CN117003789A - Preparation method of methyl ethyl cyclosiloxane - Google Patents
Preparation method of methyl ethyl cyclosiloxane Download PDFInfo
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- CN117003789A CN117003789A CN202310804384.1A CN202310804384A CN117003789A CN 117003789 A CN117003789 A CN 117003789A CN 202310804384 A CN202310804384 A CN 202310804384A CN 117003789 A CN117003789 A CN 117003789A
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- methyl ethyl
- silicone oil
- cyclosiloxane
- methylethyl
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- -1 methyl ethyl Chemical group 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920002545 silicone oil Polymers 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 238000005336 cracking Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000005977 Ethylene Substances 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 14
- 239000007789 gas Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 238000003776 cleavage reaction Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 230000007017 scission Effects 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- 230000006837 decompression Effects 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 19
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- HFRICAKEFCIBMJ-UHFFFAOYSA-N [dimethyl(trimethylsilyloxy)silyl]oxy-ethyl-dimethylsilane Chemical compound CC[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C HFRICAKEFCIBMJ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical group C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- FDJVUTSAGSRHAY-UHFFFAOYSA-N 2,4,6,8,10-pentaethyl-2,4,6,8,10-pentamethyl-1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane Chemical compound CC[Si]1(C)O[Si](C)(CC)O[Si](C)(CC)O[Si](C)(CC)O[Si](C)(CC)O1 FDJVUTSAGSRHAY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 4
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 4
- 239000005048 methyldichlorosilane Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 description 3
- 239000005046 Chlorosilane Substances 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- KMPBCFZCRNKXSA-UHFFFAOYSA-N 2,2,4,4,6,6-hexaethyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 KMPBCFZCRNKXSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920001558 organosilicon polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SNGQPGAJJZSLIY-UHFFFAOYSA-N CN(C1=CC=CC=C1)C.[N].[N] Chemical compound CN(C1=CC=CC=C1)C.[N].[N] SNGQPGAJJZSLIY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PNECSTWRDNQOLT-UHFFFAOYSA-N dichloro-ethyl-methylsilane Chemical compound CC[Si](C)(Cl)Cl PNECSTWRDNQOLT-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006462 rearrangement reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
Abstract
The invention relates to the technical field of siloxane preparation, and discloses a preparation method of methyl ethyl cyclosiloxane, which comprises the following steps: and adding the high-hydrogen-content silicone oil and ethylene gas under the condition of a Kasite catalyst to prepare methyl ethyl silicone oil, and then cracking the methyl ethyl silicone oil into tetramethyl tetraethyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane to obtain the methyl ethyl cyclosiloxane. According to the invention, the methyl ethyl silicone oil is prepared by adding the high-hydrogen silicone oil and ethylene under the condition of a Kasite catalyst, and then the methyl ethyl silicone oil is cracked into the tetramethyl tetraethyl cyclotetrasiloxane and the pentamethyl pentacyclopentasiloxane, so that the preparation process is simpler and cleaner, the adoption of strong corrosive raw materials is avoided, the byproducts are reduced, and the yield and purity of the product are improved.
Description
Technical Field
The invention relates to the technical field of siloxane preparation, in particular to a preparation method of methyl ethyl cyclosiloxane.
Background
The organosilicon polymer with the main chain structure of the polydimethylsiloxane is difficult to meet the requirements of low-temperature resistant materials and cold-heat resistant materials in extremely cold weather conditions and special fields. When methyl functional group part of the side chain or the end group of the siloxane is substituted by ethyl functional group, methyl ethyl polysiloxane is obtained, and the crystallization temperature of the polymer is reduced due to the fact that the regularity of the dimethyl siloxane structure is destroyed, so that the cold resistance of the organosilicon polymer material can be enhanced. At present, the main preparation method of methyl ethyl polysiloxane is that hexaethyl cyclotrisiloxane or triethyl trimethyl cyclotrisiloxane is adopted for ring-opening polymerization, and the hexaethyl cyclotrisiloxane or the triethyl trimethyl cyclotrisiloxane is mainly obtained by a Grignard method, and the steps are complicated, the cost is high, and the pollution is large. The other method is mainly a hydrosilylation method of hydrogen-containing chlorosilane, has large corrosion to equipment, is easy to corrode and perforate an autoclave by hydrogen chloride, has large risk, and has complex process, a plurality of strong acid procedures and a plurality of byproducts.
