CN111620895A - Process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium - Google Patents
Process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium Download PDFInfo
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- CN111620895A CN111620895A CN202010463272.0A CN202010463272A CN111620895A CN 111620895 A CN111620895 A CN 111620895A CN 202010463272 A CN202010463272 A CN 202010463272A CN 111620895 A CN111620895 A CN 111620895A
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- Prior art keywords
- sodium
- cyclopentadienyl
- methyl
- cyclopentadiene
- cyclopentadiene dimer
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- 238000000034 method Methods 0.000 title claims abstract description 23
- AXTNEYPUUFCBII-UHFFFAOYSA-N sodium;5-methylcyclopenta-1,3-diene Chemical compound [Na+].C[C-]1C=CC=C1 AXTNEYPUUFCBII-UHFFFAOYSA-N 0.000 title claims abstract description 15
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 58
- 239000011734 sodium Substances 0.000 claims abstract description 55
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000002904 solvent Substances 0.000 claims abstract description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 26
- IYQYZZHQSZMZIG-UHFFFAOYSA-N tricyclo[5.2.1.0(2.6)]deca-3,8-diene, 4.9-dimethyl Chemical compound C1C2C3C=C(C)CC3C1C=C2C IYQYZZHQSZMZIG-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 13
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008096 xylene Substances 0.000 claims abstract description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 5
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 208000005156 Dehydration Diseases 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 125000004436 sodium atom Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- -1 methyl cyclopentadienyl Chemical group 0.000 claims 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- UDIPTWFVPPPURJ-UHFFFAOYSA-M Cyclamate Chemical compound [Na+].[O-]S(=O)(=O)NC1CCCCC1 UDIPTWFVPPPURJ-UHFFFAOYSA-M 0.000 description 8
- 239000000625 cyclamic acid and its Na and Ca salt Substances 0.000 description 8
- 229960001462 sodium cyclamate Drugs 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- ANHQLUBMNSSPBV-UHFFFAOYSA-N 4h-pyrido[3,2-b][1,4]oxazin-3-one Chemical group C1=CN=C2NC(=O)COC2=C1 ANHQLUBMNSSPBV-UHFFFAOYSA-N 0.000 description 4
- 241000220317 Rosa Species 0.000 description 4
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 description 4
- 230000036632 reaction speed Effects 0.000 description 4
- QNGLIBBVTNARBG-UHFFFAOYSA-N 1-methylcyclopenta-1,3-diene;sodium Chemical compound [Na].CC1=CC=CC1 QNGLIBBVTNARBG-UHFFFAOYSA-N 0.000 description 2
- 239000006079 antiknock agent Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- DEIHRWXJCZMTHF-UHFFFAOYSA-N [Mn].[CH]1C=CC=C1 Chemical compound [Mn].[CH]1C=CC=C1 DEIHRWXJCZMTHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/04—Sodium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of lead-free gasoline antiknock, in particular to a process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium, which comprises the following steps of mixing metal sodium and cyclopentadiene dimer or methyl cyclopentadiene dimer in a molar ratio of 2: 1-2: 1.1, mixing in an autoclave, adding one solvent selected from tetrahydrofuran, toluene, xylene, diethylene glycol ether, tetraethylene glycol ether, 1, 4-dioxane or a composite solvent thereof, and reacting for 40-60 minutes at the temperature of 200-300 ℃ under the anhydrous and oxygen-free environment condition to obtain cyclopentadienyl sodium or methyl cyclopentadienyl sodium, wherein the molar ratio of metal sodium to the solvent is 1: 1-1: 6. the invention provides a process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium in a kettle by directly taking cyclopentadiene dimer and methyl cyclopentadiene dimer as raw materials, which overcomes the defects of long reaction flow, low raw material utilization rate, high production cost, poor environmental protection caused by generating polymer waste and the like in the prior art.
Description
Technical Field
The invention relates to the field of lead-free gasoline antiknock agents, in particular to a process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium.
