CN103450250A - Preparation method of methyl ethyl cyclosiloxane - Google Patents
Preparation method of methyl ethyl cyclosiloxane Download PDFInfo
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- CN103450250A CN103450250A CN2013104224011A CN201310422401A CN103450250A CN 103450250 A CN103450250 A CN 103450250A CN 2013104224011 A CN2013104224011 A CN 2013104224011A CN 201310422401 A CN201310422401 A CN 201310422401A CN 103450250 A CN103450250 A CN 103450250A
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- methylethyl
- dichlorosilane
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- hydrolyzate
- temperature
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- -1 methyl ethyl Chemical group 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- PNECSTWRDNQOLT-UHFFFAOYSA-N dichloro-ethyl-methylsilane Chemical compound CC[Si](C)(Cl)Cl PNECSTWRDNQOLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- PPFOGBSWFQJMKW-UHFFFAOYSA-N 2,4,6,8-tetraethyl-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(C)O[Si](C)(CC)O[Si](C)(CC)O[Si](C)(CC)O1 PPFOGBSWFQJMKW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009835 boiling Methods 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 27
- 150000002431 hydrogen Chemical class 0.000 claims description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005336 cracking Methods 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 20
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 239000010703 silicon Substances 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- VFZPJBWVHVHZDH-UHFFFAOYSA-N CC[SiH]1O[SiH](CC)O[SiH](CC)O1.CN(C)C Chemical compound CC[SiH]1O[SiH](CC)O[SiH](CC)O1.CN(C)C VFZPJBWVHVHZDH-UHFFFAOYSA-N 0.000 claims description 17
- 238000007259 addition reaction Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- 239000012044 organic layer Substances 0.000 claims description 10
- 229940038384 octadecane Drugs 0.000 claims description 9
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical group CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 230000007017 scission Effects 0.000 claims description 8
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 7
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- 238000010504 bond cleavage reaction Methods 0.000 claims description 5
- 239000006166 lysate Substances 0.000 claims description 5
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 3
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 14
- 239000005977 Ethylene Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract 5
- 239000000413 hydrolysate Substances 0.000 abstract 2
- 238000006459 hydrosilylation reaction Methods 0.000 abstract 2
- DGLJYEKNUTVPAE-UHFFFAOYSA-N 2,4,6-triethyl-2,4,6-trimethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC[Si]1(C)O[Si](C)(CC)O[Si](C)(CC)O1 DGLJYEKNUTVPAE-UHFFFAOYSA-N 0.000 abstract 1
- 238000004132 cross linking Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 10
- 229920001558 organosilicon polymer Polymers 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000003776 cleavage reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003747 Grignard reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AORAHZWCSRUYRD-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound C[Si]1(O[SiH2]O[SiH2]O1)CC AORAHZWCSRUYRD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The invention discloses a preparation method of methyl ethyl cyclosiloxane. The method comprises the following steps of: placing methyldichlorosilae into an autoclave for hydrosilylation with ethylene under the action of platinum catalyst, and then rectifying the reactant to obtain methyl ethyl dichlorosilane; dripping the methyl ethyl dichlorosilane into dilute acid solution for hydrolyzation and obtaining hydrolysate; performing pyrolysis to the hydrolysate under the action of high boiling point solvents and base catalysts, and finally rectifying the pyrolysis product to obtain trimethyl triethyl cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane. The methyl ethyl cyclosiloxane is prepared by hydrosilylation of the methyldichlorosilae and the ethylene so as to greatly improve the product yield, reduce the production cost and enlarge the reaction device based on the demands to improve the capacity; the solvent is used in the pyrolysis process so as to reduce material crosslinking, improve the pyrolysis speed, reduce the pyrolysis temperature and decrease the usage amounts of the base catalysts; the method has the advantages of high efficiency and low energy consumption, etc.
Description
Technical field
The present invention relates to a kind of preparation method of cyclosiloxane, particularly relate to a kind of preparation method of methylethyl cyclosiloxane.
Background technology
As everyone knows, trimethylammonium triethyl cyclotrisiloxane and tetramethyl-tetraethyl-cyclotetrasiloxane are important organosilane monomers, can be used for synthetic ethylated organosilicon polymer, ethylated organosilicon polymer can be in lower elasticity and the sealing property of keeping of very low temperature (Tg=-135 ℃), and the energy life-time service, can be used for the special dimensions such as aerospace, space exploration.
