CN1821284A - Method for catalytically synthesizing small molecular hydroxy silicon oil by potassium hydroxide - Google Patents
Method for catalytically synthesizing small molecular hydroxy silicon oil by potassium hydroxide Download PDFInfo
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- CN1821284A CN1821284A CN 200610038165 CN200610038165A CN1821284A CN 1821284 A CN1821284 A CN 1821284A CN 200610038165 CN200610038165 CN 200610038165 CN 200610038165 A CN200610038165 A CN 200610038165A CN 1821284 A CN1821284 A CN 1821284A
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- potassium hydroxide
- silicon oil
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- hydroxy silicon
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Abstract
The present invention provides potassium hydroxide catalyzed process of synthesizing small molecular hydroxyl silicon oil. The synthesis process is one ring-opening polymerization process with methyl silane as main material, toluene as reaction buffering agent, potassium hydroxide as catalyst, and sulfuric acid as the neutralizing agent. The material composition includes methyl silane 100 weight portions, potassium hydroxide 10-70 weight portions, toluene 70-120 weight portions, and sulfuric acid 8.5-60 weight portions. The technological conditions include reaction temperature 100-150deg.c, reaction time 2-7 hr, hydrolysis temperature 30-70deg.c, hydrolysis time 1-3 hr and stirring rotation speed higher than 70 rpm. The synthesized small molecular hydroxyl silicon oil has obvious effect of improving mixed silicon rubber structure.
Description
Technical field
The present invention relates to vitochemical general method, be meant a kind of method especially with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil.
Background technology
The method of producing at present hydroxy silicon oil is to be solvent with acetic acid, carries out ring-opening polymerization with methyl cyclosiloxane and aceticanhydride under the condition of an acidic catalyst, uses acetic acid and acetate in the aqueous hydrolysis neutralization reaction of sodium bicarbonate and yellow soda ash again.This production method is because neutralization is incomplete, product can be because of the existence generation dehydrating condensation of acetate in storage process, it is big that viscosity becomes, 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.
Summary of the invention
Technical problem to be solved by this invention just is to overcome incomplete, the product defective that hydroxy radical content descends in storage process of existing hydroxy silicon oil production neutralization, provide a kind of with the buffer reagent of toluene as reaction, make catalyzer with potassium hydroxide the methyl cyclosiloxane is carried out ring-opening polymerization under the condition of certain temperature and pressure, again with the sulfuric acid neutralization that is hydrolyzed, toluene is sloughed in decompression at last, and to make viscosity be 20～40CS, and hydroxy radical content is at the micromolecular hydroxyl silicone oil more than 2～12%.It is raw material that method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil of the present invention adopts the methyl cyclosiloxane, with toluene as reaction buffer, make catalyzer with potassium hydroxide, sulfuric acid is made neutralizing agent and carry out ring-opening polymerization in water, and (1) raw-material constituent mass part proportioning is: the methyl cyclosiloxane is 100 mass parts, potassium hydroxide 10～70 mass parts, toluene 70～120 mass parts, sulfuric acid 8.5～60 mass parts; (2) process control condition: 100～150 ℃ of temperature of reaction, 2～7 hours reaction times, 30～70 ℃ of hydrolysis temperatures, hydrolysis time 1～3 hour, mixing speed are greater than 70 rev/mins.The methyl cyclosiloxane that the present invention uses comprises methyl mixed methylcyclosiloxane (trade name DMC) and octamethylcyclotetrasiloxane (trade name D4), and the specification of main raw material(s) is listed in table 1.
Table 1 main raw material(s) specification
| Material name | Specification | The place of production |
| The methyl cyclosiloxane | Content 〉=99.50% | Ji Hua company, Japan XINYUE |
| Potassium hydroxide | Technical pure or analytical pure | Jiangsu |
| Toluene | Technical pure or analytical pure | Jiangsu |
| Sulfuric acid | Technical grade content 〉=90% | Zhenjiang vitriol works |
| Water | Tap water | Raise middle Running-water Company |
When synthesizing small molecular hydroxy silicon oil is produced, measure by starting material set of dispense ratio earlier, respectively dimethyl cyclosiloxane, toluene, potassium hydroxide are added polymeric kettle then, open to stir and heat up 100～150 ℃ of controlled temperature, 2～7 hours reaction times; Cool off behind the stopped reaction, when temperature is reduced to below 60 ℃, with material send into prepare 6～15% aqueous sulfuric acids in and still in, 30～70 ℃ of control hydrolysis temperature, hydrolysis 1～3 hour, static layering, the organic liquor on upper strata add water cleans 1～2 time, and static layering is put and anhydrated again, then the organic layer material is further sent into and taken off in low still or the thin-film evaporator, heat up and control 90～110 ℃ of temperature of charge, vacuum tightness 0.04～0.08MPa, toluene is sloughed in decompression, makes micromolecular hydroxyl silicone oil.Micromolecular hydroxyl silicone oil final product quality index is as follows:
(1) viscosity 20～40CS; (polymerization degree is about 5～10)
(2) hydroxy radical content 2～12%.