Background
Cyclopentadienyl Manganese Tricarbonyl (CMT), Methylcyclopentadienyl Manganese Tricarbonyl (MMT) have been used as unleaded gasoline antiknock agents. There are many patent reports on the synthesis and application of CMT and MMT (see patent information of Chinese patent application No. CN00122359.3, and Chinese patent application No. CN02142341.5, etc.); however, in the existing CMT and MMT production technology, one of the key steps is the production of cyclopentadienyl sodium and methyl cyclopentadienyl sodium.
The existing production mode usually adopts a liquid-phase depolymerization or gas-phase depolymerization process to crack cyclopentadiene dimer (DCPD) and methyl cyclopentadiene dimer (MDCPD) into monomers at a certain temperature, the monomers are stored under the low-temperature protection of less than 0 ℃, and the monomers and the metal sodium sand are reacted at the low temperature of less than 10 ℃ to form the catalyst. However, this process has disadvantages of slow reaction speed, long reaction time (about 20 hours), and consumption of a large amount of cold energy to prevent re-polymerization of cyclopentadiene monomer and methylcyclopentadiene monomer. Therefore, the actual reaction results in slow reaction speed, long reaction time, large consumption of cold energy, low depolymerization rate of cyclopentadiene dimer and methylcyclopentadiene dimer, low utilization rate of cyclopentadiene monomer and methylcyclopentadiene, and generation of more polymer waste.
Therefore, a new process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium is needed at present, so as to overcome the problems of high production cost, need of adding a refrigeration device, a gas phase depolymerization device or a liquid phase depolymerization device and the like in the prior art.
Disclosure of Invention
Aiming at the defects of the prior art, the invention overcomes the defects of long reaction flow, low utilization rate of raw materials, high production cost, poor environmental protection caused by generating polymer waste and the like in the prior art, provides a process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium in a kettle by directly using cyclopentadiene dimer and methyl cyclopentadiene dimer as raw materials, and is used for overcoming the defects in the prior art.
The technical scheme adopted by the invention is as follows: a process for producing sodium cyclopentadienyl or sodium methylcyclopentadienyl comprising contacting sodium metal with a mixture of cyclopentadiene dimer or methylcyclopentadiene dimer in a molar ratio of 2: 1-2: 1.1, mixing in an autoclave, adding one solvent selected from tetrahydrofuran, toluene, xylene, diethylene glycol ether, tetraethylene glycol ether, 1, 4-dioxane or a composite solvent thereof, and reacting for 40-60 minutes at the temperature of 200-300 ℃ under the anhydrous and oxygen-free environment condition to obtain cyclopentadienyl sodium or methyl cyclopentadienyl sodium, wherein the molar ratio of metal sodium to the solvent is 1: 1-1: 6.
the molar ratio of the metal sodium to the solvent is 1: 1-1: 3.
the metal sodium is a sodium rod or a sodium block.
The content of cyclopentadiene dimer or methyl cyclopentadiene dimer in the raw material of cyclopentadiene dimer or methyl cyclopentadiene dimer is not less than 80%.
The reaction is the substitution reaction of molten sodium atom and methylene hydrogen atom on cyclopentadiene and methyl cyclopentadiene molecule at 200-300 deg.c and in anhydrous and oxygen-free environment.
The anhydrous condition is that the water content of the cyclopentadiene dimer or the methyl cyclopentadiene dimer is not more than 100ppm after the distillation and the dehydration treatment of a molecular sieve.
The water content is 50-80 ppm.
Before heating to the reaction temperature, the mixture is intensively stirred at the temperature of 110-120 ℃.
The stirring speed of the stirring is 200-400 rpm.
The anaerobic condition is that the reaction atmosphere is high-purity nitrogen, and the purity of the high-purity nitrogen is not less than 99.9%.