At present, ethylated organosilicon polymer is mainly by hexaetcycletrisiloxane (D
3 et) and octamethylcyclotetrasiloxane (D
4) and a small amount of vinyl monomer copolymerization make (CN102532548A), although the method can be improved the resistance to low temperature of organosilicon polymer, owing to being copolyreaction, D
3 etand D
4open-loop rate there are differences, be difficult to the homogeneity that guarantees that on the silica chain, ethyl distributes, according to another the Borisov.S.N. report, under the prerequisite of identical ethyl content, the methylethyl organosilicon polymer has better physical and mechanical properties than diethyl organosilicon polymer, and D
3 etexpensive, and prepare ethylated organosilicon polymer with the homopolymerization of methylethyl ring body, can address the above problem, cost is lower.Therefore, exploitation methylethyl cyclosiloxane is significant.
In synthesizing of methylethyl cyclosiloxane, in patent CN101597303A, propose to carry out grignard reaction synthesizing methyl ethyl dialkoxy silicane under certain condition with methyl trialkoxysilane and halogen ethane, be hydrolyzed again, cracking, rectifying obtain the methylethyl cyclotrisiloxane, there are two point defects in the method: the one, and there is certain risk in grignard reaction, yield is low, complicated operation, production capacity is low, the utilization ratio of equipment is low, cost is high, also with by products such as a large amount of magnesium halides, producing, easily cause environmental pollution, is not desirable industrialized preparing process; The 2nd, the scission reaction excess Temperature, mass-and heat-transfer is poor, easily causes material crosslinked, reduces yield.
Summary of the invention
The objective of the invention is the deficiency existed in order to overcome prior art, provide that a kind of yield is high, cost is low, the preparation method of simple to operate, the methylethyl cyclosiloxane that is applicable to large-scale production.
The present invention can reach by following measure.
A kind of preparation method of methylethyl cyclosiloxane, it is characterized in that comprising the steps: that (1) choosing adds methyl hydrogen dichlorosilane and platinum catalyst in autoclave, stir, heating, pass into again ethene, at 35 ~ 80 ℃ of temperature, 0.2MPa carry out addition reaction of silicon with hydrogen under ~ 2MPa pressure, after reaction finishes, material rectifying obtains the methylethyl dichlorosilane, described platinum catalyst is Platinic chloride, the Platinic chloride massfraction is 0.01% ~ 1%, the mass ratio of Platinic chloride and methyl hydrogen dichlorosilane is 1:1000 ~ 1:1000000, the mol ratio of methyl hydrogen dichlorosilane and ethene is 1:0.9 ~ 1:1.5,
(2) at 30 ~ 80 ℃ of temperature, the methylethyl dichlorosilane is added drop-wise in 0.1mol/L ~ 3mol/L dilute acid soln and is hydrolyzed, standing, organic layer is washed to neutrality, obtains hydrolyzate, and the mass ratio of described dilute acid soln and methylethyl dichlorosilane is 3:1 ~ 1:2,
(3) add high boiling solvent and alkaline catalysts in hydrolyzate, described high boiling solvent is n-Hexadecane, octadecane, hexadecanol, stearyl alcohol, phenyl ether, the mixture of one or more in mineral oil, the mass ratio of described solvent and hydrolyzate is 0.5:1 ~ 5:1, described alkaline catalysts is sodium hydroxide, potassium hydroxide, cesium hydroxide, and one or more the mixture in silicon alkoxide, the consumption of alkaline catalysts is 0.5% ~ 5% of hydrolyzate quality, at 100 ~ 220 ℃ of temperature, cracking under 13Pa ~ 2600Pa pressure, the rectifying lysate obtains trimethylammonium triethyl cyclotrisiloxane and tetramethyl-tetraethyl-cyclotetrasiloxane.
Described under high boiling solvent and alkaline catalysts effect the cracking hydrolyzate, last rectifying lysate obtains in trimethylammonium triethyl cyclotrisiloxane and the described addition reaction of silicon with hydrogen of tetramethyl-tetraethyl-cyclotetrasiloxane, the preferred 1:1 ~ 1:1.1 of the mol ratio of methyl hydrogen dichlorosilane and ethene.
