CN102850550A - Di-hydroxyl silicone oil synthetic method - Google Patents
Di-hydroxyl silicone oil synthetic method Download PDFInfo
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- CN102850550A CN102850550A CN2011101798655A CN201110179865A CN102850550A CN 102850550 A CN102850550 A CN 102850550A CN 2011101798655 A CN2011101798655 A CN 2011101798655A CN 201110179865 A CN201110179865 A CN 201110179865A CN 102850550 A CN102850550 A CN 102850550A
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- dichlorodimethylsilane
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Abstract
The invention discloses a di-hydroxyl silicone oil synthetic method. The method includes at (-5)-41 DEG C., using dimethyldichlorosilane as raw material, using alkaline compounds as catalysts for performing interface condensation reaction for 3-8 h, to obtain di-hydroxyl silicone oil. The method is performed at conditions approximate to normal temperature and normal pressure, with moderate reaction, smooth and simple operation, and easy control. It is suitable for industrialized production.
Description
Technical field
The invention belongs to chemical field, be specifically related to the preparation method of a kind of pair of hydroxy silicon oil.
Background technology
The two hydroxy silicon oils of preparation generally adopt the preparation methods such as hydrolyzing chlorosilane method, organoalkoxysilane hydrolysis method, annular siloxane ring-opening polymerization method in the prior art.
The hydrolyzing chlorosilane method makes hydrolysis and polycondensation speed restive because when hydrolysis generates a large amount of hydrogenchloride, and therefore the two hydroxy silicon oils of preparation are relatively more difficult, operate various complexity.
The hydrolysis rate of organoalkoxysilane hydrolysis method is very slow, after stirring, reactant needs to place more than the 20h, and long reaction time, and contain unhydrolysed alkoxyl group in the product, productive rate is not high.
The ring opening catalyst of annular siloxane ring-opening polymerization method generally adopts strong acid such as sulfuric acid, acidic white earth or storng-acid cation exchange resin.The method complicated operation, be hydrolyzed not thorough, residual tart flavour.Reaction not exclusively.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of reaction temperature and, the preparation method of two hydroxy silicon oils simple to operate.
The preparation method of of the present invention pair of hydroxy silicon oil is as follows: dichlorodimethylsilane and the catalyzer that will be dissolved in organic solvent carry out liquid-liquid two-phase polycondensation reaction 3～8h in the time of-5～41 ℃.Reaction is carried out separatory after finishing, washing, and drying obtains two hydroxy silicon oils.
Preferably, described liquid-liquid two-phase polycondensation reaction is at room temperature carried out; Further preferably, under 0～10 ℃, carry out, more preferably, under 5 ℃, carry out.
Preferably, the reaction times is 3～5h.
Described organic solvent is selected from the one or more kinds of mixed solvents in methylene dichloride, trichloromethane, benzene and the toluene.Preferably, described organic solvent is methylene dichloride.
Described catalyzer comprises alkaline aqueous solution, and the solute of described alkaline aqueous solution is selected from one or more in alkali metal hydroxide, alkaline earth metal hydroxides, quaternary ammonium hydroxide and the ammoniacal liquor; A kind of in preferred sodium hydroxide, potassium hydroxide and the calcium hydroxide, more preferably sodium hydroxide.
The solute of described alkaline aqueous solution and the mol ratio of dichlorodimethylsilane are 2.01～2.40: 1, are preferably 2.05～2.10: 1.
Among the preparation method of the present invention, can also suitably add phase-transfer catalyst, described phase-transfer catalyst is selected from one or more in quaternary ammonium salt, ionogenic surfactant and the nonionic surface active agent.
In the phase-transfer catalyst, the preferred distearyl dimethyl ammonium chloride of quaternary ammonium salt, the preferred Sodium dodecylbenzene sulfonate of ionogenic surfactant, nonionic surface active agent preferred alkyl phenol polyethenoxy ether (APEO) or high-carbon fatty alcohol polyoxyethylene ether (AEO).
The consumption of described phase-transfer catalyst is 0.1～2% of dichlorodimethylsilane molar fraction.
Preferably, among the preparation method of the present invention, the dichlorodimethylsilane that is dissolved in organic solvent can be added drop-wise in the alkaline aqueous solution, in 0.5～2h, dropwise, pH is in 7～11 scope in control, and then preferred pH proceeds to react 1～7h in 7～8 scope.
Preferably, among the preparation method of the present invention, can in alkaline aqueous solution, drip the dichlorodimethylsilane that is dissolved in organic solvent, in 0.5～2h, dropwise, pH is in 7～9 scope in control, and then preferred pH proceeds to react 1～7h in 7～8 scope.
In a preferred technical scheme, the reaction equation that the present invention prepares two hydroxy silicon oils is as follows:
Wherein, n is 8～48 integer.
Reaction organic solvent of the present invention can be recycled, and the aqueous solution need not neutralization, and the salt that obtains can be used for industrial and agricultural production.
