CN103626622A - Method for preparing methyl cyclopentadiene dimer - Google Patents
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- CN103626622A CN103626622A CN201310528807.8A CN201310528807A CN103626622A CN 103626622 A CN103626622 A CN 103626622A CN 201310528807 A CN201310528807 A CN 201310528807A CN 103626622 A CN103626622 A CN 103626622A
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- cyclopentadiene
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- pentadiene dimer
- cycle pentadiene
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Abstract
The invention discloses a method for preparing a methyl cyclopentadiene dimmer. The method comprises the following steps: (1) preparing a cyclopentadiene monomer; (2) preparing a cyclopentadiene salt; (3) preparing a methyl cyclopentadiene mixture; (4) preparing the methyl cyclopentadiene dimmer. According to the method, the cyclopentadiene dimmer is split into the cyclopentadiene monomer at high temperature and the cyclopentadiene monomer reacts with phthalimide salt or succinimide salt so as to obtain the cyclopentadiene salt, the cyclopentadiene salt further reacts with a methylation reagent so as to obtain the methyl cyclopentadiene mixture, and the methyl cyclopentadiene dimmer is prepared through dimerization reaction and reduced-pressure rectification. According to the method disclosed by the invention, all raw materials are ordinary reagents, the reaction condition is gentle, the operation method and the post-treatment process are simple, no metallic sodium is used, wastewater with acid and alkali is not generated in the production process, the production security is good, pollution is prevented, and both the product yield and the purity are ideal.
Description
Technical field
The present invention relates to fine chemicals preparing technical field, be specifically related to a kind of method of preparing methyl cycle pentadiene dimer.
Background technology
Methyl cycle pentadiene dimer, referred to as DMCPD, is methyl cyclopentadiene monomer (referred to as MCPD) through Pintsch process.It is a kind of important broad-spectrum fine chemical product.It is synthetic gasoline octane promoter on the one hand---the critical materials of methyl cyclopentadienyl tricarbonyl manganese (referred to as MMT).On the other hand, it can be used to synthesized high-performance electronic package material---the sub-tetrahydrophthalic anhydride (referred to as MNA) of methylene in methyl.In addition for the synthesis of organometallic compound derivative as CP
2tiCl
2, senior essence and flavoring agent and reactive flame retardant, etc., and purposes scope is also in continuous expansion.Yet because the direct sources of methyl cycle pentadiene dimer is limited, the study on the synthesis of therefore carrying out methyl cycle pentadiene dimer (referred to as DMCPD) has very important theoretical investigation value and realistic meaning.
At present methyl cycle pentadiene dimer is had to more preparation method, but mainly by extraction separation and two kinds of approach of chemical synthesis, obtain target product methyl cycle pentadiene dimer.Extraction separation refers to from petroleum cracking C
5-6the methyl cycle pentadiene dimer extracting in cut.Lanzhou University's Zhao Yingchun Master's thesis in 2007 discloses from cracking C
5-6in cut, extract the method for cycle pentadiene dimer, methyl cycle pentadiene dimer.Yet at C
5-6in cut, extract methyl cycle pentadiene dimer content few, therefore without practical application in industry, be worth.Chemical synthesis comprises following three kinds: (1) sodium method: cyclopentadiene (CPD) reacts with sodium Metal 99.5 and generates cyclopentadienyl sodium salt in solvent, then uses methylating reagent, as CH
3cl, CH
3br, methyl-sulfate and methylcarbonate, carry out alkylated reaction to cyclopentadiene sodium salt and make methyl cyclopentadiene (MCPD) monomer, finally by dimerization reaction, makes methyl cycle pentadiene dimer.Though this route speed of response is fast, transformation efficiency is higher, US 4547603A for example, CN101205168A, Zhang Wei-Shenyang Institute of Chemical Technology Master's thesis-2
006,but owing to using inflammable sodium Metal 99.5 and producing inflammable and explosive hydrogen, reaction conditions is extremely strict, wayward.(2) phase transfer catalysis process: be by cyclopentadiene monomers, liquid caustic soda under phase-transfer catalyst, at 0-5 ℃, react synthesizing methyl cyclopentadiene monomers with methylating reagent, then through dimerization reaction, rectification under vacuum makes methyl cycle pentadiene dimer.Such as Wei Rongbao etc.-Hebei chemical industry-
1985, Luo Minyi etc.-CN1785942A-
2006.Adopt this technique to have three large technical difficulties, purity is low, only can reach 90%, and in order to reduce cyclopentadiene dimerization, whole reaction need be reacted at 0-5 ℃, and this makes again the reaction times long, and cannot avoid cyclopentadiene dimerization completely, thereby make per pass conversion be less than 50%, per pass conversion is low, bring again exceptional hardship to dimer rectifying; Also have a large amount of salkali waste, catalyzer and sodium-chlor to coexist, cannot adopt simple method to process this alkali waste water.(3) acid, base catalysis method: take cycle pentadiene dimer, methyl alcohol is raw material, make methyl cyclopentadiene monomer, then through dimerization reaction, rectification under vacuum makes methyl cycle pentadiene dimer in fixed-bed reactor by catalytic methylation.Such as CN200510039232.9, Sun Linbing etc.-catalysis journal-2006, Liu Xiaozhi etc.-Shenyang Institute of Chemical Technology journal-1998.The advantage of the method is that the preparation method of catalyzer is simple, or the transformation efficiency of cyclopentadiene (≤50%), poor selectivity (≤60%), productive rate extremely low (≤30%), and cycle pentadiene dimer raw material exists depolymerization difficulty, blocking pipe and catalyzer to be easy to the shortcomings such as carbon distribution, inactivation, regeneration period be short in preparation process, or produce acid, alkaline industrial waste water, affect environment.