Described platinum catalyst is Platinic chloride, it can be dissolved in Virahol, tetrahydrofuran (THF) equal solvent or be prepared into the Ka Shi catalyzer to use, and wherein Platinic chloride is dissolved in Virahol and uses better, Platinic chloride massfraction preferably 0.03% ~ 0.5%.
Preferred 1:10000 ~ the 1:100000 of the mass ratio of described Platinic chloride and methyl hydrogen dichlorosilane.
Preferably 35 ~ 65 ℃ of the temperature of described addition reaction of silicon with hydrogen, be preferably 40 ~ 55 ℃.
Preferred 0.4MPa ~ the 1MPa of the reaction pressure of described addition reaction of silicon with hydrogen.
Material rectifying after described addition reaction of silicon with hydrogen, the purity of the methylethyl dichlorosilane obtained is more preferably greater than 99.5%, the purity of methylethyl dichlorosilane is lower than 99%, in product, the silicoorganic compound content of trifunctional is higher, to there is a certain amount of reticulated structure in hydrolyzate, be unfavorable for the cracking of hydrolyzate.
Preferably 40 ~ 60 ℃ of the temperature of reaction of described hydrolytic process.
The concentration of the dilute acid soln of described hydrolytic process is 0.5 mol/L ~ 1mol/L preferably, and dilute acid soln concentration is lower than 0.1mol/L, and hydrolysis rate is slow, and reaction not exclusively; Dilute acid soln concentration, higher than 3mol/L, has the HCI gas evolution in hydrolytic process on the one hand, pollutes, and after the washing, organic layer is difficult to washing to neutral on the other hand, is unfavorable for operation.
Preferred 2:1 ~ the 1:1 of the mass ratio of described dilute acid soln and methylethyl dichlorosilane.
The preferred hexadecanol of high boiling solvent in described step 3 and octadecane.
Preferred 1:1 ~ the 3:1 of the mass ratio of described high boiling solvent and hydrolyzate.
The consumption of described alkaline catalysts is hydrolyzate quality preferably 1% ~ 2%.
Preferably 120 ~ 180 ℃ of described scission reaction temperature.
The reaction pressure of described cracking process is 13 Pa ~ 2600Pa preferably.
The present invention carries out addition reaction of silicon with hydrogen by methyl hydrogen dichlorosilane and ethene and prepares the methylethyl dichlorosilane, has significantly improved product yield, has reduced production cost, and iodine equipment as required, improves production capacity; Cracking process, by the use of solvent, has reduced material crosslinked, has improved rate of cleavage, has reduced cracking temperature, has reduced the usage quantity of alkaline catalysts, has efficiency high, low power consumption and other advantages.
Embodiment
Below in conjunction with embodiment, further illustrate.
The preparation method of a kind of methylethyl cyclosiloxane provided by the invention comprises the steps: that (1) is under the platinum catalyst effect, and methyl hydrogen dichlorosilane is carried out addition reaction of silicon with hydrogen with ethene in autoclave, and then rectifying obtains the methylethyl dichlorosilane; (2) the methylethyl dichlorosilane is splashed in dilute acid soln and is hydrolyzed, obtain hydrolyzate; (3) cracking hydrolyzate under high boiling solvent and alkaline catalysts effect, last rectifying lysate obtains trimethylammonium triethyl cyclotrisiloxane and tetramethyl-tetraethyl-cyclotetrasiloxane.
Concrete grammar is to add methyl hydrogen dichlorosilane and platinum catalyst in autoclave, stirs, and heating, pass into ethene, at 35 ~ 80 ℃ of temperature, under 0.2MPa ~ 2MPa pressure, carries out addition reaction of silicon with hydrogen, and after reaction finishes, material rectifying obtains the methylethyl dichlorosilane; Then at 30 ~ 80 ℃ of temperature, the methylethyl dichlorosilane is added drop-wise in 0.1mol/L ~ 3mol/L dilute acid soln and is hydrolyzed, standing, organic layer is washed to neutrality, obtains hydrolyzate; Add high boiling solvent and alkaline catalysts in hydrolyzate, at 100 ~ 220 ℃ of temperature, cracking under 13Pa ~ 2600Pa pressure, last rectifying lysate obtains trimethylammonium triethyl cyclotrisiloxane and tetramethyl-tetraethyl-cyclotetrasiloxane.