Liquid involved in the present invention-liquid two-phase polycondensation reaction belongs to surface reaction, refers to the chemical reaction between out-phase (each surrounding medium).That is, according to characteristic and lip-deep various chemical classes, content, existence and the character of surface in contact between the two-phase, and the various chemical reactions that occur under certain conditions.
Reaction can be carried out in various intermittences or flow reactor.The example of this class reactor has intermittently or the stirred reactor of continuous flow, and stirs tower or recirculation system flow reactor.
The present invention adopts interfacial to utilize the two hydroxy silicon oils of surface reaction preparation, and the preparation method carries out under near the condition of normal temperature and normal pressure, reaction temperature and, steadily, contain hardly acids in the reaction product (such as, HCl) impurity; Reaction times is short, generally can finish in 3-8h; Simple to operate, easy control is suitable for suitability for industrialized production.
Embodiment
In order to make those skilled in the art implement better the present invention, by way of example rather than the mode that limits provide the following example.
Embodiment 1
Get methylene dichloride (100mL) solution that contains the 50g dichlorodimethylsilane, splash into temperature and be in 0 ℃ the 77.91g sodium hydroxide solution (40wt%), maintain the temperature at 5 ℃, 0.5h drips off, and stirs; System pH is between 10-11 in the monitoring reaction course.After dropwising, room temperature reaction 3h.Leave standstill, layering separates, and washes organic phase with water three times, methylene dichloride and small molecules (the ring body polymkeric substance is such as hexamethyl cyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentaandoxane (D5)) are removed in underpressure distillation.Get the two hydroxy silicon oils of 17g, viscosity is 15cSt, and hydroxy radical content is 1.97%.
Embodiment 2
Get methylene dichloride (60mL) solution that contains the 50g dichlorodimethylsilane, splash into temperature and be in the mixing solutions of 0 ℃ 77.91g sodium hydroxide solution (40wt%) and 0.1g octadecyl sodium sulfonate, maintain the temperature at 5 ℃, 0.5h drips off, and stirs; System pH is between 9-10 in the monitoring reaction course.After dropwising, room temperature reaction 3h.Leave standstill, layering separates, and washes organic phase with water three times, and methylene dichloride and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 20g, viscosity is 19cSt, and hydroxy radical content is 1.75%.
Embodiment 3
Be that 0 ℃ 81.39g sodium hydroxide solution (40wt%) splashes in toluene (80mL) solution that contains the 50g dichlorodimethylsilane with temperature, maintain the temperature at 5 ℃, 0.5h drips off, and stirs; System pH is between 7-8 in the monitoring reaction course.After dropwising, room temperature reaction 3h.Leave standstill, layering separates, and washes organic phase with water three times, and toluene and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 18.5g, viscosity is 25cSt, and hydroxy radical content is 1.35%.
Embodiment 4
Get trichloromethane (120mL) solution that contains the 100g dichlorodimethylsilane, splash into temperature and be in 0 ℃ the 158.91g sodium hydroxide solution (40wt%), maintain the temperature at 5 ℃, 0.5h drips off, and stirs; System pH is between 10-11 in the monitoring reaction course.After dropwising, room temperature reaction 3h.Leave standstill, layering separates, and washes organic phase with water three times, and trichloromethane and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 36g, viscosity is 20cSt, and hydroxy radical content is 1.72%.
Embodiment 5
Get benzene (90mL) solution that contains the 50g dichlorodimethylsilane, splash into temperature and be in 3 ℃ the 79.84g ammoniacal liquor (35%), maintain the temperature at 15 ℃, 0.5h drips off, and stirs; System pH is between 9-10 in the monitoring reaction course.After dropwising, room temperature reaction 3h.Leave standstill, layering separates, and washes organic phase with water three times, and benzene and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 16g, viscosity is 16cSt, and hydroxy radical content is 1.89%.
Embodiment 6
Get methylene dichloride (100mL) mixing solutions that contains 50g dichlorodimethylsilane and 4.52g distearyl dimethyl ammonium chloride, splash into temperature and be in 10 ℃ the 79.04g ammoniacal liquor (35%), maintain the temperature at 15 ℃, 0.5h drips off, and stirs; System pH is between 10-11 in the monitoring reaction course.After dropwising, room temperature reaction 8h.Leave standstill, layering separates, and washes organic phase with water three times, and methylene dichloride and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 25g, viscosity is 27cSt, and hydroxy radical content is 1.31%.
Embodiment 7
Get the trichloromethane (50mL) and toluene (50mL) mixing solutions that contain 50g dichlorodimethylsilane and 2g alkylphenol polyoxyethylene (APEO), splash into temperature in-5 ℃ the 296.14g tetramethylammonium hydroxide aqueous solution (25wt%), maintain the temperature at 5 ℃, 1h drips off, and stirs; System pH is between 7-11 in the monitoring reaction course.After dropwising, 41 ℃ of reaction 5h.Leave standstill, layering separates, and washes organic phase with water three times, and trichloromethane and toluene and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 24.8g, viscosity is 32cSt, hydroxy radical content 1.21%.
