CN1660882A - Method for preparing oxane trisilicate of containing glucosyacylamino - Google Patents
Method for preparing oxane trisilicate of containing glucosyacylamino Download PDFInfo
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- CN1660882A CN1660882A CN 200410092453 CN200410092453A CN1660882A CN 1660882 A CN1660882 A CN 1660882A CN 200410092453 CN200410092453 CN 200410092453 CN 200410092453 A CN200410092453 A CN 200410092453A CN 1660882 A CN1660882 A CN 1660882A
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- trisiloxanes
- glucosyacylamino
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- silanol
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Abstract
A process for preparing trisiloxane containing glucosylamido used as the assistant of agricultural chemical to decrease the surface tension of water includes catalytic reaction between hexamethyl disiloxane and aminosilane to obtain aminotrisiloxane, and reacting on lacton gluconate in methanol.
Description
Technical field
The present invention relates in molecule, form siliceous bonding, be with or without the compound that nitrogen, oxygen or bond with carbon reaction obtain, especially relate to a kind of preparation method who contains the trisiloxanes of glucosyacylamino.
Background technology
The method of the sugared amide group siloxanes of existing preparation, as German patent DE 4,318,539 have announced a kind of method for preparing sugared amide group siloxanes, by aminosiloxane and sugar lactone reaction, obtain product.But aminosiloxane is to be obtained by hydrosilation reaction by allyl amine.Wagner R. (Applied Organometallic Chemistry, 1996,10,421) reported a kind of method for preparing sugared amide group trisiloxanes, obtain hydrogeneous trisiloxanes by silane containing hydrogen and hexamethyldisiloxane reaction, do the reaction of catalyzer and allyl amine with Platinic chloride again and obtain amino trisiloxanes, with the sugar lactone reaction, obtain product then.
These method synthetic siloxanes, its building-up process all has hydrosilation reaction, and this reaction catalyst system therefor Platinic chloride price is more expensive; And the toxicity of allyl amine is very big.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, the preparation method of low, the nontoxic trisiloxanes that contains glucosyacylamino of a kind of cost is provided.
The preparation method who contains the trisiloxanes of glucosyacylamino of the present invention may further comprise the steps:
1. by hexamethyldisiloxane, aminosilane and basic catalyst, be 60～120 ℃, preferably react under 70～100 ℃ the situation in temperature of reaction; Wherein the mole proportioning of hexamethyldisiloxane and aminosilane is 1～20: 1, preferably 2～10: 1, and the mole dosage of catalyzer is a catalyzer: hexamethyldisiloxane and aminosilane mole sum=0.1～10: 100; After reaction is finished, make the basic catalyst inactivation, underpressure distillation obtains amino trisiloxanes;
2. amino trisiloxanes and Gluconolactone are made solvent at methyl alcohol, and temperature of reaction is 60～70 ℃, preferably reacts under the situation of methanol eddy; The mole proportioning of wherein amino trisiloxanes and Gluconolactone is 1～2: 1, preferably 1: 1; After reaction was finished, steaming desolventized, and obtains the glucosyacylamino trisiloxanes.
Aforesaid aminosilane comprises aminopropyl dimethoxy-methyl silane, aminopropyl diethoxymethyl silane, aminoethyl aminopropyl dimethoxy-methyl silane, aminoethyl aminopropyl diethoxymethyl silane etc.
Aforesaid basic catalyst can comprise: alkali metal hydroxide such as sodium hydroxide, potassium hydroxide etc., silicon alkoxide such as sodium silanolate, silanol potassium etc., such as quaternary ammonium hydroxide such as Tetramethylammonium hydroxide quaternary phosphonium hydroxide such as Si butyl phosphonium hydroxides etc., silanol quaternary ammonium salt such as tetramethyl-silanol ammonium etc., silanol quaternary alkylphosphonium salt such as tetrabutyl silanol Phosphonium etc.
The aforesaid basic catalyst inactivation that makes is when basic catalyst is alkali metal hydroxide, silicon alkoxide, adds sour catalyst neutralisation, makes it inactivation; When basic catalyst was quaternary ammonium hydroxide, quaternary phosphonium hydroxide, silanol quaternary ammonium salt, silanol quaternary alkylphosphonium salt, thermal degradation made it inactivation.
