CN101735258B - Method for preparing micromolecular hydroxyl silicone oil - Google Patents
Method for preparing micromolecular hydroxyl silicone oil Download PDFInfo
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- CN101735258B CN101735258B CN2009101556273A CN200910155627A CN101735258B CN 101735258 B CN101735258 B CN 101735258B CN 2009101556273 A CN2009101556273 A CN 2009101556273A CN 200910155627 A CN200910155627 A CN 200910155627A CN 101735258 B CN101735258 B CN 101735258B
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Abstract
The invention discloses a method for preparing micromolecular hydroxyl silicone oil. The method comprises the followings steps of: dissolving hexamethylcyclotrisiloxane in acetone or tetrahydrofuran, adding ammonia spirit, of which the percentage concentration by weight is 20 to 30 percent, while stirring, after reaction, separating an oil phase on the upper layer, and purifying the oil phase to prepare the micromolecular hydroxyl silicone oil. The method has the advantages of simple and convenient production flow, strong operability, easy industrialization realization, low equipment investment cost, stable operation and safety properties, low-priced and easily bought raw materials, quick reaction and generation speeds, good product quality and the like.
Description
Technical field
Organosilicon derived product development research of the present invention field relates in particular to a kind of method for preparing micromolecular hydroxyl silicone oil.
Background technology
It is main chain with the Si-O key that organosilicon material is one type, on the Si atom, introduces the macromolecular compound of organic group as half organic, half inorganic structure of side chain again.It has performances such as good heatproof characteristic, dielectricity, weathering resistance, antioxidant, nontoxic no burn into physiology inertia and low surface tension, thereby is widely used in aerospace, military technique, electric industry, weaving papermaking, building industry, chemical industry, metal and fields such as paint industry, medical medical treatment.By the end of 2008; Whole world organosilicon industry having developed into product population is above 2,500,000 tons; Sales volume breaks through 12,000,000,000 dollars important new chemical materials industry, and it is bringing into play the effect that becomes more and more important to the development world new high-tech material technology and the upgrading and optimization of industrial structure.
Organosilicon product mainly is divided into silicone oil, Zylox, silicone resin and silane coupling agent four big classes.Wherein, Silicone oil and secondary processing product thereof be in the organosilicon product application surface the widest with one of maximum kind of consumption, in the back arrangement of lubricating oil, working oil, diffusion pump oil, shockproof oil, transformer oil, oil polish, medical treatment, makeup, thermal barrier, high temperature lubricating, fiber and fabric, improve the achieving success of aspects such as performance and the application of Zylox and resin.Low-molecular-weight hydroxyl silicone oil is claimed micromolecular hydroxyl silicone oil again; It is as a kind of important silicone oil product; Having good structure control effect, is the constitution controller of preparation high-performance high-temperature silicon disulfide rubber material, and generally addition is 4～6% in the high-temp glue prescription.In addition; The low-molecular-weight hydroxyl silicone oil emulsion also is used for the arrangement of fabric in a large number; Also can be used as the additive of plastics and the good treatment agent of filler silylanization; The home market annual requirement is more than 10,000 tons, and along with the continuous expansion of the market demand of products such as domestic melting silicone rubber and plastics, its application prospect will be more wide.
One Chinese patent application 200810014222.3 discloses a kind of compound method of short-chain hydroxyl silicone oil.It measures various raw materials by starting material component proportioning earlier, respectively acidic white earth, water, acetone, cyclotetrasiloxane is added then and is equipped with in the there-necked flask of reflux, under whipped state, adds the vitriol oil; Under the control reaction temperature condition, react, after having reacted, add Natural manganese dioxide and stirred 10 minutes; Suction filtration; To filtrate and distill recovery acetone down at 45 ℃, and then the adding aqueous sodium carbonate neutralizes standing demix under the temperature control condition with Rotary Evaporators; Organic layer to the upper strata adds water cleaning 1～2 time again, and standing demix is put and anhydrated again, then organic layer is sent into Rotary Evaporators and is warming up to 95 ℃, and low-boiling-point substance is sloughed in decompression, makes micromolecular hydroxyl silicone oil.
