CN103450250B - A kind of preparation method of methyl ethyl cyclosiloxane - Google Patents
A kind of preparation method of methyl ethyl cyclosiloxane Download PDFInfo
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- CN103450250B CN103450250B CN201310422401.1A CN201310422401A CN103450250B CN 103450250 B CN103450250 B CN 103450250B CN 201310422401 A CN201310422401 A CN 201310422401A CN 103450250 B CN103450250 B CN 103450250B
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- dichlorosilane
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- methylethyl
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- -1 methyl ethyl Chemical group 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 46
- PNECSTWRDNQOLT-UHFFFAOYSA-N dichloro-ethyl-methylsilane Chemical compound CC[Si](C)(Cl)Cl PNECSTWRDNQOLT-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000413 hydrolysate Substances 0.000 claims abstract description 23
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 23
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 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
- 238000005336 cracking Methods 0.000 claims abstract description 19
- 238000006459 hydrosilylation reaction 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
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 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
- 239000006166 lysate Substances 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 6
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 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
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 12
- 239000012044 organic layer Substances 0.000 claims description 10
- 230000003301 hydrolyzing effect Effects 0.000 claims description 9
- 229940038384 octadecane Drugs 0.000 claims description 9
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 7
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 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
- 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
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 13
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 230000007423 decrease Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003776 cleavage reaction Methods 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000007017 scission Effects 0.000 abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052740 iodine Inorganic materials 0.000 abstract description 2
- 239000011630 iodine Substances 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 239000012043 crude product Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 229920001558 organosilicon polymer Polymers 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000003747 Grignard reaction Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 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
- 239000000178 monomer Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 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
- 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
- 230000015572 biosynthetic 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
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution 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
- DCAYPVUWAIABOU-NJFSPNSNSA-N hexadecane Chemical group CCCCCCCCCCCCCCC[14CH3] DCAYPVUWAIABOU-NJFSPNSNSA-N 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
- 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
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction 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 the preparation method of a kind of methyl ethyl cyclosiloxane, comprise the steps: one, under platinum catalyst effect, methyl hydrogen dichlorosilane carries out hydrosilylation in autoclave with ethene, and then rectifying obtains Methylethyl dichlorosilane；Two, Methylethyl dichlorosilane is instilled hydrolysis in dilute acid soln, obtain hydrolysate；Three, under high boiling solvent and base catalyst effect, hydrolysate is cracked, last rectifying lysate obtains trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane, methyl hydrogen dichlorosilane and ethene are carried out hydrosilylation and prepare Methylethyl dichlorosilane by the present invention, product yield is greatly improved, reduce production cost, and can iodine equipment as required, improve production capacity；The cracking process use by solvent, decreases material crosslinking, improves rate of cleavage, reduce cracking temperature, decrease the usage amount of base catalyst, have efficiency high, low power consumption and other advantages.
Description
Technical field
The present invention relates to the preparation method of a kind of cyclosiloxane, particularly relate to the preparation method of a kind of methyl ethyl cyclosiloxane.
Background technology
It is known that, trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane are important organic silicon monomers, can be used for synthesizing ethylated organosilicon polymer, ethylated organosilicon polymer can keep elastic and sealing property under ultralow temperature (Tg=-135 DEG C), and energy Long-Time Service, can be used for the special dimension such as Aero-Space, space exploration.
At present, ethylated organosilicon polymer is mainly by hexaetcycletrisiloxane (D3 Et) and octamethylcy-clotetrasiloxane (D4) and a small amount of vinyl monomer copolymerization make (CN102532548A), although the method can improve the resistance to low temperature of organosilicon polymer, but owing to being copolyreaction, D3 EtAnd D4Open-loop rate there are differences, it is difficult to ensure that the uniformity of ethyl distribution on silica chain, reports according to another Borisov.S.N., on the premise of identical ethyl content, Methylethyl organosilicon polymer has physically better mechanical performance, and D than diethyl organosilicon polymer3 EtExpensive, and prepare ethylated organosilicon polymer with Methylethyl ring body homopolymerization and can solve the problems referred to above, cost is relatively low.Therefore, exploitation methyl ethyl cyclosiloxane is significant.
