CN102206347A - Method for synthesizing hydroxyl polysiloxane - Google Patents
Method for synthesizing hydroxyl polysiloxane Download PDFInfo
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- CN102206347A CN102206347A CN 201110113387 CN201110113387A CN102206347A CN 102206347 A CN102206347 A CN 102206347A CN 201110113387 CN201110113387 CN 201110113387 CN 201110113387 A CN201110113387 A CN 201110113387A CN 102206347 A CN102206347 A CN 102206347A
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Abstract
The invention discloses a method for synthesizing hydroxyl polysiloxane. The method comprises the following steps of: (1) weighing a reaction monomer and alkali, adding into a reactor, and stirring at the temperature of between 40 and 80 DEG C for 0.5 to 2 hours; (2) adding deionized water and amine into the reactor, preserving the heat at the temperature of between 40 and 80 DEG C and reacting with stirring for 4 to 9 hours; and (3) performing water washing on a product until the product is neutral, and vacuumizing to obtain a hydroxyl polysiloxane product. The method for synthesizing the hydroxyl polysiloxane is simple and practical and is low in cost.
Description
Technical field
The present invention relates to the synthetic of polysiloxane, relate in particular to a kind of method of synthesis of hydroxy polysiloxane.
Background technology
The organopolysiloxane molecule has following properties: (1) excellent electric insulating, flame retardant resistance, weathering resistance; (2) ideal physiology and unreactiveness, toxicological harmless, pollution of ecological environment not; (3) second-order transition temperature is low, the high-and low-temperature resistance performance is good, high temperature rheology is little; (4) low surface tension causes easily sprawls film-forming properties, defoaming, hydrophobicity and oilness.Can form segmented copolymer with other macromolecular material.Particularly, organic siloxane emulsion is used for the padding finishing of fabric, can not only effectively isolate fiber, avoids fiber directly to contact with fiber, and the frictional coefficient of fiber surface is reduced, and makes fiber be easy to relatively sliding and shows flexibility.The fabric of organic siloxane emulsion arrangement has following advantage: (1) comfort feel, and ideal is gentle, cunning, bullet, endure performance; Good crease resistance, drape; (2) certain water resisting property, air permeability and good; (3) anti-friction of fabric, tearing toughness increase, and sewability strengthens; (4) blending/chemical ﹠ blended fabric has imitative cotton, imitative fiber crops, simulate wool or imitative silk effect; (5) make the dimensional stabilizing of fabrics such as cotton, fiber crops, hair, silk, shrink resistance improves.Therefore, organopolysiloxane synthesize on industrial application significant.
The Hyde of nineteen fifty-nine Dow Corning company etc. has applied for the patent of letex polymerization legal system hydroxy silicone emulsion first.Letex polymerization legal system hydroxy silicone emulsion, used raw material are D4 (octamethylcyclotetrasiloxane), emulsifying agent and catalyzer.Earlier that emulsifying agent is soluble in water during preparation, be added dropwise to D4 again and disperse, use acid or alkaline induced polymerization then.70 ° of C ~ 90 ° C of temperature of reaction, reaction times 8 ~ 10h.Post neutralization is finished in reaction so that acid, alkaline catalysts is ineffective.Make raw material, Witco 1298 Soft Acid with D4 and do that catalyzer, anion surfactant such as Sodium dodecylbenzene sulfonate are made emulsifying agent, water is dispersion medium, 80 ° of C ~ 90 ° the silicon breast that C reaction 8h makes, i.e. negatively charged ion hydroxy silicone emulsions.Make raw material with D4, cats product such as dodecyl benzyl dimethyl ammonium chloride or cetyl trimethylammonium bromide, octadecyl trimethyl ammonium chloride are made emulsifying agent, alkali metal hydroxide such as KOH, NaOH make catalyzer, the hydroxy silicone emulsion that makes through letex polymerization, i.e. cationic hydroxy silicon breast.Cationic hydroxy silicon breast relative molecular mass is less, and less stable can not use by compatibility with resin anion(R.A) or auxiliary agent, even a spot of resin anion(R.A) also can cause it that the breakdown of emulsion floating oil takes place in the work body lotion, so be restricted on using.
At present industrial intermittence commonly used, two step method synthesis of hydroxy polysiloxane promptly was monomer with the cyclosiloxane, and highly basic is catalyzer, aggregates into the high-molecular weight polysiloxane earlier, and further hydrolysis obtains the hydroxyl polysiloxane again.This method reaction process is wayward, unstable product quality, and energy consumption is big simultaneously.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of synthetic method of hydroxyl polysiloxane simple, with low cost.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of synthesis of hydroxy polysiloxane may further comprise the steps:
(1) takes by weighing reaction monomers and alkali, join in the reactor, stirred 0.5 ~ 2 hour down at 40 ~ 80 ℃;
(2) add deionized water and amine in reactor, 40 ~ 80 ℃ of insulated and stirred were reacted 4 ~ 9 hours;
(3) product water is washed till neutrality, vacuumizes again, promptly obtains product of the present invention.
