trisiloxane surfactant that connects base, it is characterized in that take the low carbon chain glycidyl ether as the ethanamide dimerization trisiloxane surfactant that connects base structural formula as:
Above-mentioned preparation method take the low carbon chain glycidyl ether as the ethanamide dimerization trisiloxane surfactant that connects base prepares according to the following steps: (1) aminoethyl aminopropyl trisiloxane synthetic:
In the dry there-necked flask of the 50mL with agitator, thermometer, add aminoethyl aminopropyl methyl dimethoxysilane and hexamethyldisiloxane mixture, the mol ratio of aminoethyl aminopropyl methyl dimethoxysilane and hexamethyldisiloxane is 1:5, make catalyzer with potassium hydroxide, the add-on of catalyzer is 0.45% of reactant total mass,, with the air in the nitrogen purge there-necked flask, with oil bath, heat to 100 ℃ of back flow reaction 4h; Reaction finishes, and reclaims unreacted hexamethyldisiloxane, and the light yellow transparent liquid that obtains is placed in separating funnel, with deionized water repetitive scrubbing to aqueous pH values, is 8; Remove moisture remaining in residuum and obtain weak yellow liquid aminoethyl aminopropyl trisiloxane; Described potassium hydroxide is obtained by the vacuum-drying that is crushed into powder of hydroxide flake potassium;
(2) oxyethyl group modification aminoethyl aminopropyl trisiloxane is synthetic:
In the dry there-necked flask of the 50mL with agitator, thermometer, add aminoethyl aminopropyl trisiloxane and Virahol, stirring is warmed up to 40 ℃, to the slow ethylene glycol diglycidylether and the aqueous isopropanol that prepare in advance of dropping in there-necked flask, complete above-mentioned dropping process with 1.5h, the mol ratio of the amount of aminoethyl aminopropyl trisiloxane and glycidyl ether is 2:1; After dropwising, be warmed up to 50-60 ℃ of reaction 2.5-3h, reaction finishes to remove Virahol, and remaining mixture is placed in the separating funnel deionized water wash, removes unreacted glycidyl ether; Obtain faint yellow oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid;
(3) organic silicon surfactant is synthetic:
oxyethyl group modification aminoethyl aminopropyl trisiloxane liquid and anhydrous ethanol solvent are mixed to join in dry 50mL there-necked flask, stirring is warmed up to 30-40 ℃, to in there-necked flask slowly the diacetyl oxide and the ethanolic soln that prepare in advance of dropping carry out acylation reaction, complete above-mentioned dropping process with 1h, the mol ratio of the amount of oxyethyl group modification aminoethyl aminopropyl trisiloxane and diacetyl oxide is 1:4, after dropwising, be warmed up to 50-60 ℃, continue reaction 1-2h, reaction finishes except desolventizing, residuum is 50 ℃ of dry 3h in air dry oven, obtain the brown color thick liquid, be take the low carbon chain glycidyl ether as connecting the ethanamide dimerization trisiloxane surfactant of base.
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| CN103406068B (en) * | 2013-08-21 | 2015-01-07 | 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 |
| 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 |
| KR20220045042A (en) | 2019-08-22 | 2022-04-12 | 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 | Siloxane derivatives of amino acids with surface-active properties |
| EP4076369A1 (en) | 2019-12-19 | 2022-10-26 | AdvanSix Resins & Chemicals LLC | Surfactants for use in personal care and cosmetic products |
| KR20220116518A (en) * | 2019-12-19 | 2022-08-23 | 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 | Surfactants for agricultural products |
| EP4077616A1 (en) | 2019-12-20 | 2022-10-26 | AdvanSix Resins & Chemicals LLC | Surfactants for cleaning products |
| KR20220114639A (en) | 2019-12-20 | 2022-08-17 | 어드밴식스 레진즈 앤드 케미컬즈 엘엘씨 | Surfactants for use in health care products |
| CN115151623B (en) | 2019-12-31 | 2023-09-12 | 艾德凡斯化学公司 | Surfactant for oil and gas production |
| DK4101009T3 (en) | 2020-02-05 | 2024-06-10 | Advansix Resins & Chemicals Llc | SURFACTANTS FOR ELECTRONICS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660883A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Polyglycol modified trisilicate containing glucose amide group and preparation method |
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
| CN1663672A (en) * | 2004-12-28 | 2005-09-07 | 中国日用化学工业研究院 | Dipolytrisiloxane surfactant containing glucose amide and its preparation method |
| CN102010437A (en) * | 2010-11-04 | 2011-04-13 | 中国日用化学工业研究院 | Polyethylene glycol-modified glycosyl group-containing tetrasiloxane and synthesizing method thereof |
-
2012
- 2012-03-08 CN CN2012100590404A patent/CN102614808B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660883A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Polyglycol modified trisilicate containing glucose amide group and preparation method |
| CN1660882A (en) * | 2004-12-28 | 2005-08-31 | 中国日用化学工业研究院 | Method for preparing oxane trisilicate of containing glucosyacylamino |
| CN1663672A (en) * | 2004-12-28 | 2005-09-07 | 中国日用化学工业研究院 | Dipolytrisiloxane surfactant containing glucose amide and its preparation method |
| CN102010437A (en) * | 2010-11-04 | 2011-04-13 | 中国日用化学工业研究院 | Polyethylene glycol-modified glycosyl group-containing tetrasiloxane and synthesizing method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Adsorption and Aggregation Behavior of Tetrasiloxane-Tailed Surfactants Containing Oligo(ethylene oxide) Methyl Ether and a Sugar Moiety;Guoyong Wang等;《Journal of Physical Chemistry B》;20110317;第115卷(第14期);全文 * |
| Carbohydrate-Modified Siloxane Surfactants and Their Adsorption and Aggregation Behavior in Aqueous Solution;Wang Guoyong等;《Journal of Physical Chemistry B》;20100503;第114卷(第20期);全文 * |
| ed Siloxane Surfactants and Their Adsorption and Aggregation Behavior in Aqueous Solution.《Journal of Physical Chemistry B》.2010,第114卷(第20期),6872-6877. |
| Guoyong Wang等.Adsorption and Aggregation Behavior of Tetrasiloxane-Tailed Surfactants Containing Oligo(ethylene oxide) Methyl Ether and a Sugar Moiety.《Journal of Physical Chemistry B》.2011,第115卷(第14期),3811-3818. |
| Wang Guoyong等.Carbohydrate-Modifi |
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