With micromolecular hydroxyl silicone oil of the present invention and the contrast of method of acetic acid hydroxy silicon oil, be example with trade mark HD-1 method of acetic acid hydroxy silicon oil, related data is listed in table 2:
The contrast of table 2 potassium hydroxide method hydroxy silicon oil and method of acetic acid hydroxy silicon oil
| Project | The potassium hydroxide method hydroxy silicon oil | Method of acetic acid hydroxy silicon oil (HD-1) |
| Rerum natura | The transparent odorlessness of appearance colorless | Appearance colorless or faint yellow slightly tart flavour |
| Condensation | Temperature can not change more than 100 ℃ | Temperature can taken off-the OH condensation more than 100 ℃, and viscosity increases |
| Use storage period in the rubber unvulcanizate | Resistive connection structure voltinism can be good, and storage period is than long more than 1 times with HD-1 | Anti-structurizing is relatively poor, and storage period is short |
Advantage of the present invention is 20～40CS with regard to the viscosity that the method that is to adopt the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil makes, hydroxy radical content is at 2～12% micromolecular hydroxyl silicone oil, the stability of the performance when having guaranteed micromolecular hydroxyl silicone oil as the anti-antistructurizing agent of silicon rubber gross rubber and as synthetic other organosilicon polysiloxane intermediate product.Micromolecular hydroxyl silicone oil of the present invention can not occur more than 100 ℃ taking off in temperature-and OH condensation, viscosity increase phenomenon, and resistive connection structure voltinism can be better in silicon rubber gross rubber is used, and storage period is than prolonging more than 1 times with the method for acetic acid hydroxy silicon oil.Therefore the present invention has tangible effect to improving the silicon rubber gross rubber structurizing.
Embodiment
Below be embodiments of the invention, the actual use of the present invention is not limited to embodiment.
Embodiment 1 potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil
(1) starting material
Methyl cyclosiloxane (DMC) content 〉=99.50%, 160 liter, about 153.5 kilograms;
The toluene technical pure, 128 liters, about 110 kilograms;
15.5 kilograms of potassium hydroxide technical pures;
Sulfuric acid industry level content 〉=90%, 13.5 kilogram;
(2) production unit
Among 1 of 500L polymeric kettle, the 1000L and 1 of still, 1000L take off 1 of low still and 1M
21 of thin-film evaporator, 1 in vacuum pump, 5～6 of receivers.
(3) production control condition
110～120 ℃ of polymeric reaction temperatures, 4 hours reaction times;
The hydrolysis neutral temperature is below 60 ℃, hydrolysis time 2.5 hours;
70 rev/mins of mixing speed;
Take off 90～110 ℃ of low molecule temperature, vacuum tightness 0.04～0.08MPa
When synthesizing small molecular hydroxy silicon oil carries out, in the 500L polymeric kettle, add 160 liters of methyl cyclosiloxane (DMC) and 128 liters of toluene, 15.5 kilograms of potassium hydroxide, open the stirring temperature reaction, controlled temperature reacted 4 hours at 110～120 ℃, stopped cooling.When temperature of charge below 60 ℃ the time, with hydrolysis in 6% sulphuric acid soln that material joins among the 1000L and still has prepared 2 hours, static layering, put sub-cloud water, the upper strata organic liquor add water clean 2 times again static layering put and anhydrate, organic layer is added 1000L takes off 100～110 ℃ of decompressions that heat up of low still and slough toluene; Or organic layer stored in the receiver, slough toluene with being pumped into the thin-film evaporator decompression, make micromolecular hydroxyl silicone oil.Product viscosity 39.8CS, hydroxy radical content are 2.5%, as the anti-antistructurizing agent of silicon rubber gross rubber.
Embodiment 2 potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil
(1) starting material
Methyl cyclosiloxane (D4) content 〉=99.50%, 110 liter, about 105.5 kilograms;
The toluene technical pure, 145 liters, about 125.5 kilograms;
73.5 kilograms of potassium hydroxide technical pures;
Sulfuric acid industry level content 〉=90%, 63 kilogram;
(2) production unit
Among 1 of 500L polymeric kettle, the 1000L and 1 of still, 1000L take off 1 of low still and 1M
21 of thin-film evaporator, 1 in vacuum pump, 5～6 of receivers.
(3) production control condition
130～140 ℃ of temperature of reaction, 4 hours reaction times;
Hydrolysis temperature is below 60 ℃, hydrolysis time 2 hours;
70 rev/mins of mixing speed
90～110 ℃ of thin-film evaporator intensification controlled temperature.