Wherein, described reaction monomers is hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) or dimethyl siloxane mixed methylcyclosiloxane (DMC).
Described alkali is sodium hydroxide or potassium hydroxide.
Described amine is quadrol or 3,3'-diamino dipropylamine.
The mol ratio of described deionized water and reaction monomers is 1:10-250.
The mol ratio of described alkali and reaction monomers is 1:10 ~ 30.
The mol ratio of described amine and reaction monomers is 1:3 ~ 25.
In the method for synthesis of hydroxy polysiloxane of the present invention, deionized water, alkali and amine are catalysts, and under three's common katalysis, reaction monomers generation bulk polymerization generates the hydroxyl polysiloxane.Simultaneously, if find only water and alkali and reaction monomers reaction in the present invention's research, under above-mentioned reaction conditions, this reaction can not be carried out, and does not have the hydroxyl polysiloxane to generate; If only with alkali and amine and reaction monomers reaction, reaction can not be carried out; If only water and amine do not have or have only the minute quantity reaction monomers that polymerization can take place; Have only three and usefulness, just can reach good catalytic effect, reaction could be carried out smoothly.
In addition, the amine that uses in the method for synthesis of hydroxy polysiloxane of the present invention is the stronger amine of alkalescence, and what use among the present invention is quadrol or 3,3'-diamino dipropylamine, but be not limited to these two kinds, other similarly also can be with in the present invention.Simultaneously, among the present invention, amine and alkali such as are not in reaction at the mole proportionings, and amine should excessive adding.
Compared with prior art, the invention has the beneficial effects as follows:
The inventive method is an one-step synthesis, and under the common katalysis of minor amount of water, alkali and amine, reaction monomers generation mass polymerization generates the hydroxyl polysiloxane, and its reaction unit is simple, reaction process is simple, be convenient to realize that the while is also more efficient.The starting material that use in this process are conventional substances in addition, and the reaction conditions gentleness neither needs high temperature also not need protection of inert gas, and not only reaction safety is good, have saved cost simultaneously greatly.More stable by the inventive method synthetic product performance, produce easier may command, easier industrialization has favorable industrial application prospect.
Embodiment
For ease of the present invention is further understood, now describe the present invention in conjunction with specific embodiments.
Embodiment 1
Take by weighing 3 mol D4 and place reactor, add 0.3 mol sodium hydroxide, stirred 1 hour down, add 0.3 mol deionized water then at 60 ℃, 0.1 mol quadrol, keeping temperature is 60 ℃, continues to stir 6 hours, obtains the heavy-gravity transparent liquid.Product is washed to neutrality with deionized water, vacuumizes and remove monomer, obtain product.
Embodiment 2
Take by weighing 3 mol D4 and place reactor, add 0.25 mol sodium hydroxide, stirred 0.5 hour down at 80 ℃, add 0.05 mol deionized water then, 0.8 mol 3,3'-diamino dipropylamine, keeping temperature is 80 ℃, continues to stir 5 hours, obtains the heavy-gravity transparent liquid.Product is washed to neutrality with deionized water, vacuumizes and remove monomer, obtain product.
Embodiment 3
Take by weighing 3 mol D3 and place reactor, add 0.1 mol sodium hydroxide, stirred 2 hours down, add 0.012 mol deionized water then at 40 ℃, 0.2 mol quadrol, keeping temperature is 40 ℃, continues to stir 4 hours, obtains the heavy-gravity transparent liquid.Product is washed to neutrality with deionized water, vacuumizes and remove monomer, obtain product.
Embodiment 4
Take by weighing 3 mol DMC and place reactor, add 0.2 mol sodium hydroxide, stirred 1.5 hours down at 50 ℃, add 0.1 mol deionized water then, 0.6 mol 3,3'-diamino dipropylamine, keeping temperature is 50 ℃, continues to stir 8 hours, obtains the heavy-gravity transparent liquid.Product is washed to neutrality with deionized water, vacuumizes and remove monomer, obtain product.
Embodiment 5
Take by weighing 3 mol DMC and place reactor, add 0.15 mol sodium hydroxide, stirred 2 hours down, add 0.2 mol deionized water then at 70 ℃, 0.4 mol quadrol, keeping temperature is 70 ℃, continues to stir 9 hours, obtains the heavy-gravity transparent liquid.Product is washed to neutrality with deionized water, vacuumizes and remove monomer, obtain product.
