CN105801861A - Method for preparing superfine powder silicon resin from organic silicon high-boiling residues - Google Patents
Method for preparing superfine powder silicon resin from organic silicon high-boiling residues Download PDFInfo
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Abstract
The invention discloses a method for preparing superfine powder silicon resin from organic silicon high-boiling residues.The method comprises the following steps that A, organic silicon high-boiling residues are vaporized; B, water steam and gaseous high-boiling residues are fed into a jet reactor respectively and sprayed out through oppositely-arranged atomization nozzles to be subjected to a hydrolysis reaction, solid superfine powder silicon resin and gaseous by-product HCl are generated; C, silicon resin powder, water steam and the HCl gas are pressed into a gas-solid cyclone separator, and the superfine powder silicon resin solid is obtained after cyclone separation.According to the method, reaction by-product organic silicon high-boiling residues hard to process are converted into two by-products capable of being adopted or directly sold, the problems of safety hazards and environment pollution caused by a large number of organic silicon high-boiling residues are solved, the additional value of a factory is greatly added, and the income is improved.The obtained product can be used as an additive or filler, and the higher additional value can be obtained after the product is sold.
Description
Technical field
The present invention relates to the post-processing approach of a kind of organosilicon high-boiling product, be specifically related to a kind of method that organosilicon high-boiling product prepares superfines silicones.
Background technology
Organosilicon high-boiling product be methyl chlorosilane monomer building-up process produces a kind of yellow, with the high boiling point chlorosilane mixture of penetrating odor and aggressive, based on silicon-silicon bond, silico-carbo-silicon, silicon-oxygen-silicon bound, soluble Cu, Zn, Al remaining possibly together with synthetic reaction and a small amount of fine silica powder.The density of organosilicon high-boiling product is about 1.13g/cm3, boiling range is 80～215 DEG C.
Along with the fast development of world's silicone industry, the yield of methylchlorosilane is increasing, causes a large amount of output of organosilicon high-boiling product；Adopt in direct synthesis methylchlorosilane technique, often one ton of crude monomer of synthesis, the high-boiling components of appointment generation 5%～10%.Current high-boiling components complex treatment process, commercial value is low, and a large amount of overstocking piles storehouse, brings serious environmental protection pressure and potential safety hazard, and causes efficient resource waste；Therefore, organosilicon high-boiling product Appropriate application, with obtain the higher product of added value become organic monomer factory extremely urgent need solve problem.
The comprehensive utilization of high-boiling components has been used as a large amount of research work by silicone industry in foreign countries monomer factory, and main methods is that high-boiling components Pintsch process or catalytic pyrolysis are prepared into single silane, but, crack reacting condition is very harsh.The reaction temperature of Pintsch process, up to 300～900 DEG C, just can make the silicon-silicon bond in high-boiling components rupture；At such high temperatures, carbon deposition phenomenon is very serious.The reaction temperature of catalytic pyrolysis decreases, but catalyst amount is very big, cannot realize recycling, and reaction cost is high；The high selectivity of catalyst also tends to make the fractions in high-boiling components to crack；Before cracking reaction, high-boiling components need to process through pre-distillation, and otherwise solid residue easily makes catalyst poisoning, and in product, effective ingredient dimethyldichlorosilane content is few.As can be seen here, using cleavage method to process organosilicon high-boiling product, have high input cost height, and severe reaction conditions is unfavorable for industrialization promotion.
High-boiling components is made silicone oil, waterproofing agent of organosilicon, silicones or releasing agent mainly through alcoholysis and hydrolysis by silicone industry in China monomer factory.
Chinese patent CN101514244A discloses a kind of method that organosilicon high-boiling product prepares high boiling point silicon oil, it is hydrolyzed including alcohol, neutralizes, organosilicon high-boiling product is hydrolyzed in the mixed liquor of alcohol and water, backflow 1～4h, reactant is purged again, the hydrogen chloride being subsequently adding in carbamide, zinc oxide and ammonium hydrogen carbonate and dissolving in system with nitrogen.Chinese patent CN101456955B also discloses that the method for a kind of organosilicon synthesis high boiling point silicon oil, solves the problem that carbamide in existing method, flux and ammonium hydrogen carbonate consumption are excessive；Mainly comprise the steps that the organosilicon high-boiling product of 700 weight portions and the methanol that 350～420 weight portions, temperature are 115～128 DEG C are injected alcoholysis reaction tower by (1), carry out alcoholysis reaction, discharge hydrogen chloride gas；(2) reactor is neutralized by injecting after deacidification 2～3h in above-mentioned reactant inflow deacidification reactor；(3) step 1, step 2 are repeated；(4) in and reactor in add weight portion be 15～16 water, the carbamide of 200～220, the zinc oxide of 30～40 and 100～140 sodium bicarbonate, be neutralized reaction；(5) reactant after neutralizing, through layering, filtration, obtains high boiling point silicon oil product.In above-mentioned technique, reaction needed raw material is many, and the molal weight of product is difficult to control to, last handling process complex operation, target product separation difficulty, has certain difficulty in commercial production.