When synthesizing small molecular hydroxy silicon oil carries out, add 110 liters of methyl cyclosiloxane (D4) and 145 liters of toluene, 73.5 kilograms of potassium hydroxide in the 500L polymeric kettle, open the stirring temperature reaction, controlled temperature is at 130～140 ℃, reacted 4 hours, and stopped to stir and cool off.When temperature of charge below 60 ℃ the time, with hydrolysis in 15% sulphuric acid soln that material joins among the 1000L and still has prepared 3 hours, static layering, put sub-cloud water, the upper strata organic liquor add water clean 1 time again static layering put and anhydrate, low still is taken off in the organic layer adding or toluene is sloughed in 90～110 ℃ of decompressions of thin-film evaporator intensification, makes micromolecular hydroxyl silicone oil.Product viscosity 21.5CS, hydroxy radical content 11.75% is as the anti-antistructurizing agent of silicon rubber gross rubber.
Claims (10)
1, a kind of method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil, it is characterized in that adopting the methyl cyclosiloxane is raw material, with toluene as reaction buffer, make catalyzer with potassium hydroxide, sulfuric acid is made neutralizing agent and carry out ring-opening polymerization in water, and (1) raw-material constituent mass part proportioning is: the methyl cyclosiloxane is 100 mass parts, potassium hydroxide 10～70 mass parts, toluene 70～120 mass parts, sulfuric acid 8.5～60 mass parts; (2) process control condition: 100～150 ℃ of temperature of reaction, 2～7 hours reaction times, 30～70 ℃ of hydrolysis temperatures, hydrolysis time 1～3 hour, mixing speed are greater than 70 rev/mins.
2, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that the methyl cyclosiloxane adopts the methyl mixed methylcyclosiloxane.
3, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that the methyl cyclosiloxane adopts octamethylcyclotetrasiloxane.
4, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that methyl cyclosiloxane content 〉=99.50% that uses, and potassium hydroxide is technical pure, and toluene is technical pure, and sulfuric acid is technical grade, content 〉=90%.
5, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that synthetic micromolecular hydroxyl silicone oil final product quality index is viscosity 20～40CS, hydroxy radical content 2～12%.
6, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1, it is characterized in that the starting material add-on: methyl cyclosiloxane (DMC) is 160 liters, and toluene is 128 liters, and potassium hydroxide is 15.5 kilograms, and sulfuric acid is 13.5 kilograms.
7, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1, it is characterized in that the starting material add-on: methyl cyclosiloxane (D4) is 110 liters, and toluene is 145 liters, and potassium hydroxide is 73.5 kilograms, and sulfuric acid is 63 kilograms.
8, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that synthetic micromolecular hydroxyl silicone oil final product quality index is product viscosity 39.8CS, and hydroxy radical content is 2.5%.
9, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1 is characterized in that synthetic micromolecular hydroxyl silicone oil final product quality index is product viscosity 21.5CS, hydroxy radical content 11.75%.
10, the method with the potassium hydroxide catalysed synthesizing small molecular hydroxy silicon oil according to claim 1, it is characterized in that sulfuric acid do neutralizing agent in and be mixed with 6～15% aqueous sulfuric acids in the still.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127227A (en) * | 2010-12-27 | 2011-07-20 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN104151348A (en) * | 2014-07-21 | 2014-11-19 | 鲁西化工集团股份有限公司硅化工分公司 | Recovery process for by-products produced by cracking of organosilicone monomers |
| CN108440757A (en) * | 2018-03-29 | 2018-08-24 | 李卓瑾 | A kind of constitution controller and production technology |
| KR102229794B1 (en) * | 2019-04-16 | 2021-03-23 | 주식회사 코이코리아 | Siloxane and method for manufacturing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0927735A1 (en) * | 1998-01-02 | 1999-07-07 | Hüls Aktiengesellschaft | Process for the production of non-reactive aminosilicone oils |
| CN1539884A (en) * | 2003-04-23 | 2004-10-27 | 上海西利康高新技术合作公司 | Non-ion type latex of hydroxy silicone oil and preparation method |
-
2006
- 2006-01-27 CN CNB2006100381653A patent/CN100400569C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127227A (en) * | 2010-12-27 | 2011-07-20 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN102127227B (en) * | 2010-12-27 | 2013-03-13 | 蓝星化工新材料股份有限公司江西星火有机硅厂 | Low viscosity hydroxyl terminated polysiloxane and preparation method thereof |
| CN104151348A (en) * | 2014-07-21 | 2014-11-19 | 鲁西化工集团股份有限公司硅化工分公司 | Recovery process for by-products produced by cracking of organosilicone monomers |
| CN104151348B (en) * | 2014-07-21 | 2016-06-08 | 鲁西化工集团股份有限公司硅化工分公司 | A kind of organosilane monomer cracking byproduct recovery process |
| CN108440757A (en) * | 2018-03-29 | 2018-08-24 | 李卓瑾 | A kind of constitution controller and production technology |
| KR102229794B1 (en) * | 2019-04-16 | 2021-03-23 | 주식회사 코이코리아 | Siloxane and method for manufacturing the same |
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| CN100400569C (en) | 2008-07-09 |
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