The trisiloxanes that contains glucosyacylamino that the present invention is prepared, the lowest surface tension of its aqueous solution are 21～22mN/m, and micelle-forming concentration is 5 * 10
-4～7 * 10
-4Mol/L; Its aqueous solution is 10～20 ° at the minimal contact angle of quartz surfaces, shows that its spreadability is very good, can be used as inert ingredient and is used for formulation of pesticide, and the promotion agricultural chemicals is sprawled plant leaf surface, increases drug effect.Its using method and other inert ingredient are similar.
The trisiloxanes that contains glucosyacylamino that the present invention is prepared, its advantage is the deficiency that has overcome original technology, has avoided the hydrosilation reaction step in original technology, reduced reaction process, and then avoided the toxicity of allyl amine, and catalyzer is cheap, and cost is low.
Embodiment
Below in conjunction with embodiment the present invention is made an explanation.
Embodiment 1
In reactor, add hexamethyldisiloxane 1.62kg, aminoethyl aminopropyl dimethoxy-methyl silane 2.06kg, Tetramethylammonium hydroxide 1.82g, heating for dissolving, temperature are controlled at 100 ℃, react after 4 hours, heat up and are heated to 130 ℃, make catalyst deactivation.Decompression steams aminoethyl aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 8 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.1mN/m, and micelle-forming concentration is 5.4 * 10
-4Mol/L is 14 ° at the minimal contact angle of quartz surfaces.
Embodiment 2
In reactor, add hexamethyldisiloxane 8.10kg, aminopropyl diethoxymethyl silane 1.91kg, potassium hydroxide 168g, heating for dissolving, temperature are controlled at 120 ℃, react after 5 hours, add the acetic acid catalyst neutralisation, make it inactivation, boil off unreacted hexamethyldisiloxane then.Decompression steams the aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 10 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.2mN/m, and micelle-forming concentration is 6.4 * 10
-4Mol/L is 13 ° at the minimal contact angle of quartz surfaces.
Embodiment 3
In reactor, add hexamethyldisiloxane 16.20kg, aminopropyl dimethoxy-methyl silane 1.63kg, Si butyl phosphonium hydroxides 151.8g, heating for dissolving, temperature is controlled at 80 ℃, reacts after 4 hours, heats up and is heated to 110 ℃, make catalyst deactivation, boil off unreacted hexamethyldisiloxane simultaneously.Decompression steams the aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 8 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.3mN/m, and micelle-forming concentration is 6.3 * 10
-4Mol/L is 16 ° at the minimal contact angle of quartz surfaces.
Embodiment 4
In reactor, add hexamethyldisiloxane 24.30kg, aminoethyl aminopropyl diethoxymethyl silane 2.34kg, silanol potassium 3.328kg, heating for dissolving, temperature are controlled at 90 ℃, react after 5 hours, add the acetic acid catalyst neutralisation, make it inactivation, boil off unreacted hexamethyldisiloxane then.Decompression steams aminoethyl aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 10 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.2mN/m, and micelle-forming concentration is 5.5 * 10
-4Mol/L is 15 ° at the minimal contact angle of quartz surfaces.
Embodiment 5
In reactor, add hexamethyldisiloxane 32.40kg, aminoethyl aminopropyl dimethoxy-methyl silane 2.06kg, tetramethyl-silanol ammonium 342.3g, heating for dissolving, temperature is controlled at 60 ℃, reacts after 4 hours, heats up and is heated to 130 ℃, make catalyst deactivation, boil off unreacted hexamethyldisiloxane simultaneously.Decompression steams aminoethyl aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 8 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.2mN/m, and micelle-forming concentration is 5.3 * 10
-4Mol/L is 17 ° at the minimal contact angle of quartz surfaces.