The invention has the beneficial effects that: first, the present invention comprises mixing sodium metal with cyclopentadiene dimer or methylcyclopentadiene dimer in a molar ratio of 2: 1-2: 1.1, mixing in an autoclave, adding one solvent selected from tetrahydrofuran, toluene, xylene, diethylene glycol ether, tetraethylene glycol ether, 1, 4-dioxane or a composite solvent thereof, and reacting for 40-60 minutes at the temperature of 200-300 ℃ under the anhydrous and oxygen-free environment condition to obtain cyclopentadienyl sodium or methyl cyclopentadienyl sodium, wherein the molar ratio of metal sodium to the solvent is 1: 1-1: 6, thereby reducing devices such as low-temperature refrigeration, depolymerization and low-temperature storage of cyclopentadiene dimer (DCPD) and methylcyclopentadiene dimer (DMCPD), reducing equipment investment, expanding the concentration range of the available main raw materials and simplifying the process flow; secondly, the metal sodium is a sodium rod or a sodium block, so that the metal sodium is prevented from being ground, and the industrial implementation is easy; thirdly, the invention accelerates the mixing and reaction speed by strongly stirring at the temperature of 110-120 ℃ before heating to the reaction temperature, so that the invention has simple operation, improves the production efficiency, greatly reduces the production cost and does not generate the polymer waste of cyclopentadiene or methylcyclopentadiene, thereby having good social and economic benefits and being a product which is easy to popularize and use.
Detailed Description
A process for producing sodium cyclopentadienyl or sodium methylcyclopentadienyl comprising contacting sodium metal with a mixture of cyclopentadiene dimer or methylcyclopentadiene dimer in a molar ratio of 2: 1-2: 1.1 mixing in an autoclave, when the metal sodium is present in a molar ratio greater than 2: 1, the reaction speed is high, but sodium particles are remained after the reaction and metal sodium is wasted, and conversely, when the molar ratio of the metal sodium to the cyclopentadiene dimer or the methylcyclopentadiene dimer is more than 2: 1.1, it is difficult to ensure that the cyclopentadiene dimer or methyl cyclopentadiene dimer is fully reacted, so that the produced solution is in an unsaturated state, and one solvent or a compound solvent of tetrahydrofuran, toluene, xylene, diethylene glycol ether, tetraethylene glycol ether, 1, 4-dioxane is added to react for 40-60 minutes at the temperature of 200-300 ℃ under anhydrous and oxygen-free environment conditions to obtain cyclopentadienyl sodium or methyl cyclopentadienyl sodium, wherein the molar ratio of the metal sodium to the solvent is 1: 1-1: 6.
the molar ratio of the metallic sodium to the solvent is preferably 1: 1-1: 3, more solvent can increase the capacity of the reaction solution, thus the reaction is inconvenient to carry out, less solvent is difficult to meet the reaction requirement, and the molar ratio of the metal sodium to the solvent is 1: 1-1: 6, but in order to avoid excessive mixing waste impurities in the product, the molar ratio of the metal sodium to the solvent is 1: 1-1: 3; the metal sodium is a sodium rod or a sodium block; the content of cyclopentadiene dimer or methyl cyclopentadiene dimer in the raw material of cyclopentadiene dimer or methyl cyclopentadiene dimer is not less than 80%.
The reaction is the substitution reaction of molten sodium atom and methylene hydrogen atom on cyclopentadiene and methyl cyclopentadiene molecule at 200-300 deg.c and no water and no oxygen environment; the anhydrous condition is that the water content of the cyclopentadiene dimer or the methylcyclopentadiene dimer is not more than 100ppm after the distillation and the molecular sieve dehydration treatment; the water content is preferably 50-80 ppm; before the reaction temperature is heated, strong stirring is carried out at the temperature of 110-120 ℃; the stirring speed of the stirring is 200-400 rpm, so that the mixing and the reaction are convenient to carry out; the anaerobic condition is that the reaction atmosphere is high-purity nitrogen, and the purity of the high-purity nitrogen is not less than 99.9%.