Chinese patent CN101712761B discloses a kind of method of preparing organic silicon resin from organic silicon high-boiling materials, concretely comprise the following steps: dripping percentage by weight in organosilicon high-boiling product is the methanol of 50～60%, methanol time for adding is 1～2 hour, drip off rear alcoholysis 2～3 hours, then heat to 60～70 DEG C of dehydrochlorinations 1～2 hour；Control temperature below 60 DEG C, logical ammonia, as pH ≈ 7, stops logical ammonia, filter, filtering after filtering residue solvent wash, merging filtrate distills to obtain the thick product of organic siliconresin, is subsequently adding bleaching agent bleaching, filter, decolorising agent after filtration is heated to reflux De contamination 1～2 time together with the solvent of its equivalent, filters distillation, obtains organic siliconresin product.Chinese patent CN102675642A discloses a kind of method utilizing chlorosilane high-boiling components to prepare organic siliconresin, with the mixture of water, alcohol and benzene class for bed material, chlorosilane high-boiling components is dissolved in benzene kind solvent, make the benzene class solution that mass concentration is 30～70%, under agitation drop in bed material and be hydrolyzed, hydrolysis temperature 0 DEG C～60 DEG C, 2～5 hours response time；Prepolymer 90 DEG C～200 DEG C temperature, polycondensation 2～24 hours under 0.4 × 101.3kPa～0.001 × 101.3kPa pressure conditions, obtain under room temperature as the organic siliconresin of solid-state.But, in the above-mentioned method preparing organic siliconresin, it is necessary to using virose methanol or benzene class as reaction dissolvent, and last handling process is loaded down with trivial details, the quality of target product is not sufficiently stable, amplify and in environmental protection and quality control, have very big pressure after producing.
Therefore, research and develop that a kind of environmental protection pressure is little, product quality is controlled, the processing method of the simple organosilicon high-boiling product of post processing is very necessary.
Summary of the invention
For solving the problems referred to above that prior art exists, it is an object of the invention to provide a kind of method that organosilicon high-boiling product prepares superfines silicones, the method does not use organic solvent, course of reaction and last handling process simple, the quality of product is easily controlled, and is suitable for industrial amplification production.
For achieving the above object, the technical solution adopted in the present invention is:
A kind of organosilicon high-boiling product prepares the method for superfines silicones, comprises the steps of
A, organosilicon high-boiling product is sent in the carburator that temperature is 170～230 DEG C vaporize；
B, the steam conveying pipe that excessive water steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in injection reactor is gradually increased, and silicone powders and steam, HCl gas is pressed into gas-solid cyclone separator in the lump, namely obtains superfines silicone resin solids after cyclonic separation；The HCl that cyclonic separation goes out enters absorption tower water cyclic absorption, by-product hydrochloric acid.
The boiling range of described organosilicon high-boiling product is 80～215 DEG C.
Further improvement of the present invention is in that: the charge-mass ratio of described organosilicon high-boiling product and steam is 100:10～80, it is preferred to 100:15～50, it is most preferred that 100:25～40.
Further improvement of the present invention is in that: in described step C, silicone powders, steam, HCl gas are sent into by the middle part of cyclone separator, isolated HCl gas and steam are separated by cyclone separator top, and isolated superfines silicones is by cyclone separator bottom collection.
Further improvement of the present invention is in that: in described step C, and isolated HCl is after cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
Further improvement of the present invention is in that: described superfines silicate resinous product uses as fire retardant or filler.