In the synthesis of methyl ethyl cyclosiloxane, in patent CN101597303A, proposition methyl trialkoxysilane and halogen ethane carry out grignard reaction synthesizing methyl ethyl dialkoxy silicane under certain condition, be hydrolyzed, crack, rectifying obtains Methylethyl cyclotrisiloxane, there are two point defects in the method: one is that grignard reaction exists certain risk, yield is low, operation complexity, production capacity is low, the utilization rate of equipment is low, cost is high, also produce with accessory substances such as a large amount of magnesium halides, easily cause environmental pollution, be not preferable industrialized preparing process；Two is that cracking reaction temperature is too high, and mass-and heat-transfer is poor, easily causes material crosslinking, reduces yield.
Summary of the invention
The invention aims to the deficiency overcoming prior art to exist, it is provided that a kind of yield height, low cost, simple to operate, be applicable to the preparation method of the methyl ethyl cyclosiloxane of large-scale production.
The present invention can be reached by following measure.
A kind of preparation method of methyl ethyl cyclosiloxane, it is characterized in that comprising the steps: that (1) choosing adds methyl hydrogen dichlorosilane and platinum catalyst in autoclave, stirring, heating, it is passed through ethene again, at a temperature of 35 ~ 80 DEG C, hydrosilylation is carried out under 0.2MPa ~ 2MPa pressure, reaction terminates rear material rectifying and obtains Methylethyl dichlorosilane, described platinum catalyst is chloroplatinic acid, chloroplatinic acid mass fraction is 0.01% ~ 1%, chloroplatinic acid is 1:1000 ~ 1:1000000 with the mass ratio of methyl hydrogen dichlorosilane, methyl hydrogen dichlorosilane is 1:0.9 ~ 1:1.5 with the mol ratio of ethene,
(2) at a temperature of 30 ~ 80 DEG C, Methylethyl dichlorosilane being added drop-wise in 0.1mol/L ~ 3mol/L dilute acid soln hydrolysis, stand, organic layer is washed to neutrality, obtains hydrolysate, and described dilute acid soln is 3:1 ~ 1:2 with the mass ratio of Methylethyl dichlorosilane,
(3) in hydrolysate, high boiling solvent and base catalyst are added, described high boiling solvent is hexadecane, octadecane, hexadecanol, octadecyl alcolol, diphenyl ether, the mixture of one or more in mineral oil, described solvent is 0.5:1 ~ 5:1 with the mass ratio of hydrolysate, described base catalyst is NaOH, potassium hydroxide, cesium hydroxide, and the mixture of one or more in silicon alkoxide, the consumption of base catalyst is the 0.5% ~ 5% of hydrolysate quality, at a temperature of 100 ~ 220 DEG C, crack under 13Pa ~ 2600Pa pressure, rectifying lysate obtains trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane.
Described cracking hydrolysate under high boiling solvent and base catalyst effect, last rectifying lysate obtains in the hydrosilylation described in trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane, methyl hydrogen dichlorosilane and the preferred 1:1 ~ 1:1.1 of mol ratio of ethene.
Described platinum catalyst is chloroplatinic acid, can be dissolved in isopropanol, oxolane equal solvent or be prepared as Ka Shi catalyst and use, and chloroplatinic acid is wherein dissolved in isopropanol use preferably, chloroplatinic acid mass fraction preferably 0.03% ~ 0.5%.
Described chloroplatinic acid and the preferred 1:10000 ~ 1:100000 of mass ratio of methyl hydrogen dichlorosilane.
The temperature of described hydrosilylation preferably 35 ~ 65 DEG C, preferably 40 ~ 55 DEG C.
Preferred 0.4MPa ~ the 1MPa of reaction pressure of described hydrosilylation.
Material distillation process after described hydrosilylation, the purity of the Methylethyl dichlorosilane obtained is more preferably greater than 99.5%, the purity of Methylethyl dichlorosilane is less than 99%, in product, the organo-silicon compound content of trifunctional is higher, hydrolysate will exist a certain amount of network structure, be unfavorable for the cracking of hydrolysate.