For example, chinese patent publication No. CN111995754a discloses a method for preparing diethyl silicone oil by subjecting methyldichlorosilane to a cleavage rearrangement reaction with a vinyl high boiling substance (waste generated in the production of vinyl ends) and thereby hydrolyzing. In view of the large corrosion of chlorosilane to equipment and high reaction temperature, the catalyst nitrogen-nitrogen dimethylaniline is a carcinogen, which is not beneficial to the health of workers. The Chinese patent publication No. CN114933705A discloses a method for preparing ethyl silicone oil by using methyldichlorosilane and ethylene as raw materials, water as a solvent and chloroplatinic acid as a catalyst. The Chinese patent publication No. CN103450250A discloses a method for preparing methyl ethyl dichlorosilane by hydrosilylation of methyl dichlorosilane and ethylene in an autoclave under the condition of chloroplatinic acid catalyst, and then cracking under alkaline condition after hydrolysis to obtain a mixture of tetramethyl tetraethyl cyclotetrasiloxane or trimethyl triethyl cyclotrisiloxane. Obviously, chloroplatinic acid is dissolved in a large amount of water and then loses activity, and methyl dichlorosilane is hydrolyzed to obtain hydrogen-containing silicone oil, so that the scheme is not feasible, and the yield and purity of the product are low.
Disclosure of Invention
In order to overcome the problems of complex preparation, large pollution and high risk of methyl ethyl cyclosiloxane prepared by the prior art route, the invention provides a preparation method of methyl ethyl cyclosiloxane, which adopts high-hydrogen silicone oil and ethylene to carry out addition under the condition of a Kasite catalyst to prepare methyl ethyl silicone oil, and then the methyl ethyl silicone oil is cracked into tetramethyl tetraethyl cyclosiloxane and pentamethyl pentacyclopentasiloxane, so that the preparation process is simpler and cleaner.
The aim of the invention is realized by the following technical scheme: a method for preparing methylethyl cyclosiloxane, comprising the following steps: and adding the high-hydrogen-content silicone oil and ethylene gas under the condition of a Kasite catalyst to prepare methyl ethyl silicone oil, and then cracking the methyl ethyl silicone oil into tetramethyl tetraethyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane to obtain the methyl ethyl cyclosiloxane.
Compared with the prior art, the invention does not adopt hydrogen-containing chlorosilane as a reactant and chloroplatinic acid as a catalyst, but adopts high hydrogen-containing silicone oil and ethylene gas to carry out addition reaction under the condition of a Karster catalyst, and the methyl ethyl silicone oil is prepared and then cracked to obtain the methyl ethyl cyclosiloxane. The whole reaction process is simpler, the adoption of strong corrosive raw materials is avoided, the tetramethyl tetraethyl cyclotetrasiloxane and the pentamethyl pentacyclopentasiloxane can be obtained by direct pyrolysis, the yield and the purity of the pyrolysis product are high, and the byproducts are few.
Preferably, the hydrogen content in the high hydrogen silicone oil is 1 to 1.62%.
Preferably, the addition amount of the Kasite catalyst accounts for 0.08-0.12% of the mass of the high-hydrogen silicone oil.
Preferably, the addition is performed by introducing ethylene gas under a nitrogen atmosphere to a pressure of 1 to 8atm.
Preferably, the reaction condition of the addition is that the temperature is raised to 80-90 ℃ for reaction for 4-12 hours.
Preferably, an organic solvent is added in the addition process, and the organic solvent is a solvent which does not contain carboxyl, hydroxyl, sulfur, phosphorus and nitrogen. The organic solvent is octamethyl cyclotetrasiloxane or toluene, more preferably octamethyl cyclotetrasiloxane.
After the octamethyl cyclotetrasiloxane is added, the viscosity of the system can be reduced, so that the reaction rate is accelerated, and the reaction time is shortened; but also can improve the total yield of the cracking reaction.
Preferably, the cleavage is: methyl ethyl silicone oil and sulfonic acid resin are mixed and then subjected to decompression and cracking.
Preferably, the sulfonic acid resin is added in an amount of more than 5% by mass of the methyl ethyl silicone oil.
The sulfonic acid resin is used as a catalyst to accelerate the reaction, and may be a perfluorosulfonic acid resin or a conventional sulfonic acid resin (containing no fluorine), more preferably a perfluorosulfonic acid resin.
Preferably, the temperature of the reduced pressure pyrolysis is 105 to 115 ℃.
Preferably, the pressure of the reduced pressure pyrolysis is 800 to 1200Pa.
Compared with the prior art, the invention has the following beneficial effects:
(1) The high hydrogen silicone oil and ethylene are added under the condition of a Kasite catalyst to prepare methyl ethyl silicone oil, and then the methyl ethyl silicone oil is cracked into tetramethyl tetraethyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane, so that the preparation process is simpler and cleaner, the adoption of strong corrosive raw materials is avoided, byproducts are reduced, and the yield and purity of the product are improved;
(2) In the addition reaction process, conditions such as hydrogen content of high-hydrogen-content silicone oil, pressure of ethylene gas, reaction parameters and the like can influence the ratio of methyl to ethyl in methyl ethyl silicone oil, and further can influence the composition of a cracking product and the yield and purity of the product, so that the parameter conditions in the invention are mutually matched and influence each other, and tetramethyl tetraethyl cyclotetrasiloxane and tetramethyl pentacyclopentasiloxane with high yield and high purity can be obtained.