Product performance by method preparation of the present invention are stable, and reaction process is simple, easier control, low production cost simultaneously.When the said products was used for the softness of cotton fibre and water repellent finish, its effect and industrial goods were suitable.
Claims (7)
1. the method for a synthesis of hydroxy polysiloxane is characterized in that may further comprise the steps:
(1) takes by weighing reaction monomers and alkali, join in the reactor, stirred 0.5 ~ 2 hour down at 40 ~ 80 ℃;
(2) add deionized water and amine in reactor, 40 ~ 80 ℃ of insulated and stirred were reacted 4 ~ 9 hours;
(3) product water is washed till neutrality, vacuumizes again, promptly obtains product of the present invention.
2. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: described reaction monomers is hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) or dimethyl siloxane mixed methylcyclosiloxane (DMC).
3. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: described alkali is sodium hydroxide or potassium hydroxide.
4. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: described amine is quadrol or 3,3'-diamino dipropylamine.
5. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: the mol ratio of described deionized water and reaction monomers is 1:10-250.
6. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: the mol ratio of described alkali and reaction monomers is 1:10 ~ 30.
7. the method for synthesis of hydroxy polysiloxane according to claim 1 is characterized in that: the mol ratio of described amine and reaction monomers is 1:3 ~ 25.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110113387 CN102206347A (en) | 2011-05-04 | 2011-05-04 | Method for synthesizing hydroxyl polysiloxane |
| CN201210108385.4A CN102649844B (en) | 2011-05-04 | 2012-04-14 | Preparation method of functionalized terminal group polysiloxane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110113387 CN102206347A (en) | 2011-05-04 | 2011-05-04 | Method for synthesizing hydroxyl polysiloxane |
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| CN102206347A true CN102206347A (en) | 2011-10-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 201110113387 Pending CN102206347A (en) | 2011-05-04 | 2011-05-04 | Method for synthesizing hydroxyl polysiloxane |
| CN201210108385.4A Expired - Fee Related CN102649844B (en) | 2011-05-04 | 2012-04-14 | Preparation method of functionalized terminal group polysiloxane |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210108385.4A Expired - Fee Related CN102649844B (en) | 2011-05-04 | 2012-04-14 | Preparation method of functionalized terminal group polysiloxane |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649844A (en) * | 2011-05-04 | 2012-08-29 | 石振东 | Preparation method of functionalized terminal group polysiloxane |
| CN102965954A (en) * | 2012-11-29 | 2013-03-13 | 常熟市新达纬编厂 | Preparation method of waterproof cotton fabric |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112962159A (en) * | 2021-03-01 | 2021-06-15 | 太仓逸枫化纤有限公司 | High-strength polyester filament yarn, preparation method and preparation device |
| CN114044905B (en) * | 2021-10-06 | 2023-01-06 | 复旦大学 | A kind of preparation method of end group functionalized polydimethylsiloxane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230632A (en) * | 1979-03-07 | 1980-10-28 | Sws Silicones Corporation | Preparation of heat stable silicone fluids |
| CN101386679A (en) * | 2008-10-23 | 2009-03-18 | 南京工业大学 | A kind of preparation method of cationic hydroxy silicone oil emulsion |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007036069A1 (en) * | 2007-08-01 | 2009-02-05 | Wacker Chemie Ag | Multi-stage process for the preparation of aminoalkyl-containing organopolysiloxanes |
| CN101838393B (en) * | 2010-04-29 | 2012-04-04 | 山东大学 | A kind of synthetic method of high molecular weight ethylpolysiloxane |
| CN102206347A (en) * | 2011-05-04 | 2011-10-05 | 石振东 | Method for synthesizing hydroxyl polysiloxane |
-
2011
- 2011-05-04 CN CN 201110113387 patent/CN102206347A/en active Pending
-
2012
- 2012-04-14 CN CN201210108385.4A patent/CN102649844B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4230632A (en) * | 1979-03-07 | 1980-10-28 | Sws Silicones Corporation | Preparation of heat stable silicone fluids |
| CN101386679A (en) * | 2008-10-23 | 2009-03-18 | 南京工业大学 | A kind of preparation method of cationic hydroxy silicone oil emulsion |
Non-Patent Citations (1)
| Title |
|---|
| 《化工生产与技术》 20070425 王高雄等 羟基硅油乳液的研究与应用进展 第40-43页 1-7 第14卷, 第2期 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649844A (en) * | 2011-05-04 | 2012-08-29 | 石振东 | Preparation method of functionalized terminal group polysiloxane |
| CN102965954A (en) * | 2012-11-29 | 2013-03-13 | 常熟市新达纬编厂 | Preparation method of waterproof cotton fabric |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649844B (en) | 2014-09-10 |
| CN102649844A (en) | 2012-08-29 |
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Open date: 20111005 |