Described methylethyl dichlorosilane is by under platinum catalyst exists, and methyl hydrogen dichlorosilane and ethene carry out in autoclave that addition reaction of silicon with hydrogen makes.
In described addition reaction of silicon with hydrogen, the mol ratio of methyl hydrogen dichlorosilane and ethene is 1:0.9 ~ 1:1.5, preferably 1:1 ~ 1:1.1.
Described platinum catalyst is Platinic chloride, it can be dissolved in Virahol, tetrahydrofuran (THF) equal solvent or be prepared into the Ka Shi catalyzer and use, wherein Platinic chloride is dissolved in Virahol and uses better, the Platinic chloride massfraction is 0.01% ~ 1%, preferably 0.03% ~ 0.5%.
The mass ratio of described Platinic chloride and methyl hydrogen dichlorosilane is 1:1000 ~ 1:1000000, preferably 1:10000 ~ 1:100000.
The temperature of described addition reaction of silicon with hydrogen is 35 ~ 80 ℃, preferably 35 ~ 65 ℃, is preferably 40 ~ 55 ℃.
The reaction pressure of described addition reaction of silicon with hydrogen is 0.2MPa ~ 2MPa, preferably 0.4MPa ~ 1MPa.
Material rectifying after described addition reaction of silicon with hydrogen, the purity of the methylethyl dichlorosilane obtained should be greater than 99%, more preferably greater than 99.5%.
The purity of methylethyl dichlorosilane is lower than 99%, and in product, the silicoorganic compound content of trifunctional is higher, in hydrolyzate, will have a certain amount of reticulated structure, is unfavorable for the cracking of hydrolyzate.
The hydrolysis reaction of described step (2) carries out in dilute acid soln, and dilute acid soln is one or both the mixture in hydrochloric acid, sulfuric acid.
The temperature of reaction of described hydrolytic process is 30 ~ 80 ℃, preferably 40 ~ 60 ℃.
The concentration of the dilute acid soln of described hydrolytic process is 0.1 mol/L ~ 3mol/L, preferably 0.5 mol/L ~ 1mol/L.
Dilute acid soln concentration is lower than 0.1mol/L, and hydrolysis rate is slow, and reaction not exclusively; Dilute acid soln concentration, higher than 3mol/L, has the HCI gas evolution in hydrolytic process on the one hand, pollutes, and after the washing, organic layer is difficult to washing to neutral on the other hand, is unfavorable for operation.
The mass ratio of described dilute acid soln and methylethyl dichlorosilane is 3:1 ~ 1:2, preferably 2:1 ~ 1:1.
The cracking process of described step (3) is that alkali carries out as catalyzer under high boiling solvent exists.
Add high boiling solvent in scission reaction, make the reaction system viscosity degradation, conduct heat evenly, can not produce the local superheating phenomenon, the fine generation of controlling disproportionation reaction, reduce crosslinked, and the system viscosity reduces, molecular diffusion speed is accelerated, and has improved rate of cleavage, and can effectively reduce the usage quantity of alkaline catalysts.
Described solvent is one or more the mixture in n-Hexadecane, octadecane, hexadecanol, stearyl alcohol, phenyl ether, mineral oil, wherein is preferably hexadecanol and octadecane.
The mass ratio of described solvent and hydrolyzate is 0.5:1 ~ 5:1, preferably 1:1 ~ 3:1.
Described alkaline catalysts is sodium hydroxide, potassium hydroxide, cesium hydroxide, and one or more the mixture in silicon alkoxide.
The consumption of described alkaline catalysts is 0.5% ~ 5% of hydrolyzate quality, preferably 1% ~ 2%.
Described scission reaction temperature is 100 ~ 220 ℃, preferably 120 ~ 180 ℃.
The reaction pressure of described cracking process is 13 Pa ~ 2600Pa.
embodiment 1:
To the aqueous isopropanol (massfraction of Platinic chloride is 0.05%) that adds 600g methyl hydrogen dichlorosilane, 20g Platinic chloride in the autoclave of 1L, stir, be heated to 35 ℃, pass into ethylene reaction in still, temperature of reaction is controlled at 40 ~ 50 ℃, the still internal pressure is controlled at 0.4MPa ~ 0.6Mpa, until the still internal pressure rises, stop passing into ethene, about 3.5h of reaction times, commonly enter ethene 152g, by still temperature rise to 70 ~ 80 ℃, maintain 0.5h, reaction finishes, obtain methylethyl dichlorosilane crude product 760g, selectivity is 89%.By crude product rectifying, obtain methylethyl dichlorosilane product 601g, purity is 99.45%, yield 83%.
