CN101173044A - Method for producing 107 adhesive by comprehensive utilization of organosilicon hydrolyzation material loop separation - Google Patents
Method for producing 107 adhesive by comprehensive utilization of organosilicon hydrolyzation material loop separation Download PDFInfo
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- CN101173044A CN101173044A CNA2007101344938A CN200710134493A CN101173044A CN 101173044 A CN101173044 A CN 101173044A CN A2007101344938 A CNA2007101344938 A CN A2007101344938A CN 200710134493 A CN200710134493 A CN 200710134493A CN 101173044 A CN101173044 A CN 101173044A
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Abstract
The invention relates to the field of organic silicon, in particular to a preparation method ofsulfuration silicon rubber by comprehensively utilizing an organic silicon hydrolyzing material. The invention firstly separates a linear body from a cyclic body of the organic silicon hydrolyzing material; under the condition of nitrogen circular dehydration, the separated linear body is added with basic catalysts for shrinking and polymerizing, and then the organic silicon organic phosphate is added for neutralization, finally, the alpha, omega-hydroxy polydimethylsiloxanediol is obtained. The separated cyclic body can be used for preparing high-temperature sulfuration silicon rubber and other organic silicon polymers. The invention has the advantages of mild reaction conditions, low reaction temperature requirements, simple process flow and convenient operation; the unit energy consumption is remarkably reduced because of saving the step of separating the low molecule.
Description
Technical field
The present invention relates to field of organic silicon, be specifically related to a kind of method that organosilicon hydrolyzation material prepares sulphurated siliastic that fully utilizes.
Background technology
α, alpha, omega-dihydroxy polydimethyl siloxane (being called for short 107 glue) is the sizing that room temperature vulcanized silicone rubber overwhelming majority kind is used, room temperature vulcanized silicone rubber is except that the characteristic with high-temperature silicon disulfide rubber, also have and make advantages such as simple, easy to use, of a great variety, that utilization is wide, can the scene be shaped on the spot, it obtains widespread use as tackiness agent, sealing agent, in-place forming agent etc. in social economy.Therefore, the synthesis technique of 107 glue and quality product are having a strong impact on the use range and the effect of room temperature vulcanized silicone rubber.Industrial 107 glue preparation technologies commonly used are divided into polymerization, degraded, broken enzyme and remove four steps of low molecular weight volatile thing at present, and the shortcoming of this type of technology is: (1) adopts D
4Or DMC polymerization under the basic catalyst effect, have the raw materials cost height, technology is numerous and diverse, facility investment is big, and quality product is difficult to control, viscosity poor repeatability and product adhesive property.The shortcoming that physicals is relatively poor relatively; (2) adopt organosilicon hydrolyzation material or the polymerization under alkalescence or an acidic catalyst effect of organosilicon small molecules thread, it is strict to polymerization unit, and an acidic catalyst neutralization is also difficult; (3) above-mentioned existing technology all exists product to take off low step, and the production cycle is prolonged, and energy consumption increases, and product yield reduces (general conversion rate of products only is 75%～90%), and production efficiency is low.
US4,250,290 have introduced a kind of technology of continuous processing scale operation hydroxyl polysiloxane, polyreaction is carried out in static mixer, is catalyzer with the siloxanes potassium alcoholate, and temperature of reaction is 160 ℃～190 ℃, polymerization pressure 1.17MPa, water are chain termination agent, add at twice.Add at the static mixer front end for the first time, add-on is 0.01%～0.05%, adds in the polymerization rear end for the second time.Material enters in another static mixer and mixes with silica-based phosphoric acid ester after the polymerization then, in the material and after enter vapour liquid separator, this separator absolute pressure is 5～10mmHg, promptly gets hydroxyl polysiloxane product after removing low molecule, and product viscosity is 5～500PaS.
US4,310,679 have introduced acid catalysis equilibrium polymerization method, produce the hydroxyl polysiloxane by DMC or dimethyldichlorosilane(DMCS) hydrolyzate through the acid catalysis balance.Temperature of reaction is 90 ℃, and reactor is a stirring tank, and acidic white earth is made catalyzer, by controlling reaction time, produces the α of certain viscosity scope, ω-hydroxyl polysiloxane.Japan, special public clear 55-7,855 and US3,694,405 introduction methods and above-mentioned resemble process.