Example 1: tetrahydrofuran (THF) is used as a solvent, and in the first step, 95 percent of cyclopentadiene dimer (DCPD) is distilled and dehydrated by a molecular sieve to reach 50-80ppm of water; secondly, after the autoclave is cleaned, dried and checked by an air tightness test, 800ml of Tetrahydrofuran (THF) solvent, 46g of sodium blocks and 155ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 40 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at the temperature of 25-30 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose-colored methylcyclopentadiene sodium solution, simultaneously opening the high-pressure kettle to detect the condition of the sodium ring, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium ring.
Example 2: tetrahydrofuran (THF) is used as a solvent, and in the first step, 95 percent of cyclopentadiene dimer (DCPD) is distilled and dehydrated by a molecular sieve to reach 50-80ppm of water; secondly, after the autoclave is cleaned, dried and checked by an air tightness test, 800ml of Tetrahydrofuran (THF) solvent, 46g of sodium block and 185ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 50 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at the temperature of 25-30 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose-colored methylcyclopentadiene sodium solution, simultaneously opening the high-pressure kettle to detect the condition of the sodium ring, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium ring.
Example 3: using dimethylbenzene as a solvent, and distilling 95 percent of cyclopentadiene dimer (DCPD) and dehydrating by a molecular sieve to obtain 50-80ppm of water in the first step; step two, after the high-pressure autoclave is cleaned, dried and checked by an air tightness test, 800ml of xylene solvent, 46g of sodium block and 155ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 40 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at 40 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose sodium cyclopentadiene solution, simultaneously opening the high-pressure kettle to check the condition of sodium cyclamate, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium cyclamate.
Example 4: using dimethylbenzene as a solvent, and distilling 95 percent of cyclopentadiene dimer (DCPD) and dehydrating by a molecular sieve to obtain 50-80ppm of water in the first step; secondly, after the high-pressure kettle is cleaned, dried and checked by an air tightness test, 800ml of xylene solvent, 46g of sodium block and 185ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 50 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at 40 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose sodium cyclopentadiene solution, simultaneously opening the high-pressure kettle to check the condition of sodium cyclamate, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium cyclamate.
Example 5: taking tetraethylene glycol ether as a solvent, and distilling 95 percent of cyclopentadiene dimer (DCPD) and dehydrating by a molecular sieve to obtain 50-80ppm of water in the first step; secondly, after the autoclave is cleaned, dried and checked by an air tightness test, 800ml of tetraethylene glycol ether solvent, 46g of sodium block and 155ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 50 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at the temperature of 60 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose sodium cyclopentadiene solution, simultaneously opening the high-pressure kettle to check the condition of sodium cyclamate, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium cyclamate.
Example 6: taking tetraethylene glycol ether as a solvent, and distilling 95 percent of cyclopentadiene dimer (DCPD) and dehydrating by a molecular sieve to obtain 50-80ppm of water in the first step; secondly, after the high-pressure kettle is cleaned, dried and checked by an air tightness test, 800ml of tetraethylene glycol ether solvent, 46g of sodium block and 185ml of 95 percent cyclopentadiene dimer are added; thirdly, replacing the mixture for 3 times by high-purity nitrogen, namely, heating the mixture to between 110 and 120 ℃, strongly stirring the mixture, and controlling the temperature to be between 200 and 300 ℃ for about 60 minutes to finish the reaction; fourthly, after the reaction is finished, cooling the high-pressure kettle, and checking that the pressure of the residual hydrogen in the high-pressure kettle is about 1.5Mpa at the temperature of 60 ℃ so as to ensure that the reaction is finished; fifthly, when the residual pressure in the high-pressure kettle is 0.5 Mpa, opening a discharge valve to press rose sodium cyclopentadiene solution, simultaneously opening the high-pressure kettle to check the condition of sodium cyclamate, observing that no sodium particles are left at the bottom of the reaction kettle, and completely reacting the sodium cyclamate.
The invention provides a process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium in a kettle by directly taking cyclopentadiene dimer and methyl cyclopentadiene dimer as raw materials, which can overcome the defects of long reaction process, low raw material utilization rate, high production cost, poor environmental protection caused by generating polymer waste and the like in the prior art, so that the invention has wide market prospect.