Embodiment 8
Get the toluene (30mL) and methylene dichloride (50mL) mixing solutions that contain 50g dichlorodimethylsilane and 1g high-carbon fatty alcohol polyoxyethylene ether (AEO), splash into temperature and be in 5 ℃ the 39.52g tetramethylammonium hydroxide aqueous solution (25wt%), maintain the temperature at 5 ℃, 2h drips off, and stirs; System pH is between 7-11 in the monitoring reaction course.After dropwising, 41 ℃ of reaction 5h.Leave standstill, layering separates, and washes organic phase with water three times, and toluene and methylene dichloride and small molecules are removed in underpressure distillation.Get the two hydroxy silicon oils of 26g, viscosity is 40cSt, hydroxy radical content 0.95%.
Although, above with a general description of the specific embodiments the present invention having been done detailed description, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements all belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. the preparation method of two hydroxy silicon oils is characterized in that, dichlorodimethylsilane and the catalyzer that will be dissolved in organic solvent carry out liquid-liquid two-phase polycondensation reaction 3～8h in the time of-5～41 ℃, obtain two hydroxy silicon oils.
2. method according to claim 1 is characterized in that, described organic solvent is selected from the one or more kinds of mixed solvents in methylene dichloride, trichloromethane, benzene and the toluene.
3. method according to claim 2 is characterized in that, described organic solvent is methylene dichloride.
4. method according to claim 1 is characterized in that, described catalyzer comprises alkaline aqueous solution, and the solute of described alkaline aqueous solution is selected from one or more in alkali metal hydroxide, alkaline earth metal hydroxides, quaternary ammonium hydroxide and the ammoniacal liquor.
5. method according to claim 4 is characterized in that, the solute of described alkaline aqueous solution and the mol ratio of dichlorodimethylsilane are 2.01～2.40: 1.
6. method according to claim 5 is characterized in that, the solute of described alkaline aqueous solution and the mol ratio of dichlorodimethylsilane are 2.05～2.10: 1.
7. method according to claim 1 is characterized in that, described catalyzer also comprises phase-transfer catalyst, and described phase-transfer catalyst is selected from one or more in quaternary ammonium salt, ionogenic surfactant and the nonionic surface active agent.
8. method according to claim 7 is characterized in that, the consumption of described phase-transfer catalyst is 0.1～2% of dichlorodimethylsilane molar fraction.
9. each described method is characterized in that according to claim 1-8, and the dichlorodimethylsilane that will be dissolved in organic solvent is added drop-wise in the alkaline aqueous solution, dropwises in 0.5～2h, and pH is in 8～11 scope in control, then proceeds to react 1～7h.
10. each described method is characterized in that according to claim 1-8, drips the dichlorodimethylsilane that is dissolved in organic solvent in alkaline aqueous solution, dropwises in 0.5～2h, and pH is in 7～9 scope in control, then proceeds to react 1～7h.
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| CN201110179865.5A CN102850550B (en) | 2011-06-29 | 2011-06-29 | Di-hydroxyl silicone oil synthetic method |
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| CN201110179865.5A CN102850550B (en) | 2011-06-29 | 2011-06-29 | Di-hydroxyl silicone oil synthetic method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942820A (en) * | 2019-03-26 | 2019-06-28 | 浙江置正有机硅有限公司 | A kind of preparation method of aminomethyl phenyl hydroxy silicon oil and oil water separator for the preparation of aminomethyl phenyl hydroxy silicon oil |
| CN115612564A (en) * | 2022-10-24 | 2023-01-17 | 句容宁武高新技术发展有限公司 | Water-soluble oil stain emulsifier and synthesis method thereof |
| CN116656248A (en) * | 2023-06-10 | 2023-08-29 | 广东简彩纸业科技有限公司 | Non-backing paper self-adhesive label paper |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995098A (en) * | 2006-09-22 | 2007-07-11 | 刘造时 | Method for producing short chain hydroxy silicone oil |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995098A (en) * | 2006-09-22 | 2007-07-11 | 刘造时 | Method for producing short chain hydroxy silicone oil |
Non-Patent Citations (1)
| Title |
|---|
| 王高雄等: "羟基硅油乳液的研究与应用进展", 《化工生产与技术》, vol. 14, no. 2, 25 April 2007 (2007-04-25), pages 40 - 43 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942820A (en) * | 2019-03-26 | 2019-06-28 | 浙江置正有机硅有限公司 | A kind of preparation method of aminomethyl phenyl hydroxy silicon oil and oil water separator for the preparation of aminomethyl phenyl hydroxy silicon oil |
| CN115612564A (en) * | 2022-10-24 | 2023-01-17 | 句容宁武高新技术发展有限公司 | Water-soluble oil stain emulsifier and synthesis method thereof |
| CN116656248A (en) * | 2023-06-10 | 2023-08-29 | 广东简彩纸业科技有限公司 | Non-backing paper self-adhesive label paper |
| CN116656248B (en) * | 2023-06-10 | 2023-12-19 | 广东简彩纸业科技有限公司 | Non-backing paper self-adhesive label paper |
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