Embodiment 6
In reactor, add hexamethyldisiloxane 16.20kg, aminopropyl dimethoxy-methyl silane 1.63kg, tetrabutyl silanol Phosphonium 4.679kg, heating for dissolving, temperature is controlled at 70 ℃, reacts after 5 hours, heats up and is heated to 110 ℃, make catalyst deactivation, boil off unreacted hexamethyldisiloxane simultaneously.Decompression steams the aminopropyl trisiloxanes, and the Gluconolactone of mole numbers such as adding is made solvent with methyl alcohol, is heated to backflow, reacts 10 hours.Steaming desolventizes methyl alcohol, promptly gets product.The lowest surface tension of its aqueous solution of surveying with the K12 surface tension instrument is 21.1mN/m, and micelle-forming concentration is 6.4 * 10
-4Mol/L is 14 ° at the minimal contact angle of quartz surfaces.
Claims (14)
1, a kind of preparation method who contains the trisiloxanes of glucosyacylamino is characterized in that may further comprise the steps:
(1), be to react under 60～120 ℃ the situation in temperature of reaction by hexamethyldisiloxane, aminosilane and basic catalyst; Wherein the mole proportioning of hexamethyldisiloxane and aminosilane is 1～20: 1, and the mole dosage of catalyzer is a catalyzer: hexamethyldisiloxane and aminosilane mole sum=0.1～10: 100; After reaction is finished, make the basic catalyst inactivation, underpressure distillation obtains amino trisiloxanes;
(2) amino trisiloxanes and Gluconolactone are made solvent at methyl alcohol, and temperature of reaction is to react under 60～70 ℃ the situation; The mole proportioning of wherein amino trisiloxanes and Gluconolactone is 1～2: 1; After reaction was finished, steaming desolventized, and obtains the glucosyacylamino trisiloxanes.
2, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that temperature of reaction is 70～100 ℃.
3, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1, the mole proportioning that it is characterized in that hexamethyldisiloxane and aminosilane preferably 2～10: 1.
4, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that amino trisiloxanes and Gluconolactone are to react under the situation of methanol eddy.
5, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that the mole proportioning preferably 1: 1 of amino trisiloxanes and Gluconolactone.
6, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that described aminosilane comprises aminopropyl dimethoxy-methyl silane, aminopropyl diethoxymethyl silane, aminopropyl trimethoxysilane, aminoethyl aminopropyl dimethoxy-methyl silane, aminoethyl aminopropyl diethoxymethyl silane or aminoethyl aminopropyl trimethoxysilane.
7, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that described basic catalyst comprises alkali metal hydroxide, silicon alkoxide, quaternary ammonium hydroxide, quaternary phosphonium hydroxide, silanol quaternary ammonium salt or silanol quaternary alkylphosphonium salt.
8, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described alkali metal hydroxide is sodium hydroxide or potassium hydroxide.
9, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described silicon alkoxide is sodium silanolate or silanol potassium.
10, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described quaternary ammonium hydroxide is a Tetramethylammonium hydroxide.
11, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described quaternary phosphonium hydroxide is a Si butyl phosphonium hydroxides.
12, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described silanol quaternary ammonium salt is a tetramethyl-silanol ammonium.
13, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 7 is characterized in that described silanol quaternary alkylphosphonium salt is a tetrabutyl silanol Phosphonium.