Above-mentioned several method all can obtain methyl cycle pentadiene dimer, but exist that product yield is low, the shortcoming such as complex operation, poor stability, pollution are large, be not suitable for suitability for industrialized production.
summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provide that a kind of technique is simple, production security good, produce and hold the manageable novel method of preparing methyl cycle pentadiene dimer.
The ultimate principle of this novel method can be described with following formula:
The present invention realizes in the following way, a kind of method of preparing methyl cycle pentadiene dimer, and concrete steps are as follows:
(1) preparation of cyclopentadiene monomers: take cycle pentadiene dimer as raw material, under 240-320 ℃ and condition of normal pressure, be cracked into fast cyclopentadiene monomers by dropping mode;
(2) preparation of cyclopentadienyl salt: the cyclopentadiene monomers of step 1 preparation is added drop-wise in the dichloromethane solution that contains inferior amine salt and is reacted, reaction finishes to filter to obtain under rear nitrogen protection cyclopentadienyl salt dichloromethane solution, the cyclopentadiene monomers adding in reaction system and inferior amine salt mol ratio are (1.5～1): 1, and room temperature reaction 3-6h;
(3) preparation of methyl cyclopentadiene mixture: in the cyclopentadienyl salt dichloromethane solution of step 2 preparation, add methylating reagent, low-temp reaction, after reaction finishes, filtration makes methyl cyclopentadiene mixture, in reaction system, the mol ratio of methylating reagent and cyclopentadiene is 1:(1～1.2), temperature of reaction is-5～15 ℃, the reaction times is 4～6h;
(4) preparation of methyl cycle pentadiene dimer: the methyl cyclopentadiene mixture that step 3 is prepared reacts through heated polymerizable, normal pressure reclaims dichloromethane solvent, then concentrating under reduced pressure rectifying obtains methyl cycle pentadiene dimer; In heated polymerizable reaction process, polymeric reaction temperature is 30～120 ℃, and the reaction times is 4～6h.
In order to obtain better technique effect, in the inventive method, in step 1, Pintsch process temperature is preferably 280～300 ℃, by dropping mode, adds cycle pentadiene dimer; In step 2, the cyclopentadiene monomers adding and inferior amine salt mol ratio are preferably 1:1, and room temperature reaction is preferably 4h; In step 2, described inferior amine salt is one or more combinations in phthalic imidine salt, succsinic acid imide salt; In step 3, the preferred 1:1 of the mol ratio of methylating reagent and cyclopentadiene, temperature of reaction is preferably 5 ℃, and the reaction times is preferably 5h; Described methylating reagent is a halomethane, one or more combinations in methyl-sulfate, methylcarbonate, methanesulfonic methyl esters, trifluoromethanesulfonic acid methyl esters, dme, methylamine; In step 4, polymeric reaction temperature is preferably 30～120 ℃, and polymerization reaction time is preferably 4h; In step 4, concentrating under reduced pressure rectifying pressure is 10～1000Pa; In step (4), concentrating under reduced pressure rectifying pressure is preferably 100Pa; In step 4, concentrating under reduced pressure rectification temperature is 80～100 ℃.
The advantages such as the present invention obtains methyl cyclopentadiene, and product yield is high, simple to operate, safe, are applicable to suitability for industrialized production.