The invention has the beneficial effects as follows:
A kind of method preparing superfines silicones by organosilicon high-boiling product of disclosure, organosilicon high-boiling product after vaporization is generated superfines silicones, simultaneously by-product hydrochloric acid with the direct haptoreaction of steam, a large amount of reluctant byproduct of reaction organosilicon high-boiling products change into two kinds can use or the side-product of direct marketing, not only solve safety and environmental issue that a large amount of organosilicon high-boiling product brings, and considerably increase the added value of factory, improve income.Products obtained therefrom superfines silicones particle diameter is little, has fire-retardant and demoulding functions, and macromolecular material has the fine compatibility, it is possible to uses as additive or filler, can obtain higher added value after sale.By-product hydrochloric acid is to be prepared by water cyclic absorption on absorption tower by byproduct of reaction, and waste gas HCl has been absorbed, and arranges almost without outside waste gas.
The additional materials of course of reaction of the present invention only has steam and water, does not use the organic solvent that toxicity is big completely, and without waste water, toxic emission, environmental protection, with low cost.The present invention uses heat transfer and the better injection reactor of mass-transfer performance to realize the continuous preparation of superfines silicones, and treating capacity is big, and reaction efficiency significantly improves；Without organosilicon high-boiling product carries out pretreatment, reacted separation process is also very simple, and operation is implemented very convenient, it is simple to expanding production.The whole process of the present invention only needs to use carburator, injection reactor, three equipment of cyclone separator, is conventional equipment, it is not necessary to great amount of investment, takes up room little, is highly convenient for existing organic silicon monomer factory and only needs transformation.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail, but embodiment is not the restriction of scope.
Injection reactor used in the present invention, including steam conveying pipe and high-boiling components conveying pipe, the end of steam conveying pipe and high-boiling components conveying pipe is positioned at sustained height, and the end of steam conveying pipe and high-boiling components conveying pipe is respectively provided with atomizer, the atomizer of two conveying pipes is oppositely arranged, it is simple to two kinds of raw materials obtain contact effect more preferably.
In the examples below that, the boiling range of the organosilicon high-boiling product used is 80～215 DEG C, and its main component is in Table 1.
Mainly comprising and the boiling point of each component of table 1 organosilicon high-boiling product
| Sequence number | Component | Boiling point/DEG C | Sequence number | Component | Boiling point/DEG C |
| 1 | C2H5MeSiCl2 | 102 | 8 | MeCl2SiOSiCl2Me | 158 |
| 2 | Me2CHSiCl2 | 118 | 9 | Me2ClSiCl2SiClMe2 | 178 |
| 3 | Me2CHMeSiCl2 | 119 | 10 | Me3ClSiCH2SiCl3 | 185 |
| 4 | MeCH2CH2SiCl3 | 124 | 11 | Cl3SiCH2SiCl3 | 185 |
| 5 | MeCH2CH2MeSiCl2 | 125 | 12 | CH3SiCH2SiCl2Me | 189 |
| 6 | Cl3SiSiCl3 | 146 | 13 | MeCl2SiCH2SiCl2Me | 192 |
| 7 | Me2ClSiSiCl3 | 157 | 14 | PhSiCl3 | 201 |
Embodiment 1
Follow these steps to prepare superfines silicones by organosilicon high-boiling product:
A, organosilicon high-boiling product is sent in the carburator that temperature is 185 DEG C vaporize；
B, the steam conveying pipe that steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe, the charge-mass ratio of gaseous state high-boiling components and steam is 100:18；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in hydrolytic reaction pot is gradually increased, and silicone powders and steam, HCl gas are pressed into gas-solid cyclone separator, obtain superfines silicone resin solids after cyclonic separation；Isolated HCl enters absorption tower water cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
Through weighing conversion, organic high-boiling components of every 100 weight portions prepares the superfines silicones of 85 mass parts.
Embodiment 2
Follow these steps to prepare superfines silicones by organosilicon high-boiling product:
A, organosilicon high-boiling product is sent in the carburator that temperature is 190 DEG C vaporize；
B, the steam conveying pipe that steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe, the charge-mass ratio of gaseous state high-boiling components and steam is 100:20；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in hydrolytic reaction pot is gradually increased, and silicone powders and steam, HCl gas are pressed into gas-solid cyclone separator, obtain superfines silicone resin solids after cyclonic separation；Isolated HCl enters absorption tower water cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
Through weighing conversion, organic high-boiling components of every 100 weight portions prepares the superfines silicones of 88 mass parts.