The reaction temperature of described hydrolytic process preferably 40 ~ 60 DEG C.
The concentration of the dilute acid soln of described hydrolytic process preferably 0.5 mol/L ~ 1mol/L, dilute acid soln concentration is less than 0.1mol/L, and hydrolysis rate is slow, and reaction is not exclusively；Dilute acid soln concentration is higher than 3mol/L, on the one hand has HCI gas evolution in hydrolytic process, pollutes, and on the other hand after washing, organic layer is difficult to wash neutrality, is unfavorable for operation.
Described dilute acid soln and the preferred 2:1 ~ 1:1 of mass ratio of Methylethyl dichlorosilane.
The preferred hexadecanol of high boiling solvent in described step 3 and octadecane.
Described high boiling solvent and the preferred 1:1 ~ 3:1 of mass ratio of hydrolysate.
The consumption of described base catalyst is hydrolysate quality preferably 1% ~ 2%.
Described cracking reaction temperature preferably 120 ~ 180 DEG C.
The reaction pressure of described cracking process preferably 13 Pa ~ 2600Pa.
Methyl hydrogen dichlorosilane and ethene are carried out hydrosilylation and prepare Methylethyl dichlorosilane by the present invention, and product yield is greatly improved, and reduce production cost, and can iodine equipment as required, improve production capacity；The cracking process use by solvent, decreases material crosslinking, improves rate of cleavage, reduce cracking temperature, decrease the usage amount of base catalyst, have efficiency high, low power consumption and other advantages.
Detailed description of the invention
Further illustrate below in conjunction with embodiment.
The preparation method of a kind of methyl ethyl cyclosiloxane that the present invention provides comprise the steps: (1) under platinum catalyst effect, methyl hydrogen dichlorosilane carries out hydrosilylation in autoclave with ethene, and then rectifying obtains Methylethyl dichlorosilane；(2) Methylethyl dichlorosilane is instilled hydrolysis in dilute acid soln, obtain hydrolysate；(3) cracking hydrolysate under high boiling solvent and base catalyst effect, last rectifying lysate obtains trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane.
Concrete grammar is to add methyl hydrogen dichlorosilane and platinum catalyst, stirring, heating in autoclave, is passed through ethene, carries out hydrosilylation at a temperature of 35 ~ 80 DEG C, under 0.2MPa ~ 2MPa pressure, and reaction terminates rear material rectifying and obtains Methylethyl dichlorosilane；Then at a temperature of 30 ~ 80 DEG C, Methylethyl dichlorosilane being added drop-wise in 0.1mol/L ~ 3mol/L dilute acid soln hydrolysis, stand, organic layer is washed to neutrality, obtains hydrolysate；Adding high boiling solvent and base catalyst in hydrolysate, at a temperature of 100 ~ 220 DEG C, crack under 13Pa ~ 2600Pa pressure, last rectifying lysate obtains trimethyl triethyl group cyclotrisiloxane and tetramethyl tetraethyl cyclotetrasiloxane.
Described Methylethyl dichlorosilane is that methyl hydrogen dichlorosilane and ethene carry out what hydrosilylation prepared in autoclave by the presence of platinum catalyst.
In described hydrosilylation, methyl hydrogen dichlorosilane is 1:0.9 ~ 1:1.5, preferably 1:1 ~ 1:1.1 with the mol ratio of ethene.
Described platinum catalyst is chloroplatinic acid, can be dissolved in isopropanol, oxolane equal solvent or be prepared as Ka Shi catalyst and use, and chloroplatinic acid is wherein dissolved in isopropanol use preferably, and chloroplatinic acid mass fraction is 0.01% ~ 1%, preferably 0.03% ~ 0.5%.
Described chloroplatinic acid is 1:1000 ~ 1:1000000, preferably 1:10000 ~ 1:100000 with the mass ratio of methyl hydrogen dichlorosilane.