One Chinese patent application 200710073169.X discloses a kind of working method of dimethyl hydroxyl silicon oil.It is with dimethyldichlorosilane(DMCS) and sodium hydroxide solution at normal temperatures and pressures, and directly importing with the sodium chloride aqueous solution is circulation fluid, comprises in the response circuit of recycle pump and quantizer, is hydrolyzed, layering obtains dimethyl hydroxyl silicon oil after the condensation, neutralization reaction.Not only raw materials for production are with low cost, and operation is easy controlled, the reaction times is short, production rate is high, the circulate soln reusable edible.
One Chinese patent application 90105777.0 discloses a kind of lower molecular weight α, the preparation method of ω-siloxane glycol.It is that (general formula is (RO) with organoalkoxysilane
2SiR ' R ", wherein R is Me, Et; R ', R " be respectively H, Me, Et, Ph, Vi etc.) be raw material, be catalyzer with acid (like oxalic acid, hydrochloric acid, phosphoric acid or acetic acid etc.); In excessive water, be lower than under 50 ℃ of temperature and carry out twice hydrolysis, each 1～2 minute reaction times; Product mean polymerisation degree 2～10, hydroxy radical content 1～14%, residual alkoxyl group few (below 0.2%) or nothing.Suitablely especially make silicon rubber structured control agent, also as release paper coatings, releasing agent and room temperature vulcanized silicone rubber.
One Chinese patent application 200810156229.9 discloses a kind of preparation method of micromolecular hydroxyl silicone oil.It is being that feedstock production gets with ammoniacal liquor and dimethyldichlorosilane(DMCS); The ratio of ammoniacal liquor and dimethyldichlorosilane(DMCS) is 1: 1.2～2.0 in this invention; Temperature of reaction at room temperature can be carried out; Preferred temperature is 25 ℃, and the reaction solution of ammoniacal liquor and dimethyldichlorosilane(DMCS) through deposition, washing, filtration and dry, promptly gets colourless transparent liquid again.When the yellowing situation appears in product, get final product with activated carbon decolorizing.
The main flow production technique of existing domestic production micromolecular hydroxyl silicone oil adopts basically be solvent with acetic acid, under acidic conditions, carry out ring-opening polymerization with methyl cyclosiloxane (D4 or DMC) and aceticanhydride, again with acetic acid and acetate in sodium hydrogencarbonate or the aqueous sodium carbonate hydrolysis neutralization reaction.This method is because neutralization is incomplete; Product can be because of the existence generation dehydrating condensation of acetate in storage process, and it is big that viscosity becomes, and hydroxy radical content is descended; When using as the silicon rubber gross rubber antistructurizing agent; Can cause the sizing material poor processability, troubles such as storage time shortening, thereby limited the use of hydroxy silicon oil.In addition, this technology not only reactions step is more, also has product postprocessing working procedures such as neutralization, washing, is prone to produce a large amount of industrial wastewater pollution environment in the production.(organic silicon-fluorine information, 2005 the 6th phases, 34 pages)
Summary of the invention
The invention provides a kind of method for preparing micromolecular hydroxyl silicone oil, this method is easy to operate, and is with low cost.
A kind of method for preparing micromolecular hydroxyl silicone oil may further comprise the steps:
Hexamethyl cyclotrisiloxane is dissolved in acetone or the THF, and the adding weight percent concentration is 20～30% ammonia soln under the whipped state, and upper oil phase, the purified micromolecular hydroxyl silicone oil that promptly makes of upper oil phase are separated in the reaction back.
Preferably, the purification process of described upper oil phase is following:
Water is washed till neutrality with upper oil phase under the normal temperature, carries out suction filtration after the drying, and filtrating is carried out underpressure distillation under 90～95 ℃, remove low-boiling-point substance, makes micromolecular hydroxyl silicone oil.