Claims (10)
1. A process for producing sodium cyclopentadienyl or methyl cyclopentadienyl sodium is characterized in that: comprising mixing sodium metal with cyclopentadiene dimer or methylcyclopentadiene dimer in a molar ratio of 2: 1-2: 1.1, mixing in an autoclave, adding one solvent selected from tetrahydrofuran, toluene, xylene, diethylene glycol ether, tetraethylene glycol ether, 1, 4-dioxane or a composite solvent thereof, and reacting for 40-60 minutes at the temperature of 200-300 ℃ under the anhydrous and oxygen-free environment condition to obtain cyclopentadienyl sodium or methyl cyclopentadienyl sodium, wherein the molar ratio of metal sodium to the solvent is 1: 1-1: 6.
2. the process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 1, wherein: the molar ratio of the metal sodium to the solvent is 1: 1-1: 3.
3. the process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 1, wherein: the metal sodium is a sodium rod or a sodium block.
4. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 1, wherein: the content of cyclopentadiene dimer or methyl cyclopentadiene dimer in the raw material of cyclopentadiene dimer or methyl cyclopentadiene dimer is not less than 80%.
5. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 1, wherein: the reaction is the substitution reaction of molten sodium atom and methylene hydrogen atom on cyclopentadiene and methyl cyclopentadiene molecule at 200-300 deg.c and in anhydrous and oxygen-free environment.
6. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 1, wherein: the anhydrous condition is that the water content of the cyclopentadiene dimer or the methyl cyclopentadiene dimer is not more than 100ppm after the distillation and the dehydration treatment of a molecular sieve.
7. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 6, wherein: the water content is 50-80 ppm.
8. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to any one of claims 1 to 7, wherein: before heating to the reaction temperature, the mixture is intensively stirred at the temperature of 110-120 ℃.
9. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to claim 8, wherein: the stirring speed of the stirring is 200-400 rpm.
10. The process for producing sodium cyclopentadienyl or methyl cyclopentadienyl according to any one of claims 1 to 7, wherein: the anaerobic condition is that the reaction atmosphere is high-purity nitrogen, and the purity of the high-purity nitrogen is not less than 99.9%.
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| CN202010463272.0A CN111620895A (en) | 2020-05-27 | 2020-05-27 | Process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium |
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| CN202010463272.0A CN111620895A (en) | 2020-05-27 | 2020-05-27 | Process for producing cyclopentadienyl sodium or methyl cyclopentadienyl sodium |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2942040A (en) * | 1957-09-18 | 1960-06-21 | Ethyl Corp | Manufacture of sodium cyclopentadiene from cyclopentadiene dimer |
| GB894959A (en) * | 1957-09-18 | 1962-04-26 | Ethyl Corp | Manufacture of cyclopentadienyl manganese carbonyl compounds |
| US4140491A (en) * | 1977-11-21 | 1979-02-20 | Nalco Chemical Company | Gasoline additive comprising a blend of methylcyclopentadienyl manganese tricarbonyl and certain methylcyclopentadiene dimer compounds |
| CN101541812A (en) * | 2006-11-23 | 2009-09-23 | Lg化学株式会社 | Synthesis method of metal cyclopentadienide in bulk |
-
2020
- 2020-05-27 CN CN202010463272.0A patent/CN111620895A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2942040A (en) * | 1957-09-18 | 1960-06-21 | Ethyl Corp | Manufacture of sodium cyclopentadiene from cyclopentadiene dimer |
| GB894959A (en) * | 1957-09-18 | 1962-04-26 | Ethyl Corp | Manufacture of cyclopentadienyl manganese carbonyl compounds |
| US4140491A (en) * | 1977-11-21 | 1979-02-20 | Nalco Chemical Company | Gasoline additive comprising a blend of methylcyclopentadienyl manganese tricarbonyl and certain methylcyclopentadiene dimer compounds |
| CN101541812A (en) * | 2006-11-23 | 2009-09-23 | Lg化学株式会社 | Synthesis method of metal cyclopentadienide in bulk |
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