Ger (East) DD287,521 to have introduced a kind of be raw material with the diformazan hydrolyzation material, potassium hydroxide is catalyzer, 95 ℃～180 ℃ polymerizations and remove a part of water, after reaching certain viscosity, adopt the phosphoric acid catalyst neutralisation to come termination reaction, by control product viscosity such as institute's water yield that removes and termination reaction time after raw material center line body burden, polymerization time, the polymerization.
FR-1193721 has introduced and has adopted LiOH to make the technological process of Preparation of Catalyst hydroxyl polysiloxane, and reactor is a stirring tank, and temperature of reaction is 130 ℃, the control water yield and rearrangement time, can make viscosity (30 ℃) and be the above product of viscosity arbitrarily of 4.0PaS.
In sum, the synthetic method of 107 glue can be selected different catalyzer, neutralizing agent and raw material for use, and be raw material with the ring body, to make the technology of catalyzer with KOH more, but there are the raw materials cost height in existing technology and the mentioned method of document, complex manufacturing, facility investment is big, and quality product is difficult to control, transformation efficiency is low, shortcomings such as energy consumption height.
Summary of the invention
The present invention is directed to the existing deficiency of above-mentioned industrial conventional process method, disclose a kind of method that organosilicon hydrolyzation material prepares sulphurated siliastic that fully utilizes.
The present invention collects after the ring body condensation that distills out by organosilicon hydrolyzation material is distilled earlier.The residual liquid in distillation back promptly is the solution that contains a large amount of line bodies, and these solution under the condition of nitrogen circulation dehydration, are added basic catalyst shrink polymerization, adds the phosphoric acid ester neutralization again, makes α, alpha, omega-dihydroxy polydimethyl siloxane.Separate the ring body that obtains and can be used for preparing high-temperature silicon disulfide rubber and other polymerizable organosilicon product.
The preferred potassium hydroxide of above-mentioned basic catalyst.
The preferred silica-based phosphoric acid ester of above-mentioned phosphoric acid ester.
Ring body of the present invention promptly is the abbreviation of ring body in the organosilicon methyl monomer hydrolyzation material, and the line body is the abbreviation of organosilicon methyl monomer hydrolyzation material center line body.
Organosilicon hydrolyzation material of the present invention is prepared by following method: with dimethyldichlorosilane(DMCS) in the presence of hydrochloric acid through hydrolysis, the hydrolyzate of generation is through layering, after the washing of upper strata, with the sodium carbonate solution neutralization, after the filtration promptly.Preferable methods is: with the azeotropic hydrochloric acid of dimethyldichlorosilane(DMCS) and 20%～22% (massfraction), be continuously pumped in proportion in the loop system of forming by impeller pump, tubular radiator and acidproof pipeline, preferred 10 ℃～80 ℃ of hydrolysis temperature, the hydrolyzate that generates is after layering (upper strata), washing, sodium carbonate solution neutralization with 15% promptly gets organosilicon hydrolyzation material after the filtration.
Above-mentioned described hydrolyzation material through underpressure distillation, separablely goes out ring body in reactor, vacuum tightness was preferably 1.3kPa～2.6kPa when it separated, and temperature is preferably 150 ℃～250 ℃.
Institute's line body that stays and basic catalyst shrink polymerization in separating the afterreaction still, polycondensation preferably takes place in the preferred potassium hydroxide of described basic catalyst under the nitrogen circulation dehydration conditions, preferred 50 ℃～150 ℃ of polymerization temperature.With silica-based phosphoric acid ester is in the neutralizing agent and polymerisate, preferred 50 ℃～100 ℃ of neutral temperature, in and after product be α, alpha, omega-dihydroxy polydimethyl siloxane.
Organosilicon hydrolyzation material is a colourless transparent liquid among the present invention, but does not have water breakthrough, and colourity is smaller or equal to 20, and density (25 ℃) is 0.956～0.966g/cm
3, viscosity (25 ℃) scope is 8～15 mPaS, Cl content is smaller or equal to 50ppm.
Organosilicon hydrolyzation material gained line body after separating is a colourless transparent liquid among the present invention, neutrality, and tasteless, range of viscosities is 70～150mPaS.
By the α that the inventive method obtains, the poly-two first class siloxanes range of viscosities of alpha, omega-dihydroxy are: 0.5～500PaS.
The present invention is by separating the organosilicon loop wire, and gained line system is equipped with 107 glue, the reaction conditions gentleness, and temperature of reaction requires low, and technical process is simple, and is easy to operate, and takes off low step owing to saving, and unit consumption of energy obviously reduces.