Embodiment 3
Follow these steps to prepare superfines silicones by organosilicon high-boiling product:
A, organosilicon high-boiling product is sent in the carburator that temperature is 210 DEG C vaporize；
B, the steam conveying pipe that steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe, the charge-mass ratio of gaseous state high-boiling components and steam is 100:27；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in hydrolytic reaction pot is gradually increased, and silicone powders and steam, HCl gas are pressed into gas-solid cyclone separator, obtain superfines silicone resin solids after cyclonic separation；Isolated HCl enters absorption tower water cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
Through weighing conversion, organic high-boiling components of every 100 weight portions prepares the superfines silicones of 91 mass parts.
Embodiment 4
Follow these steps to prepare superfines silicones by organosilicon high-boiling product:
A, organosilicon high-boiling product is sent in the carburator that temperature is 230 DEG C vaporize；
B, the steam conveying pipe that steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe, the charge-mass ratio of gaseous state high-boiling components and steam is 100:30；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in hydrolytic reaction pot is gradually increased, and silicone powders and steam, HCl gas are pressed into gas-solid cyclone separator, obtain superfines silicone resin solids after cyclonic separation；Isolated HCl enters absorption tower water cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
Through weighing conversion, organic high-boiling components of every 100 weight portions prepares the superfines silicones of 93 mass parts.
Superfines silicate resinous product obtained by embodiment 1 is used for the preparation of ketoxime removing type silicone sealant.
(1) preparation of common ketoxime removing type silicone sealant
The formula of described ketoxime removing type silicone sealant is:
| α, alpha, omega-dihydroxy polydimethyl siloxane | 100g |
| Dimethicone | 25g |
| Aluminium hydroxide (fire retardant) | 150g |
| Vinyl tributyl ketoximyl silane (cross-linking agent) | 2g |
| Methyl tributanoximo silane (cross-linking agent) | 13g |
| Gamma-aminopropyl-triethoxy-silane (coupling agent) | 2g |
| Dibutyl tin laurate (catalyst) | 0.2g |
The preparation method of described ketoxime removing type silicone sealant is:
A, by α that viscosity is 30mpa s, alpha, omega-dihydroxy polydimethyl siloxane, viscosity are put in planet stirring still after the dimethicone of 400pa s, aluminium hydroxide mixing to be stirred, control mixing 3h under temperature 120 DEG C, vacuum-0.1MPa condition, then pass to N2, release vacuum, obtain base material；
B, in base material add vinyl tributyl ketoximyl silane, methyl tributanoximo silane, evacuation, under vacuum-0.1MPa, 65 DEG C of conditions of temperature vacuum mixing 30min；Then pass to N2, release vacuum；
C, in step B gained material, add gamma-aminopropyl-triethoxy-silane and dibutyl tin laurate, evacuation, mix 30min under vacuum-0.095MPa, 65 DEG C of conditions of temperature；Then pass to N2, release vacuum, obtain product.It is labeled as D-1.
(2) preparation of the ketoxime removing type silicone sealant of superfines silicones is used
The formula of described ketoxime removing type silicone sealant is:
The preparation method of described ketoxime removing type silicone sealant is:
A, by α that viscosity is 30mpa s, alpha, omega-dihydroxy polydimethyl siloxane, viscosity are put in planet stirring still after the dimethicone of 400pa s, embodiment 1 superfines silicate resinous product, aluminium hydroxide mixing to be stirred, control mixing 3h under temperature 120 DEG C, vacuum-0.1MPa condition, then pass to N2, release vacuum, obtain base material；
B, in base material add vinyl tributyl ketoximyl silane, methyl tributanoximo silane, evacuation, under vacuum-0.1MPa, 65 DEG C of conditions of temperature vacuum mixing 30min；Then pass to N2, release vacuum；
C, in step B gained material, add gamma-aminopropyl-triethoxy-silane and dibutyl tin laurate, evacuation, mix 30min under vacuum-0.095MPa, 65 DEG C of conditions of temperature；Then pass to N2, release vacuum, obtain product.It is labeled as TM-1.
Take ketoxime removing type fluid sealant D-1, TM-1, measure its hardening time, hot strength, elongation at break, hardening time and density respectively, wherein hot strength and elongation at break press GB/T528-2009 mensuration, and density adopts density bottle method, measure by GJB77B-2005.
Test result is in Table 2.