Detailed Description
The technical scheme of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto:
a method for preparing methylethyl cyclosiloxane, comprising the following steps:
adding high hydrogen silicone oil (hydrogen content is 1-1.62%) and ethylene gas under the condition of a Karster catalyst, wherein the addition amount of the Karster catalyst accounts for 0.08-0.12% of the mass of the high hydrogen silicone oil, introducing ethylene gas to the pressure of 1-8 atm under the nitrogen atmosphere, and heating to 80-90 ℃ for reacting for 4-12 h to prepare methyl ethyl silicone oil; organic solvents can be added in the addition reaction process, wherein the organic solvents are solvents which do not contain carboxyl, hydroxyl, sulfur element, phosphorus element and nitrogen element.
After methyl ethyl silicone oil and sulfonic acid resin are mixed, decompression cracking is carried out under the conditions of absolute pressure of 800-1200 Pa and temperature of 105-115 ℃, the addition amount of the sulfonic acid resin is more than 5% of the mass of the methyl ethyl silicone oil, and tetramethyl tetraethyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane are obtained through cracking, so that the methyl ethyl cyclotiloxane is obtained.
Example 1
50 kg of high hydrogen silicone oil (hydrogen content 1.50%) was added to the stainless steel autoclave and nitrogen was replaced to an oxygen content of less than 1%. Ethylene was introduced and the pressure was raised to 1atm. 0.05 kg of a Kadster catalyst (pt content 3000 ppm) was added. The temperature is raised to 80 ℃ to react for 12 hours. Residual gas was removed to give 71.7 kg of crude methylethyl silicone oil. Residual silicon hydrogen was not detected.
71.7 kg of methyl ethyl silicone oil crude product is put into a cracking reaction kettle, 7 kg of repeatedly cleaned sulfonic acid resin is added, the absolute pressure is 1000Pa, the cracking is carried out at 110 ℃, the cracking product is obtained, and then the rectification and the purification are carried out. The cleavage product consisted of 54% tetramethyl tetraethyl cyclotetrasiloxane, 40% pentamethyl pentaethyl cyclopentasiloxane, 1% hexamethyldisiloxane and 5% heptamethyl ethyl trisiloxane.
Example 2
50 kg of high hydrogen silicone oil (hydrogen content: 1.50%) and 17 kg of octamethyl cyclotetrasiloxane were added to a stainless steel autoclave, and nitrogen was substituted until the oxygen content was less than 1%. Ethylene was introduced and the pressure was raised to 1atm. 0.05 kg of a Kadster catalyst (pt content 3000 ppm) was added. The temperature is raised to 80 ℃ for reaction for 6 hours. And (3) removing residual gas, and distilling out low-boiling substances and octamethyl cyclotetrasiloxane to obtain 68 kg of crude methyl ethyl silicone oil. Residual silicon hydrogen was not detected.
58 kg of methyl ethyl silicone oil crude product is put into a cracking reaction kettle, 7 kg of repeatedly cleaned sulfonic acid resin is added, the absolute pressure is 1000Pa, the cracking product is obtained through decompression and cracking at 110 ℃, and then the cracking product is purified through rectification. The cleavage product consisted of 56% tetramethyl tetraethyl cyclotetrasiloxane, 42% pentamethyl pentaethyl cyclotetrasiloxane, 4% heptamethyl ethyl trisiloxane.
Example 3
50 kg of high hydrogen silicone oil (hydrogen content: 1.50%) and 17 kg of toluene were added to a stainless steel autoclave, and nitrogen was substituted until the oxygen content was less than 1%. Ethylene was introduced and the pressure was raised to 1atm. 0.05 kg of a Kadster catalyst (pt content 3000 ppm) was added. The temperature is raised to 80 ℃ for reaction for 6 hours. Removing residual gas, distilling out low-boiling-point substances and toluene to obtain 68 kg of crude methyl ethyl silicone oil. Residual silicon hydrogen was not detected.
68 kg of methyl ethyl silicone oil crude product is put into a cracking reaction kettle, 7 kg of repeatedly cleaned sulfonic acid resin is added, the absolute pressure is 1000Pa, the cracking product is obtained through decompression and cracking at 110 ℃, and then the cracking product is purified through rectification. The cleavage product consisted of 54% tetramethyl tetraethyl cyclotetrasiloxane, 40% pentamethyl pentaethyl cyclopentasiloxane, 5% heptamethyl ethyl trisiloxane, 1% hexamethyldisiloxane.