The temperature of described hydrosilylation is 35 ~ 80 DEG C, preferably 35 ~ 65 DEG C, preferably 40 ~ 55 DEG C.
The reaction pressure of described hydrosilylation is 0.2MPa ~ 2MPa, preferably 0.4MPa ~ 1MPa.
Material distillation process after described hydrosilylation, the purity of the Methylethyl dichlorosilane obtained should be greater than 99%, more preferably greater than 99.5%.
The purity of Methylethyl dichlorosilane is less than 99%, and in product, the organo-silicon compound content of trifunctional is higher, will there is a certain amount of network structure, and be unfavorable for the cracking of hydrolysate in hydrolysate.
The hydrolysis of described step (2) is carried out in dilute acid soln, and dilute acid soln is one or both the mixture in hydrochloric acid, sulfuric acid.
The reaction temperature of described hydrolytic process is 30 ~ 80 DEG C, preferably 40 ~ 60 DEG C.
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 less than 0.1mol/L, and hydrolysis rate is slow, and reaction is not exclusively；Dilute acid soln concentration is higher than 3mol/L, on the one hand has HCI gas evolution in hydrolytic process, pollutes, and on the other hand after washing, organic layer is difficult to wash neutrality, is unfavorable for operation.
Described dilute acid soln is 3:1 ~ 1:2, preferably 2:1 ~ 1:1 with the mass ratio of Methylethyl dichlorosilane.
The cracking process of described step (3) is in the presence of high boiling solvent, and alkali is carried out as catalyst.
High boiling solvent is added in cracking reaction, reaction system viscosity is made to decline, heat transfer is uniformly, hot-spot phenomenon will not be produced, control the generation of disproportionated reaction very well, reduce crosslinking, and system viscosity reduces, molecular diffusion rates is accelerated, and improves rate of cleavage, and can effectively reduce the usage amount of base catalyst.
Described solvent is the mixture of one or more in hexadecane, octadecane, hexadecanol, octadecyl alcolol, diphenyl ether, mineral oil, the most preferably hexadecanol and octadecane.
Described solvent is 0.5:1 ~ 5:1, preferably 1:1 ~ 3:1 with the mass ratio of hydrolysate.
Described base catalyst is the mixture of one or more in NaOH, potassium hydroxide, cesium hydroxide, and silicon alkoxide.
The consumption of described base catalyst is the 0.5% ~ 5% of hydrolysate quality, preferably 1% ~ 2%.
Described cracking reaction temperature is 100 ~ 220 DEG C, preferably 120 ~ 180 DEG C.
The reaction pressure of described cracking process is 13 Pa ~ 2600Pa.
Embodiment
1
:
600g methyl hydrogen dichlorosilane, the aqueous isopropanol (mass fraction of chloroplatinic acid is 0.05%) of 20g chloroplatinic acid is added in the autoclave of 1L, stirring, it is heated to 35 DEG C, ethylene reaction it is passed through in still, reaction temperature controls at 40 ~ 50 DEG C, in still, Stress control is at 0.4MPa ~ 0.6Mpa, until pressure rises in still, stop being passed through ethene, reaction time about 3.5h, common enter ethene 152g, by still temperature rise to 70 ~ 80 DEG C, maintaining 0.5h, reaction terminates, obtaining Methylethyl dichlorosilane crude product 760g, selectivity is 89%.By crude product rectifying, obtaining Methylethyl dichlorosilane product 601g, purity is 99.45%, yield 83%.
In 2000mL there-necked flask, add the hydrochloric acid of 1000mL 1mol/L, be heated to 45 ~ 50 DEG C, be stirred vigorously lower dropping 540g Methylethyl dichlorosilane product and be hydrolyzed, after dropping, constant temperature stirring 0.5h, stands, layering, organic layer is washed to neutrality, obtains hydrolysate.
500g hydrolysate, 750g octadecane and 9g NaOH is added to 2000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 140 ~ 160 DEG C, gather 45 ~ 86 DEG C of cuts, obtain cut 420g, yield is 84%, and wherein trimethyl triethyl group cyclotrisiloxane content is 42.26%, and tetramethyl tetraethyl cyclotetrasiloxane content is 57.38%.