Dry preferred the employing adds anhydrous magnesium sulfate toward being washed till in the neutral upper oil phase, and stirs more than half a hour.
Preferably, described temperature of reaction is 20～50 ℃, and the reaction times is 1～2 hour.
Preferably, the weight percent of hexamethyl cyclotrisiloxane, acetone or THF, ammonia soln is 1: 1～1.5: 1.5～2.
The inventive method not only Production Flow Chart is simple and easy to do, and is workable, be prone to realize industriallization, and equipment investment cost is low, and the operational safety performance is stable, and it is low and be easy to get to have material cost, and the reaction formation speed is fast, advantages such as good product quality.
Embodiment
The present invention will be helped to understand through following embodiment, but content of the present invention can not be limited.
Embodiment 1
As solvent, 25% ammoniacal liquor is catalyzer with acetone.Proportioning raw materials is: hexamethyl cyclotrisiloxane is 100 weight parts, and acetone is 100 weight parts, and 25% mass concentration ammoniacal liquor is 200 weight parts.
Experimental procedure: with acetone hexamethyl cyclotrisiloxane is dissolved earlier; Again the acetone soln adding of hexamethyl cyclotrisiloxane is equipped with in the there-necked flask of reflux; The ammonia soln of adding 25% under whipped state; Under 40 ℃ of conditions, reacted 1 hour, reaction is got upper oil phase after finishing while hot, can most of solvent be removed.
Then directly with upper oil phase at normal temperatures water be washed till neutrality, add anhydrous magnesium sulfate and stir half a hour, will filtrate behind the suction filtration and under 90～95 ℃, carry out underpressure distillation with Rotary Evaporators, slough low-boiling-point substance and promptly make micromolecular hydroxyl silicone oil.It is that 12.6%, 25 ℃ of following viscosimetric analysis is 18.5mm that product adopts the lithium aluminium hydride method to record hydroxyl value
2/ s.
Embodiment 2
As solvent, 25% ammoniacal liquor is catalyzer with acetone.Proportioning raw materials is: hexamethyl cyclotrisiloxane is 100 mass parts, and acetone is 150 mass parts, and 25% mass concentration ammoniacal liquor is 150 mass parts.
Experimental procedure: with acetone hexamethyl cyclotrisiloxane is dissolved earlier; Again hexamethyl cyclotrisiloxane solution is added and be equipped with in the there-necked flask of reflux; The ammonia soln of adding 20% under whipped state; Under 25 ℃ of conditions, reacted 2 hours, reaction is got upper oil phase after finishing while hot, can most of solvent be removed.
Then directly with upper oil phase at normal temperatures water be washed till neutrality, add anhydrous magnesium sulfate and stir half a hour, will filtrate behind the suction filtration and under 90～95 ℃, carry out underpressure distillation with Rotary Evaporators, slough low-boiling-point substance and promptly make micromolecular hydroxyl silicone oil.It is that 10.4%, 25 ℃ of following viscosimetric analysis is 22.6mm that product adopts the lithium aluminium hydride method to record hydroxyl value
2/ s.
Embodiment 3
As solvent, 25% ammoniacal liquor is catalyzer with THF.Proportioning raw materials is: hexamethyl cyclotrisiloxane is 100 mass parts, and THF is 100 mass parts, and 25% mass concentration ammoniacal liquor is 200 mass parts.
Experimental procedure: with THF hexamethyl cyclotrisiloxane is dissolved earlier; Again hexamethyl cyclotrisiloxane solution is added and be equipped with in the there-necked flask of reflux; The ammonia soln of adding 30% under whipped state; Under 40 ℃ of conditions, reacted 1 hour, reaction is got upper oil phase after finishing while hot, can most of solvent be removed.