Table 2 silicone sealant performance test data
By data above it can be seen that product of the present invention has good fire resistance, the additive as silicone sealant uses, good performance parameter can be obtained, fire-retardant rank reaches V0 level, and reduces the density of fluid sealant, has the good compatibility and result of use.
Use above-described embodiment to be used for illustrating the present invention, rather than limit the invention, in the protection domain of the claims in the present invention, any amendment that the present invention is made and change, both fall within protection scope of the present invention.
Claims (6)
1. the method that an organosilicon high-boiling product prepares superfines silicones, it is characterised in that comprise the steps of
A, organosilicon high-boiling product is sent in the carburator that temperature is 170～230 DEG C vaporize；
B, the steam conveying pipe that excessive water steam and gaseous state high-boiling components are respectively fed to injection reactor and high-boiling components conveying pipe；Steam and gaseous state high-boiling components are by the atomizer ejection being oppositely arranged, and hydrolysis occurs the contact of gas gas, generates superfines silicones and the gaseous by-product HCl of solid-state；
C, along with reaction carrying out, the pressure in injection reactor is gradually increased, and silicone powders and steam, HCl gas is pressed into gas-solid cyclone separator in the lump, namely obtains superfines silicone resin solids after cyclonic separation；The HCl that cyclonic separation goes out enters absorption tower water cyclic absorption, by-product hydrochloric acid.
2. the method that a kind of organosilicon high-boiling product according to claim 1 prepares superfines silicones, it is characterised in that: the boiling range of described organosilicon high-boiling product is 80～215 DEG C.
3. the method that a kind of organosilicon high-boiling product according to claim 2 prepares superfines silicones, it is characterised in that: the charge-mass ratio of described organosilicon high-boiling product and steam is 100:10～80.
4. the method that a kind of organosilicon high-boiling product according to claim 3 prepares superfines silicones, it is characterised in that: the charge-mass ratio of described organosilicon high-boiling product and steam is 100:15～50.
5. the method that a kind of organosilicon high-boiling product according to claim 1 prepares superfines silicones, it is characterized in that: in described step C, silicone powders, steam, HCl gas are sent into by the middle part of cyclone separator, isolated HCl gas and steam are separated by cyclone separator top, and isolated superfines silicones is by cyclone separator bottom collection.
6. the method that a kind of organosilicon high-boiling product according to claim 1 prepares superfines silicones, it is characterised in that: in described step C, isolated HCl is after cyclic absorption, and by-product mass concentration is the hydrochloric acid of 25～31%.
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| CN109319750A (en) * | 2018-11-13 | 2019-02-12 | 江西宏柏新材料股份有限公司 | A kind of method that microwave heating prepares α-siliconnitride nanobelt |
| CN109438711A (en) * | 2018-11-13 | 2019-03-08 | 江西宏柏新材料股份有限公司 | A method of synthesis, acid discharge, filtration separation integrated reaction unit and silicone resin micro mist is continuously prepared using it |
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Cited By (7)
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|---|---|---|---|---|
| CN109319750A (en) * | 2018-11-13 | 2019-02-12 | 江西宏柏新材料股份有限公司 | A kind of method that microwave heating prepares α-siliconnitride nanobelt |
| CN109438711A (en) * | 2018-11-13 | 2019-03-08 | 江西宏柏新材料股份有限公司 | A method of synthesis, acid discharge, filtration separation integrated reaction unit and silicone resin micro mist is continuously prepared using it |
| CN109438711B (en) * | 2018-11-13 | 2021-04-13 | 江西宏柏新材料股份有限公司 | Method for continuously preparing silicon resin micro powder by utilizing synthesis, acid discharge, filtering and separation integrated reaction device |
| CN113045985A (en) * | 2021-03-10 | 2021-06-29 | 中天东方氟硅材料有限公司 | Organosilicon building waterproof coating and preparation method thereof |
| CN113842870A (en) * | 2021-10-29 | 2021-12-28 | 新疆晶硕新材料有限公司 | Device and method for continuously preparing high-boiling silicone oil |
| CN114015049A (en) * | 2021-10-29 | 2022-02-08 | 山东东岳有机硅材料股份有限公司 | Preparation method of MQ silicon resin for synthesizing pressure-sensitive adhesive from organic silicon by-product |
| CN114015049B (en) * | 2021-10-29 | 2023-10-24 | 山东东岳有机硅材料股份有限公司 | Preparation method of MQ silicon resin for synthesizing pressure-sensitive adhesive from organic silicon byproducts |
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