Hydrochloric acid to adding 1000mL 1mol/L in the 2000mL there-necked flask, be heated to 45 ~ 50 ℃, drips 540g methylethyl dichlorosilane product under vigorous stirring and be hydrolyzed, dropwise rear constant temperature and stir 0.5h, standing, layering, organic layer is washed to neutrality, obtains hydrolyzate.
Add 500g hydrolyzate, 750g octadecane and 9g NaOH to the 2000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 140 ~ 160 ℃, gather 45 ~ 86 ℃ of cuts, obtain cut 420g, yield is 84%, and wherein trimethylammonium triethyl cyclotrisiloxane content is 42.26%, and tetramethyl-tetraethyl-cyclotetrasiloxane content is 57.38%.
By above-mentioned cut rectification under vacuum, obtain 160g trimethylammonium triethyl cyclotrisiloxane and 196g tetramethyl-tetraethyl-cyclotetrasiloxane, purity is respectively 99.56% and 99.60%, total recovery 85%.
embodiment 2:
To the aqueous isopropanol (massfraction of Platinic chloride is 0.05%) that adds 650g methyl hydrogen dichlorosilane, 22g Platinic chloride in the autoclave of 1L, stir, be heated to 36 ℃, pass into ethylene reaction in still, temperature of reaction is controlled at 40 ~ 50 ℃, the still internal pressure is controlled at 0.8MPa ~ 1MPa, until the still internal pressure rises, stop passing into ethene, about 3h of reaction times, commonly enter ethene 165g, by still temperature rise to 70 ~ 80 ℃, maintain 0.5h, reaction finishes, obtain methylethyl dichlorosilane crude product 820g, selectivity is 86%.By crude product rectifying, obtain methylethyl dichlorosilane product 640g, purity is 99.60%, yield 82%.
Hydrochloric acid to adding 1000mL 0.5mol/L in the 2000mL there-necked flask, be heated to 45 ~ 50 ℃, drips 550g methylethyl dichlorosilane product under vigorous stirring and be hydrolyzed, dropwise rear constant temperature and stir 0.5h, standing, layering, organic layer is washed to neutrality, obtains hydrolyzate.
Add 500g hydrolyzate, 500g octadecane and 8g KOH to the 2000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 120 ~ 150 ℃, gather 45 ~ 86 ℃ of cuts, obtain cut 405g, yield is 81%, and wherein trimethylammonium triethyl cyclotrisiloxane content is 49.32%, and tetramethyl-tetraethyl-cyclotetrasiloxane content is 50.16%.
By above-mentioned cut rectification under vacuum, obtain 174g trimethylammonium triethyl cyclotrisiloxane and 179g tetramethyl-tetraethyl-cyclotetrasiloxane, purity is respectively 99.51% and 99.58%, and total recovery is 87%.
embodiment 3:
To the tetrahydrofuran solution (massfraction of Platinic chloride is 0.05%) that adds 600g methyl hydrogen dichlorosilane, 20g Platinic chloride in the autoclave of 1L, stir, be heated to 35 ℃, pass into ethylene reaction in still, temperature of reaction is controlled at 60 ~ 70 ℃, the still internal pressure is controlled at 0.4MPa ~ 0.6MPa, until the still internal pressure rises, stop passing into ethene, about 4h of reaction times, commonly enter ethene 147g, by still temperature rise to 70 ~ 80 ℃, maintain 0.5h, reaction finishes, obtain methylethyl dichlorosilane crude product 730g, selectivity is 82%.By crude product rectifying, obtain methylethyl dichlorosilane product 531g, purity is 99.42%, yield 73%.
Hydrochloric acid to adding 1000mL 1mol/L in the 2000mL there-necked flask, be heated to 45 ~ 50 ℃, drips 540g methylethyl dichlorosilane under vigorous stirring and be hydrolyzed, dropwise rear constant temperature and stir 0.5h, standing, layering, organic layer is washed to neutrality, obtains hydrolyzate.