Then directly with upper oil phase at normal temperatures water be washed till neutrality, add anhydrous magnesium sulfate and stir half a hour, will filtrate behind the suction filtration and under 90～95 ℃, carry out underpressure distillation with Rotary Evaporators, slough low-boiling-point substance and promptly make micromolecular hydroxyl silicone oil.It is that 11.3%, 25 ℃ of following viscosimetric analysis is 19.6mm that product adopts the lithium aluminium hydride method to record hydroxyl value
2/ s.
Embodiment 4
As solvent, 25% ammoniacal liquor is catalyzer with THF.Proportioning raw materials is: hexamethyl cyclotrisiloxane is 100 mass parts, and THF is 150 mass parts, and 25% mass concentration ammoniacal liquor is 150 mass parts.
Experimental procedure: with THF hexamethyl cyclotrisiloxane is dissolved earlier; Again hexamethyl cyclotrisiloxane solution is added and be equipped with in the there-necked flask of reflux; The ammonia soln of adding 25% under whipped state; Under 25 ℃ of conditions, reacted 2 hours, reaction is got upper oil phase after finishing while hot, can most of solvent be removed.
Directly the upper oil phase water is washed till neutrality then, adds anhydrous magnesium sulfate and stir half a hour, will filtrate behind the suction filtration and under 90～95 ℃, carry out underpressure distillation, slough low-boiling-point substance and promptly make micromolecular hydroxyl silicone oil with Rotary Evaporators.It is that 9.4%, 25 ℃ of following viscosimetric analysis is 23.9mm that product adopts the lithium aluminium hydride method to record hydroxyl value
2/ s.
Claims (5)
1. method for preparing micromolecular hydroxyl silicone oil may further comprise the steps:
Hexamethyl cyclotrisiloxane is dissolved in acetone or the THF, and the adding weight percent concentration is 20～30% ammonia soln under the whipped state, and upper oil phase, the purified micromolecular hydroxyl silicone oil that promptly makes of upper oil phase are separated in the reaction back.
2. method according to claim 1 is characterized in that, the purification process of described upper oil phase is following:
Water is washed till neutrality with upper oil phase under the normal temperature, carries out suction filtration after the drying, and filtrating is carried out underpressure distillation under 90～95 ℃, remove low-boiling-point substance, makes micromolecular hydroxyl silicone oil.
3. method according to claim 2 is characterized in that: described drying means adds anhydrous magnesium sulfate toward being washed till in the neutral upper oil phase, and stirs more than half a hour.
4. method according to claim 1 is characterized in that: described temperature of reaction is 20～50 ℃, and the reaction times is 1～2 hour.
5. method according to claim 1 is characterized in that: the weight ratio of described hexamethyl cyclotrisiloxane, acetone or THF, ammonia soln is 1: 1～1.5: 1.5～2.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101556273A CN101735258B (en) | 2009-12-18 | 2009-12-18 | Method for preparing micromolecular hydroxyl silicone oil |
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| CN2009101556273A CN101735258B (en) | 2009-12-18 | 2009-12-18 | Method for preparing micromolecular hydroxyl silicone oil |
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| CN101735258B true CN101735258B (en) | 2012-07-04 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102558559B (en) * | 2011-12-30 | 2014-03-05 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Method of synthetizing small molecule hydroxyl silicone oil through using continuation method |
| CN103665381B (en) * | 2013-12-27 | 2017-01-18 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Synthesis method of hydroxyl capped polydimethylsiloxane |
| CN105754102B (en) * | 2016-04-27 | 2018-08-21 | 广州道林合成材料有限公司 | A kind of hydroxy silicon oil and its continuous preparation method |
| CN105968362A (en) * | 2016-07-25 | 2016-09-28 | 江苏久吾高科技股份有限公司 | Purifying method and device for hydroxyl silicone oil |
| CN113087908A (en) * | 2021-04-29 | 2021-07-09 | 江苏众合硅基新材料有限公司 | Preparation method of low-viscosity hydroxyl silicone oil |
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