By above-mentioned cut rectification under vacuum, obtaining 160g trimethyl triethyl group cyclotrisiloxane and 196g tetramethyl tetraethyl cyclotetrasiloxane, purity is respectively 99.56% and 99.60%, total recovery 85%.
Embodiment
2
:
650g methyl hydrogen dichlorosilane, the aqueous isopropanol (mass fraction of chloroplatinic acid is 0.05%) of 22g chloroplatinic acid is added in the autoclave of 1L, stirring, it is heated to 36 DEG C, ethylene reaction it is passed through in still, reaction temperature controls at 40 ~ 50 DEG C, in still, Stress control is at 0.8MPa ~ 1MPa, until pressure rises in still, stop being passed through ethene, reaction time about 3h, common enter ethene 165g, by still temperature rise to 70 ~ 80 DEG C, maintaining 0.5h, reaction terminates, obtaining Methylethyl dichlorosilane crude product 820g, selectivity is 86%.By crude product rectifying, obtaining Methylethyl dichlorosilane product 640g, purity is 99.60%, yield 82%.
In 2000mL there-necked flask, add the hydrochloric acid of 1000mL 0.5mol/L, be heated to 45 ~ 50 DEG C, be stirred vigorously lower dropping 550g Methylethyl dichlorosilane product and be hydrolyzed, after dropping, constant temperature stirring 0.5h, stands, layering, organic layer is washed to neutrality, obtains hydrolysate.
500g hydrolysate, 500g octadecane and 8g KOH is added to 2000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 120 ~ 150 DEG C, gather 45 ~ 86 DEG C of cuts, obtain cut 405g, yield is 81%, and wherein trimethyl triethyl group cyclotrisiloxane content is 49.32%, and tetramethyl tetraethyl cyclotetrasiloxane content is 50.16%.
By above-mentioned cut rectification under vacuum, obtaining 174g trimethyl triethyl group cyclotrisiloxane and 179g tetramethyl tetraethyl cyclotetrasiloxane, purity is respectively 99.51% and 99.58%, and total recovery is 87%.
Embodiment
3
:
600g methyl hydrogen dichlorosilane, the tetrahydrofuran solution (mass fraction of chloroplatinic acid is 0.05%) of 20g chloroplatinic acid is added in the autoclave of 1L, stirring, it is heated to 35 DEG C, ethylene reaction it is passed through in still, reaction temperature controls at 60 ~ 70 DEG C, in still, Stress control is at 0.4MPa ~ 0.6MPa, until pressure rises in still, stop being passed through ethene, reaction time about 4h, common enter ethene 147g, by still temperature rise to 70 ~ 80 DEG C, maintaining 0.5h, reaction terminates, obtaining Methylethyl dichlorosilane crude product 730g, selectivity is 82%.By crude product rectifying, obtaining Methylethyl dichlorosilane product 531g, purity is 99.42%, yield 73%.
Adding the hydrochloric acid of 1000mL 1mol/L in 2000mL there-necked flask, be heated to 45 ~ 50 DEG C, be stirred vigorously lower dropping 540g Methylethyl dichlorosilane and be hydrolyzed, after dropping, constant temperature stirring 0.5h, stands, and layering, organic layer is washed to neutrality, obtains hydrolysate.
600g hydrolysate, 800g hexadecanol, 4.5g NaOH and 4.5g KOH is added to 2000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 140 ~ 160 DEG C, gather 45 ~ 86 DEG C of cuts, obtain cut 501g, yield 83%, wherein trimethyl triethyl group cyclotrisiloxane content is 55.12%, and tetramethyl tetraethyl cyclotetrasiloxane content is 44.23%.
By above-mentioned cut rectification under vacuum, obtaining 249g trimethyl triethyl group cyclotrisiloxane and 179g tetramethyl tetraethyl cyclotetrasiloxane, purity is respectively 99.68% and 99.54%, and total recovery is 86%.