The ring body that loop wire obtains after separating can prepare high-temperature silicon disulfide rubber or other polymerizable organosilicon product with ordinary method.The method for preparing high-temperature silicon disulfide rubber is as follows:
After the ring body dehydration, add methyl ethylene ring body closure agent and Tetramethylammonium hydroxide alkali glue catalyzer and continue dehydration, polymerization in reactor heats up and decomposes alkali glue catalyzer, removes the low molecular weight volatile thing and promptly gets high-temperature sulfuration silicon rubber raw rubber.
Preferred manufacturing procedure is:
Separating obtained ring body in the dehydration still at 1.3kPa, temperature is that 30 ℃～90 ℃ following drying nitrogen bubbling dehydrations are after 3 hours, add Tetramethylammonium hydroxide alkali glue catalyzer and closure agent and continue dehydration 0.5 hour, polymerization in reactor then, polymerization temperature is preferably 50 ℃～130 ℃, equilibrium polymerization 2-9 hour, is warming up to 130 ℃～150 and decomposes alkali glue catalyzer, be 1.3kPa in vacuum tightness at last, temperature is to remove the low molecular weight volatile thing under 150 ℃～250 ℃ promptly to get high-temperature sulfuration silicon rubber raw rubber.
After the present invention separates by loop wire, mild condition when gained line system is equipped with 107 glue, conversion unit requires low, and technical process is simple, and is easy to operate.
Technical process of the present invention, product viscosity is controlled, and viscosity repeatability better need not remove low-molecular material, the product yield height, volatility is low.
Technical process of the present invention is than the common synthesis technique of industry, and it is a bit obvious, and be in particular in: the organosilicon hydrolyzation material isolate can fully utilize, and can effectively reduce raw materials cost; Technology is simple, and facility investment is few; The product yield height, the viscosity good reproducibility, volatile content is low, and product performance are stable.
Embodiment
Embodiment 1
The hydrochloric acid of 1000kg dimethyldichlorosilane(DMCS) and 1600kg 20% is continuously pumped in proportion is with in the hydronic hydrolysis kettle, hydrolysis temperature remains between 20 ℃～30 ℃, the layering of hydrolysis resultant separates, upper oil phase is after washing, add the sodium carbonate solution neutralization of 630kg 15%, product filters can obtain the 570kg organosilicon hydrolyzation material.
The 500kg organosilicon hydrolyzation material is joined underpressure distillation in the 1000L stirred autoclave, and vacuum tightness is 1.33kPa in the still, and temperature is 200 ℃, distills out about 320kg ring body.When temperature in the reactor is reduced to 85 ℃, the KOH aqueous solution that adds 18g 50%, drying nitrogen surface dehydration cycle is 85 ℃ of reaction adding 3.0Kg 1.8% silica-based phosphoric acid ester neutralizations after 5 hours down in temperature, continue to stir 3 hours, make viscosity (20 ℃) and be 2000mm
2α about/S, alpha, omega-dihydroxy polydimethyl siloxane.
Separating obtained ring body 300kg is added in the 500L stirred autoclave, in vacuum tightness is 1.33kPa, the drying nitrogen bubbling added 0.84kg Tetramethylammonium hydroxide silicon alkoxide catalyzer and 0.33kg methyl closure agent after 3 hours when temperature was 45 ℃, continued bubbling dehydration 30min.Material after the processed is warming up to 100 ℃, stirring reaction 3 hours, polymerization equilibrium afterreaction still is warming up to 150 ℃ of decomposition catalysts, in 180 ℃, removes the low molecular weight volatile thing under the vacuum tightness 1.33kPa and promptly gets raw-silastic continuously.
Embodiment 2
The hydrochloric acid of 1000kg dimethyldichlorosilane(DMCS) and 1800kg 22% is continuously pumped in proportion is with in the hydronic hydrolysis kettle, hydrolysis temperature remains between 30 ℃～40 ℃, the layering of hydrolysis resultant separates, upper oil phase is after washing, add the sodium carbonate solution neutralization of 610kg 15%, product filters can obtain the 550kg organosilicon hydrolyzation material.