Add 600g hydrolyzate, 800g hexadecanol, 4.5g NaOH and 4.5g KOH to the 2000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 140 ~ 160 ℃, gather 45 ~ 86 ℃ of cuts, obtain cut 501g, yield 83%, wherein trimethylammonium triethyl cyclotrisiloxane content is 55.12%, tetramethyl-tetraethyl-cyclotetrasiloxane content is 44.23%.
By above-mentioned cut rectification under vacuum, obtain 249g trimethylammonium triethyl cyclotrisiloxane and 179g tetramethyl-tetraethyl-cyclotetrasiloxane, purity is respectively 99.68% and 99.54%, and total recovery is 86%.
embodiment 4:
To the tetrahydrofuran solution (massfraction of Platinic chloride is 0.05%) that adds 600g methyl hydrogen dichlorosilane, 20g Platinic chloride in the autoclave of 1L, stir, be heated to 35 ℃, pass into ethylene reaction in still, temperature of reaction is controlled at 40 ~ 60 ℃, the still internal pressure is controlled at 1.2MPa ~ 1.5MPa, until the still internal pressure rises, stop passing into ethene, about 2.5h of reaction times, commonly enter ethene 147g, by still temperature rise to 70 ~ 80 ℃, maintain 0.5h, reaction finishes, obtain methylethyl dichlorosilane crude product 750g, selectivity is 85%.By crude product rectifying, obtain methylethyl dichlorosilane product 552g, yield is 77%.
Hydrochloric acid to adding 1000mL 1mol/L in the 2000mL there-necked flask, be heated to 45 ~ 50 ℃, drips 540g methylethyl dichlorosilane product under vigorous stirring and be hydrolyzed, dropwise rear constant temperature and stir 0.5h, standing, layering, organic layer is washed to neutrality, obtains hydrolyzate.
Add 600g hydrolyzate, 750g n-Hexadecane, 4.5g NaOH and 4.5g KOH to the 2000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 135 ~ 160 ℃, gather 45 ~ 86 ℃ of cuts, obtain cut 487g, yield is 81%, and wherein trimethylammonium triethyl cyclotrisiloxane content is 54.32%, and tetramethyl-tetraethyl-cyclotetrasiloxane content is 45.03%.
By above-mentioned cut rectification under vacuum, obtain 231g trimethylammonium triethyl cyclotrisiloxane and 188g tetramethyl-tetraethyl-cyclotetrasiloxane, purity is respectively 99.71% and 99.53%, and total recovery is 86.0%.
embodiment 5:
To the aqueous isopropanol (massfraction of Platinic chloride is 0.05%) that adds 600g methyl hydrogen dichlorosilane, 20g Platinic chloride in the autoclave of 1L, stir, be heated to 35 ℃, pass into ethylene reaction in still, control temperature of reaction at 35 ~ 45 ℃, the still internal pressure is controlled at 1.0MPa ~ 1.2MPa, until the still internal pressure rises, stop passing into ethene, about 3h of reaction times, commonly enter ethene 147g, by still temperature rise to 70 ~ 80 ℃, maintain 0.5h, reaction finishes, obtain methylethyl dichlorosilane crude product 730g, selectivity is 83%.By crude product rectifying, obtain methylethyl dichlorosilane product 536g, yield is 74%.
Hydrochloric acid to adding 1000mL 0.8mol/L in the 2000mL there-necked flask, be heated to 45 ~ 50 ℃, drips 530g methylethyl dichlorosilane product under vigorous stirring and be hydrolyzed, dropwise rear constant temperature and stir 0.5h, standing, layering, organic layer is washed to neutrality, obtains hydrolyzate.
Add 600g hydrolyzate, 600g octadecane, 9g KOH to the 2000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 130 ~ 150 ℃, gather 45 ~ 86 ℃ of cuts, obtain mixture 481g, yield is 80.2%, and wherein trimethylammonium triethyl cyclotrisiloxane content is 52.12%, and tetramethyl-tetraethyl-cyclotetrasiloxane content is 47.13%.
By above-mentioned cut rectification under vacuum, obtain 221g trimethylammonium triethyl cyclotrisiloxane and 183g tetramethyl-tetraethyl-cyclotetrasiloxane, purity is respectively 99.54% and 99.61%, and total recovery is 84.0%.
comparative example:
Addition reaction of silicon with hydrogen and hydrolysis reaction are with embodiment 1.