Embodiment
4
:
600g methyl hydrogen dichlorosilane, the tetrahydrofuran solution (mass fraction of chloroplatinic acid is 0.05%) of 20g chloroplatinic acid is added in the autoclave of 1L, stirring, it is heated to 35 DEG C, ethylene reaction it is passed through in still, reaction temperature controls at 40 ~ 60 DEG C, in still, Stress control is at 1.2MPa ~ 1.5MPa, until pressure rises in still, stop being passed through ethene, reaction time about 2.5h, common enter ethene 147g, by still temperature rise to 70 ~ 80 DEG C, maintaining 0.5h, reaction terminates, obtaining Methylethyl dichlorosilane crude product 750g, selectivity is 85%.By crude product rectifying, obtaining Methylethyl dichlorosilane product 552g, yield is 77%.
In 2000mL there-necked flask, add the hydrochloric acid of 1000mL 1mol/L, be heated to 45 ~ 50 DEG C, be stirred vigorously lower dropping 540g Methylethyl dichlorosilane product and be hydrolyzed, after dropping, constant temperature stirring 0.5h, stands, layering, organic layer is washed to neutrality, obtains hydrolysate.
600g hydrolysate, 750g hexadecane, 4.5g NaOH and 4.5g KOH is added to 2000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 135 ~ 160 DEG C, gather 45 ~ 86 DEG C of cuts, obtain cut 487g, yield is 81%, and wherein trimethyl triethyl group cyclotrisiloxane content is 54.32%, and tetramethyl tetraethyl cyclotetrasiloxane content is 45.03%.
By above-mentioned cut rectification under vacuum, obtaining 231g trimethyl triethyl group cyclotrisiloxane and 188g tetramethyl tetraethyl cyclotetrasiloxane, purity is respectively 99.71% and 99.53%, and total recovery is 86.0%.
Embodiment
5
:
600g methyl hydrogen dichlorosilane, the aqueous isopropanol (mass fraction of chloroplatinic acid is 0.05%) of 20g chloroplatinic acid is added in the autoclave of 1L, stirring, it is heated to 35 DEG C, ethylene reaction it is passed through in still, control reaction temperature at 35 ~ 45 DEG C, in still, Stress control is at 1.0MPa ~ 1.2MPa, until pressure rises in still, stop being passed through ethene, reaction time about 3h, common enter ethene 147g, by still temperature rise to 70 ~ 80 DEG C, maintaining 0.5h, reaction terminates, obtaining Methylethyl dichlorosilane crude product 730g, selectivity is 83%.By crude product rectifying, obtaining Methylethyl dichlorosilane product 536g, yield is 74%.
In 2000mL there-necked flask, add the hydrochloric acid of 1000mL 0.8mol/L, be heated to 45 ~ 50 DEG C, be stirred vigorously lower dropping 530g Methylethyl dichlorosilane product and be hydrolyzed, after dropping, constant temperature stirring 0.5h, stands, layering, organic layer is washed to neutrality, obtains hydrolysate.
600g hydrolysate, 600g octadecane, 9g KOH is added to 2000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 130 ~ 150 DEG C, gather 45 ~ 86 DEG C of cuts, obtain mixture 481g, yield is 80.2%, and wherein trimethyl triethyl group cyclotrisiloxane content is 52.12%, and tetramethyl tetraethyl cyclotetrasiloxane content is 47.13%.
By above-mentioned cut rectification under vacuum, obtaining 221g trimethyl triethyl group cyclotrisiloxane and 183g tetramethyl tetraethyl cyclotetrasiloxane, purity is respectively 99.54% and 99.61%, and total recovery is 84.0%.
Comparative example:
Hydrosilylation and hydrolysis are with embodiment 1.
600g hydrolysate, 4.5g NaOH and 4.5g KOH is added to 1000mL there-necked flask, crack under 133Pa pressure, pot temperature controls at 170 ~ 200 DEG C, gathers 45 ~ 86 DEG C of cuts, and rate of cleavage is the most slack-off, rising along with cracking temperature, drag crosslinks, final cut 315g, and yield is only 52%, wherein trimethyl triethyl group cyclotrisiloxane content is 53.07%, and tetramethyl tetraethyl cyclotetrasiloxane content is 46.02%.