The 500kg organosilicon hydrolyzation material is joined underpressure distillation in the 1000L stirred autoclave, and vacuum tightness is 1.6kPa in the still, and temperature is 210 ℃, distills out about 335kg ring body.When temperature in the reactor is reduced to 90 ℃, the KOH aqueous solution that adds 16.5g 50%, drying nitrogen surface dehydration cycle is 90 ℃ of reaction adding 2.8Kg 1.8% silica-based phosphoric acid ester neutralizations after 8 hours down in temperature, continue to stir 3 hours, make viscosity (20 ℃) and be 15000mm
2α about/S, alpha, omega-dihydroxy polydimethyl siloxane.
Getting separating obtained ring body 300kg adds in the 500L stirred autoclave, in vacuum tightness is 1.33kPa, the drying nitrogen bubbling added 0.84kg Tetramethylammonium hydroxide silicon alkoxide catalyzer and 0.21kg vinyl closure agent after 3 hours when temperature was 50 ℃, continued bubbling dehydration 30min.Material after the processed is warming up to 110 ℃, stirring reaction 3 hours, polymerization equilibrium afterreaction still is warming up to 150 ℃ of decomposition catalysts, in 190 ℃, removes the low molecular weight volatile thing under the vacuum tightness 1.6kPa and promptly gets raw-silastic continuously.
Claims (7)
1. one kind fully utilizes the method that organosilicon hydrolyzation material prepares silicone rubber based glue, comprise: organosilicon hydrolyzation material is distilled earlier, collect after the ring body condensation that distills out, the residual solution that is rich in the line body is under the condition of nitrogen circulation dehydration, add basic catalyst shrink polymerization, add the phosphoric acid ester neutralization again, make α, alpha, omega-dihydroxy polydimethyl siloxane.
2. the process of claim 1 wherein that polymerization temperature is 50 ℃～150 ℃.
3. the process of claim 1 wherein that distillatory vacuum tightness is 1.3kPa～2.6kPa, temperature is 150 ℃～250 ℃.
4. the process of claim 1 wherein that basic catalyst is a potassium hydroxide.
5. the process of claim 1 wherein that phosphoric acid ester is an organophosphorus ester.
6. the process of claim 1 wherein that organosilicon hydrolyzation material is obtained by following method: with dimethyldichlorosilane(DMCS) in the presence of hydrochloric acid through hydrolysis, the hydrolyzate of generation is through layering, after the washing of upper strata, with the sodium carbonate solution neutralization, after the filtration promptly.
7. the method for claim 6, wherein hydrolysis temperature is 10 ℃～80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101344938A CN101173044A (en) | 2007-10-30 | 2007-10-30 | Method for producing 107 adhesive by comprehensive utilization of organosilicon hydrolyzation material loop separation |
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| CNA2007101344938A CN101173044A (en) | 2007-10-30 | 2007-10-30 | Method for producing 107 adhesive by comprehensive utilization of organosilicon hydrolyzation material loop separation |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101928399A (en) * | 2010-08-20 | 2010-12-29 | 浙江中天氟硅材料有限公司 | Preparation method for 107 silicon rubber with controllable viscosity |
| CN101338034B (en) * | 2008-06-06 | 2011-03-16 | 浙江新安化工集团股份有限公司 | Novel process for synthesizing 107 silicon rubber |
| CN103665381A (en) * | 2013-12-27 | 2014-03-26 | 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 |
| CN104031084A (en) * | 2014-06-19 | 2014-09-10 | 鲁西化工集团股份有限公司硅化工分公司 | Loop-line separating method of organic silicon hydrolysate |
| CN104163922A (en) * | 2014-07-21 | 2014-11-26 | 鲁西化工集团股份有限公司硅化工分公司 | Concentrated-acid hydrolysis technology for dimethyl dichlorosilane under balance state |
| CN105131292A (en) * | 2015-09-29 | 2015-12-09 | 山东东岳有机硅材料有限公司 | Preparation method of low-viscosity 107 silicone rubber |
| CN105175730A (en) * | 2015-08-19 | 2015-12-23 | 湖北兴瑞化工有限公司 | Method for preparing silicone rubber from organosilicon hydrolysate |