14, a kind of preparation method who contains the trisiloxanes of glucosyacylamino as claimed in claim 1 is characterized in that the described basic catalyst inactivation that makes is when basic catalyst is alkali metal hydroxide, silicon alkoxide, adds sour catalyst neutralisation, makes it inactivation; When basic catalyst was quaternary ammonium hydroxide, quaternary phosphonium hydroxide, silanol quaternary ammonium salt, silanol quaternary alkylphosphonium salt, thermal degradation made it inactivation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410092453 CN1286846C (en) | 2004-12-28 | 2004-12-28 | Method for preparing oxane trisilicate of containing glucosyacylamino |
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| CN 200410092453 CN1286846C (en) | 2004-12-28 | 2004-12-28 | Method for preparing oxane trisilicate of containing glucosyacylamino |
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| CN1660882A true CN1660882A (en) | 2005-08-31 |
| CN1286846C CN1286846C (en) | 2006-11-29 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339385C (en) * | 2004-12-28 | 2007-09-26 | 中国日用化学工业研究院 | Polyglycol modified trisilicate containing glucose amide group and preparation method |
| CN101942097A (en) * | 2010-09-20 | 2011-01-12 | 中国日用化学工业研究院 | Method for preparing glycosyl amide modified polysiloxane |
| CN102382211A (en) * | 2011-08-30 | 2012-03-21 | 中科院广州化学有限公司 | Polymerizable nonionic silicone surfactant, its preparation method and its application |
| CN102614808A (en) * | 2012-03-08 | 2012-08-01 | 齐齐哈尔大学 | Organic silicon double-ion surfactant and preparation method thereof |
| CN102614807A (en) * | 2012-03-07 | 2012-08-01 | 中国日用化学工业研究院 | Tetrasiloxane contained dimeric glycosyl surfactant and synthesis method |
| CN103752211A (en) * | 2014-02-14 | 2014-04-30 | 北京工商大学 | Trisiloxane quaternary ammonium salt containing glucosamine groups and preparation method |
| CN104084092A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Trisiloxane gemini surfactant containing glucosamide group and preparation method of surfactant |
| CN104086577A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Organosilicon quaternary ammonium salt containing glucosamide group and preparation method of organosilicon quaternary ammonium salt |
| CN104086578A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Trisiloxane containing glucosamide group and preparation method of trisiloxane |
| CN105541894A (en) * | 2015-12-06 | 2016-05-04 | 广州市斯洛柯高分子聚合物有限公司 | Reactive type organosilicon wetting agent and preparation method thereof |
-
2004
- 2004-12-28 CN CN 200410092453 patent/CN1286846C/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339385C (en) * | 2004-12-28 | 2007-09-26 | 中国日用化学工业研究院 | Polyglycol modified trisilicate containing glucose amide group and preparation method |
| CN101942097A (en) * | 2010-09-20 | 2011-01-12 | 中国日用化学工业研究院 | Method for preparing glycosyl amide modified polysiloxane |
| CN101942097B (en) * | 2010-09-20 | 2012-09-05 | 中国日用化学工业研究院 | Method for preparing glycosyl amide modified polysiloxane |
| CN102382211B (en) * | 2011-08-30 | 2013-01-02 | 中科院广州化学有限公司 | Polymerizable nonionic silicone surfactant, preparation method and application thereof |
| CN102382211A (en) * | 2011-08-30 | 2012-03-21 | 中科院广州化学有限公司 | Polymerizable nonionic silicone surfactant, its preparation method and its application |
| CN102614807A (en) * | 2012-03-07 | 2012-08-01 | 中国日用化学工业研究院 | Tetrasiloxane contained dimeric glycosyl surfactant and synthesis method |
| CN102614808A (en) * | 2012-03-08 | 2012-08-01 | 齐齐哈尔大学 | Organic silicon double-ion surfactant and preparation method thereof |
| CN102614808B (en) * | 2012-03-08 | 2013-11-20 | 齐齐哈尔大学 | Organic silicon double-ion surfactant and preparation method thereof |
| CN103752211A (en) * | 2014-02-14 | 2014-04-30 | 北京工商大学 | Trisiloxane quaternary ammonium salt containing glucosamine groups and preparation method |
| CN103752211B (en) * | 2014-02-14 | 2015-12-09 | 北京工商大学 | A kind of trisiloxanes quaternary ammonium salt of sugary amide group and method for making |
| CN104084092A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Trisiloxane gemini surfactant containing glucosamide group and preparation method of surfactant |
| CN104086577A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Organosilicon quaternary ammonium salt containing glucosamide group and preparation method of organosilicon quaternary ammonium salt |
| CN104086578A (en) * | 2014-07-15 | 2014-10-08 | 北京工商大学 | Trisiloxane containing glucosamide group and preparation method of trisiloxane |
| CN104084092B (en) * | 2014-07-15 | 2015-12-02 | 北京工商大学 | A kind of trisiloxanes Gemini surface active agent of sugary amide group and method for making |
| CN105541894A (en) * | 2015-12-06 | 2016-05-04 | 广州市斯洛柯高分子聚合物有限公司 | Reactive type organosilicon wetting agent and preparation method thereof |
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| CN1286846C (en) | 2006-11-29 |
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