Above example is in order to illustrate the present invention, but the present invention is not limited only to above citing, and those skilled in the art content involved in the present invention is made amendment, add and replace, also belong to protection scope of the present invention.
Claims (7)
1. the preparation method of a methyl ethyl cyclosiloxane, it is characterised in that comprise the steps:
(1) in autoclave, methyl hydrogen dichlorosilane and platinum catalyst are added, stirring, heating, then
It is passed through ethene, at a temperature of 35～80 DEG C, under 0.2MPa～2MPa pressure, carries out hydrosilylation,
Reaction terminates rear material rectifying and obtains Methylethyl dichlorosilane, and described platinum catalyst is chloroplatinic acid,
Chloroplatinic acid mass fraction is 0.01%～1%, and chloroplatinic acid with the mass ratio of methyl hydrogen dichlorosilane is
1:1000～1:1000000, methyl hydrogen dichlorosilane is 1:0.9～1:1.5 with the mol ratio of ethene,
(2) at a temperature of 30～80 DEG C, Methylethyl dichlorosilane is added drop-wise to
Hydrolyzing in 0.1mol/L～3mol/L dilute acid soln, stand, organic layer is washed to neutrality, obtains water
Solving thing, described dilute acid soln is 3:1～1:2 with the mass ratio of Methylethyl dichlorosilane,
(3) adding high boiling solvent and base catalyst in hydrolysate, described high boiling solvent is
One or more in hexadecane, octadecane, hexadecanol, octadecyl alcolol, diphenyl ether, mineral oil
Mixture, described solvent is 0.5:1～5:1 with the mass ratio of hydrolysate, described base catalyst
For the mixing of one or more in NaOH, potassium hydroxide, cesium hydroxide, and silicon alkoxide
Thing, the consumption of base catalyst is the 0.5%～5% of hydrolysate quality, 100～220 DEG C of temperature
Under, cracking under 13Pa～2600Pa pressure, rectifying lysate obtains trimethyl triethyl group cyclotrisiloxane
With tetramethyl tetraethyl cyclotetrasiloxane.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
It is characterised by that chloroplatinic acid is dissolved in isopropanol use, chloroplatinic acid mass fraction preferably 0.03%～0.5%.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
It is characterised by preferred 1:10000～1:100000 of mass ratio of chloroplatinic acid and methyl hydrogen dichlorosilane；
The temperature of hydrosilylation preferably 40～55 DEG C；The reaction pressure of hydrosilylation is preferred
0.4MPa～1MPa.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
It is characterised by the reaction temperature preferably 40～60 DEG C of hydrolytic process；The dilute acid soln of hydrolytic process dense
Spend preferred 0.5mol/L～1mol/L.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
It is characterised by preferred 2:1～1:1 of mass ratio of dilute acid soln and Methylethyl dichlorosilane.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
The preferred hexadecanol of high boiling solvent being characterised by step (3) and octadecane.
The preparation method of a kind of methyl ethyl cyclosiloxane the most according to claim 1, its
It is characterised by preferred 1:1～3:1 of mass ratio of high boiling solvent and hydrolysate；The consumption of base catalyst
For hydrolysate quality 1%～2%；Cracking reaction temperature preferably 120～180 DEG C；Cracking process anti-
Answer preferred 13Pa～2600Pa of pressure.
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| RU2277538C1 (en) * | 2005-04-01 | 2006-06-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | Method for preparing alkylsilanes |
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| RU2277538C1 (en) * | 2005-04-01 | 2006-06-10 | Федеральное государственное унитарное предприятие "Государственный научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП ГНИИХТЭОС) | Method for preparing alkylsilanes |
| CN101597303A (en) * | 2009-07-09 | 2009-12-09 | 武汉市化学工业研究所有限责任公司 | The preparation method of Hexaethyl cyclotrisiloxane or triethyl trimethyl cyclotrisiloxane |
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