| CN105254893A (en) * | 2015-11-25 | 2016-01-20 | 泸州北方化学工业有限公司 | Low-viscosity 107 silicone rubber and preparation method thereof |
| CN105254894A (en) * | 2015-10-23 | 2016-01-20 | 山东东岳有机硅材料有限公司 | 107 silicone rubber preparing method |
| CN106083910A (en) * | 2016-07-04 | 2016-11-09 | 湖北兴发化工集团股份有限公司 | A kind of organosilicon hydrolyzation thing loop wire separation method and device |
| CN107177344A (en) * | 2017-05-27 | 2017-09-19 | 湖北兴瑞化工有限公司 | A kind of method that the glue of the high grade of transparency 107 is produced by raw material of Dimethyldichlorosilane hydrolysate |
| CN114790292A (en) * | 2022-04-29 | 2022-07-26 | 新疆西部合盛硅业有限公司 | Preparation process of low-viscosity 107 adhesive |
| CN116063681A (en) * | 2023-02-07 | 2023-05-05 | 山东大学 | Double-layer structure vinyl end capping Process for the preparation of polysiloxanes |
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2007
- 2007-10-30 CN CNA2007101344938A patent/CN101173044A/en active Pending
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338034B (en) * | 2008-06-06 | 2011-03-16 | 浙江新安化工集团股份有限公司 | Novel process for synthesizing 107 silicon rubber |
| CN101928399A (en) * | 2010-08-20 | 2010-12-29 | 浙江中天氟硅材料有限公司 | Preparation method for 107 silicon rubber with controllable viscosity |
| CN101928399B (en) * | 2010-08-20 | 2014-06-25 | 浙江中天氟硅材料有限公司 | Preparation method for 107 silicon rubber with controllable viscosity |
| CN103665381A (en) * | 2013-12-27 | 2014-03-26 | 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 |
| 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 |
| CN104031084A (en) * | 2014-06-19 | 2014-09-10 | 鲁西化工集团股份有限公司硅化工分公司 | Loop-line separating method of organic silicon hydrolysate |
| CN104163922B (en) * | 2014-07-21 | 2016-10-12 | 鲁西化工集团股份有限公司硅化工分公司 | A kind of dimethyldichlorosilane Concentrated acid hydrolysis technique under poised state |
| CN104163922A (en) * | 2014-07-21 | 2014-11-26 | 鲁西化工集团股份有限公司硅化工分公司 | Concentrated-acid hydrolysis technology for dimethyl dichlorosilane under balance state |
| CN105175730B (en) * | 2015-08-19 | 2018-11-20 | 湖北兴瑞化工有限公司 | A method of silicon rubber is prepared using organosilicon hydrolyzation object |
| CN105175730A (en) * | 2015-08-19 | 2015-12-23 | 湖北兴瑞化工有限公司 | Method for preparing silicone rubber from organosilicon hydrolysate |
| CN105131292B (en) * | 2015-09-29 | 2018-03-16 | 山东东岳有机硅材料有限公司 | The preparation method of the silicon rubber of low viscosity 107 |
| CN105131292A (en) * | 2015-09-29 | 2015-12-09 | 山东东岳有机硅材料有限公司 | Preparation method of low-viscosity 107 silicone rubber |
| CN105254894B (en) * | 2015-10-23 | 2018-01-09 | 山东东岳有机硅材料有限公司 | A kind of preparation method of 107 silicon rubber |
| CN105254894A (en) * | 2015-10-23 | 2016-01-20 | 山东东岳有机硅材料有限公司 | 107 silicone rubber preparing method |
| CN105254893B (en) * | 2015-11-25 | 2018-02-16 | 泸州北方化学工业有限公司 | A kind of silicon rubber of low viscosity 107 and preparation method thereof |
| CN105254893A (en) * | 2015-11-25 | 2016-01-20 | 泸州北方化学工业有限公司 | Low-viscosity 107 silicone rubber and preparation method thereof |
| CN106083910A (en) * | 2016-07-04 | 2016-11-09 | 湖北兴发化工集团股份有限公司 | A kind of organosilicon hydrolyzation thing loop wire separation method and device |
| CN106083910B (en) * | 2016-07-04 | 2018-09-28 | 湖北兴发化工集团股份有限公司 | A kind of organosilicon hydrolyzation object loop wire separation method and device |
| CN107177344A (en) * | 2017-05-27 | 2017-09-19 | 湖北兴瑞化工有限公司 | A kind of method that the glue of the high grade of transparency 107 is produced by raw material of Dimethyldichlorosilane hydrolysate |
| CN114790292A (en) * | 2022-04-29 | 2022-07-26 | 新疆西部合盛硅业有限公司 | Preparation process of low-viscosity 107 adhesive |
| CN116063681A (en) * | 2023-02-07 | 2023-05-05 | 山东大学 | Double-layer structure vinyl end capping Process for the preparation of polysiloxanes |
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