Example 4
50 kg of high hydrogen silicone oil (hydrogen content: 1.50%) and 17 kg of toluene were added to a stainless steel autoclave, and nitrogen was substituted until the oxygen content was less than 1%. Ethylene was introduced and the pressure was raised to 3atm. 0.05 kg of a Kadster catalyst (pt content 3000 ppm) was added. The temperature is raised to 80 ℃ for reaction for 6 hours. Removing residual gas, distilling out low-boiling-point substances and toluene to obtain 68 kg of crude methyl ethyl silicone oil. Residual silicon hydrogen was not detected.
68 kg of methyl ethyl silicone oil crude product is put into a cracking reaction kettle, 7 kg of repeatedly cleaned sulfonic acid resin is added, the absolute pressure is 1000Pa, the cracking product is obtained through decompression and cracking at 110 ℃, and then the cracking product is purified through rectification. The cleavage product consisted of 54% tetramethyl tetraethyl cyclotetrasiloxane, 40% pentamethyl pentaethyl cyclopentasiloxane, 5% heptamethyl ethyl trisiloxane, 1% hexamethyldisiloxane.
Example 5
50 kg of high hydrogen silicone oil (hydrogen content 1.50%) was added to the stainless steel autoclave and nitrogen was replaced to an oxygen content of less than 1%. Ethylene was introduced and the pressure was raised to 8atm. 0.05 kg of a Kadster catalyst (pt content 3000 ppm) was added. The temperature is raised to 80 ℃ for reaction for 5 hours. Residual gas was removed to give 71.7 kg of crude methylethyl silicone oil. Residual silicon hydrogen was not detected.
71.7 kg of methyl ethyl silicone oil crude product is put into a cracking reaction kettle, 7 kg of repeatedly cleaned sulfonic acid resin is added, the absolute pressure is 1000Pa, the cracking is carried out at 110 ℃, the cracking product is obtained, and then the rectification and the purification are carried out. The cleavage product consisted of 54% tetramethyl tetraethyl cyclotetrasiloxane, 40% pentamethyl pentaethyl cyclopentasiloxane, 1% hexamethyldisiloxane and 5% heptamethyl ethyl trisiloxane.
TABLE 1
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (10)
1. A method for preparing methylethyl cyclosiloxane, which is characterized by comprising the following steps: and adding the high-hydrogen-content silicone oil and ethylene gas under the condition of a Kasite catalyst to prepare methyl ethyl silicone oil, and then cracking the methyl ethyl silicone oil into tetramethyl tetraethyl cyclotetrasiloxane and pentamethyl pentacyclopentasiloxane to obtain the methyl ethyl cyclosiloxane.
2. The method for preparing methylethyl cyclosiloxane according to claim 1, wherein the hydrogen content in the high hydrogen content silicone oil is 1 to 1.62%.
3. The method for preparing methyl ethyl cyclosiloxane according to claim 1, wherein the addition amount of the Kanster catalyst is 0.08-0.12% of the mass of the high hydrogen silicone oil.
4. The method for producing methyl ethyl cyclosiloxane according to claim 1, wherein the addition is performed by introducing ethylene gas under a nitrogen atmosphere to a pressure of 1 to 8atm.
5. The method for preparing methylethyl cyclosiloxane according to any one of claims 1 to 4, wherein the reaction condition of the addition is to raise the temperature to 80 to 90 ℃ for 4 to 12 hours.
6. The method for producing methyl ethyl cyclosiloxane according to claim 5, wherein an organic solvent is added during the addition, and the organic solvent is a solvent containing no carboxyl group, hydroxyl group, sulfur element, phosphorus element and nitrogen element.
7. The method for preparing methylethyl cyclosiloxane according to claim 1, wherein the cleavage is: methyl ethyl silicone oil and sulfonic acid resin are mixed and then subjected to decompression and cracking.
8. The method for producing methyl ethyl cyclosiloxane according to claim 7, wherein the addition amount of the sulfonic acid resin is more than 5% by mass of methyl ethyl silicone oil.
9. The method for preparing methylethyl cyclosiloxane according to claim 7, wherein the temperature of the reduced pressure pyrolysis is 105-115 ℃.
10. The method for producing methylethyl cyclosiloxane according to claim 7 or 9, wherein the pressure of the reduced pressure pyrolysis is 800 to 1200pa in absolute pressure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310804384.1A CN117003789A (en) | 2023-07-03 | 2023-07-03 | Preparation method of methyl ethyl cyclosiloxane |
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|---|---|---|---|
| CN202310804384.1A CN117003789A (en) | 2023-07-03 | 2023-07-03 | Preparation method of methyl ethyl cyclosiloxane |
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| CN202310804384.1A Pending CN117003789A (en) | 2023-07-03 | 2023-07-03 | Preparation method of methyl ethyl cyclosiloxane |
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| Country | Link |
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