Add 600g hydrolyzate, 4.5g NaOH and 4.5g KOH to the 1000mL there-necked flask, cracking under 133Pa pressure, in flask, temperature is controlled at 170 ~ 200 ℃, gathers 45 ~ 86 ℃ of cuts, and rate of cleavage is obviously slack-off, rising along with cracking temperature, drag occurs crosslinked, the final cut 315g that obtains, and yield is only 52%, wherein trimethylammonium triethyl cyclotrisiloxane content is 53.07%, and tetramethyl-tetraethyl-cyclotetrasiloxane content is 46.02%.
Above embodiment is in order to the present invention to be described, but the present invention be not limited only to above for example, and those skilled in the art modification, interpolation and replacement that content involved in the present invention is made, belong to protection scope of the present invention equally.
Claims (7)
1. the preparation method of a methylethyl cyclosiloxane, is characterized in that comprising the steps:
(1) choosing adds methyl hydrogen dichlorosilane and platinum catalyst in autoclave, stir, heating, then pass into ethene, at 35 ~ 80 ℃ of temperature, under 0.2MPa ~ 2MPa pressure, carries out addition reaction of silicon with hydrogen, after reaction finishes, material rectifying obtains the methylethyl dichlorosilane, described platinum catalyst is Platinic chloride, and the Platinic chloride massfraction is 0.01% ~ 1%, and the mass ratio of Platinic chloride and methyl hydrogen dichlorosilane is 1:1000 ~ 1:1000000, the mol ratio of methyl hydrogen dichlorosilane and ethene is 1:0.9 ~ 1:1.5
(2) at 30 ~ 80 ℃ of temperature, the methylethyl dichlorosilane is added drop-wise in 0.1mol/L ~ 3mol/L dilute acid soln and is hydrolyzed, standing, organic layer is washed to neutrality, obtains hydrolyzate, and the mass ratio of described dilute acid soln and methylethyl dichlorosilane is 3:1 ~ 1:2,
(3) add high boiling solvent and alkaline catalysts in hydrolyzate, described high boiling solvent is n-Hexadecane, octadecane, hexadecanol, stearyl alcohol, phenyl ether, the mixture of one or more in mineral oil, the mass ratio of described solvent and hydrolyzate is 0.5:1 ~ 5:1, described alkaline catalysts is sodium hydroxide, potassium hydroxide, cesium hydroxide, and one or more the mixture in silicon alkoxide, the consumption of alkaline catalysts is 0.5% ~ 5% of hydrolyzate quality, at 100 ~ 220 ℃ of temperature, cracking under 13Pa ~ 2600Pa pressure, the rectifying lysate obtains trimethylammonium triethyl cyclotrisiloxane and tetramethyl-tetraethyl-cyclotetrasiloxane.
2. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that Platinic chloride is dissolved in Virahol to use, Platinic chloride massfraction preferably 0.03% ~ 0.5%.
3. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that the preferred 1:10000 ~ 1:100000 of mass ratio of Platinic chloride and methyl hydrogen dichlorosilane; Preferably 40 ~ 55 ℃ of the temperature of addition reaction of silicon with hydrogen; Preferred 0.4MPa ~ the 1MPa of the reaction pressure of addition reaction of silicon with hydrogen.
4. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that preferably 40 ~ 60 ℃ of the temperature of reaction of hydrolytic process; The concentration of the dilute acid soln of hydrolytic process is 0.5 mol/L ~ 1mol/L preferably.
5. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that the preferred 2:1 ~ 1:1 of mass ratio of dilute acid soln and methylethyl dichlorosilane.
6. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that the preferred hexadecanol of high boiling solvent and octadecane in step 3.
7. the preparation method of a kind of methylethyl cyclosiloxane according to claim 1, is characterized in that the preferred 1:1 ~ 3:1 of mass ratio of high boiling solvent and hydrolyzate; The consumption of alkaline catalysts is hydrolyzate quality preferably 1% ~ 2%; Preferably 120 ~ 180 ℃ of scission reaction temperature; The reaction pressure of cracking process is 13 Pa ~ 2600Pa preferably.
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| CN114437125A (en) * | 2022-01-25 | 2022-05-06 | 杭州四马化工科技有限公司 | Continuous cracking process for silane in wire loop body |
| CN114933705A (en) * | 2022-06-20 | 2022-08-23 | 杭州埃比森新材料有限公司 | Ethyl silicone oil and preparation method thereof |
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