Embodiment
In order further to understand summary of the invention of the present invention, with reference to the present invention of preferred example more detailed description, the example described in providing is the object in explanation only, does not form any limitation of the invention.
embodiment 1
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 280 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds in the three-necked flask that contains 1mol O-phthalic inferior amine salt and 300ml methylene dichloride again, keep 25 ℃ of reaction 4h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 1mol trifluoromethanesulfonic acid methyl esters, cold going to 5 ℃ of reaction 5h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 30 ℃ of dimerization reaction 4h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 100Pa, to obtain content be 98% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 96%.
embodiment 2
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 290 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds in the three-necked flask that contains 1mol succsinic acid imide salt and 300ml methylene dichloride again, keep 30 ℃ of reaction 3h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 1mol trifluoromethanesulfonic acid methyl esters, cold going to-5 ℃ of reaction 4h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 120 ℃ of dimerization reaction 5h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 10Pa, to obtain content be 97.3% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 91%.
embodiment 3
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 300 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds and contains 0.5mol O-phthalic inferior amine salt again, in the three-necked flask of 0.5mol succsinic acid imide salt and 300ml methylene dichloride, keep 20 ℃ of reaction 5h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 1mol methyl iodide, cold going to 0 ℃ of reaction 6h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 90 ℃ of dimerization reaction 4.5h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 1000Pa, to obtain content be 96.2% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 93%.
embodiment 4
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 240 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds in the three-necked flask that contains 1mol O-phthalic inferior amine salt and 300ml methylene dichloride again, keep 15 ℃ of reaction 6h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 1mol methyl-sulfate, cold going to 10 ℃ of reaction 4.5h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 60 ℃ of dimerization reaction 5.5h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 300Pa, to obtain content be 96.5% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 91%.
embodiment 5
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 320 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds in the three-necked flask that contains 1mol O-phthalic inferior amine salt and 300ml methylene dichloride again, keep 22 ℃ of reaction 3.5h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 1mol methylcarbonate, cold going to 15 ℃ of reaction 5.5h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 45 ℃ of dimerization reaction 6h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 500Pa, to obtain content be 96% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 90%.
embodiment 6
The three-necked flask that is equipped with thermometer and fractional distillation filling-material post is heated to 260 ℃, to splash into 66 grams be 0.5mol cycle pentadiene dimer, and through cracking fast, to obtain 66g be 1mol cyclopentadiene monomers, be cooled to 0 ℃, obtain liquid cyclopentadiene monomers, under nitrogen protection, by the 66g of firm cracking, be that 1mol cyclopentadiene monomers adds in the three-necked flask that contains 1mol O-phthalic inferior amine salt and 300ml methylene dichloride again, keep 18 ℃ of reaction 4.5h of room temperature, after reaction finishes, filter to get filtrate and be cyclopentadienyl salt dichloromethane solution, then in filtrate, add 0.2mol methanesulfonic methyl esters, the mixed solution of 0.3mol dme and 0.5mol methylamine, cold going to 8 ℃ of reaction 5h, filter to obtain methyl cyclopentadiene mixture.Methyl cyclopentadiene mixture is after 75 ℃ of dimerization reaction 5h, normal pressure reclaims dichloromethane solvent, being decompressed to the concentrated rectifying of 50Pa, to obtain content be 97% methyl cycle pentadiene dimer product again, and the methyl cycle pentadiene dimer yield of cycle pentadiene dimer of take is 94%.
Claims (10)
1. a method of preparing methyl cycle pentadiene dimer, step is as follows:
(1) preparation of cyclopentadiene monomers: take cycle pentadiene dimer as raw material, under 240-320 ℃ and condition of normal pressure, be cracked into fast cyclopentadiene monomers by dropping mode;
(2) preparation of cyclopentadienyl salt: the cyclopentadiene monomers of step 1 preparation is added drop-wise in the dichloromethane solution that contains inferior amine salt and is reacted, reaction finishes to filter to obtain under rear nitrogen protection cyclopentadienyl salt dichloromethane solution, the cyclopentadiene monomers adding in reaction system and inferior amine salt mol ratio are (1.5～1): 1, and room temperature reaction 3-6h;
(3) preparation of methyl cyclopentadiene mixture: in the cyclopentadienyl salt dichloromethane solution of step 2 preparation, add methylating reagent, low-temp reaction, after reaction finishes, filtration makes methyl cyclopentadiene mixture, in reaction system, the mol ratio of methylating reagent and cyclopentadiene is 1:(1～1.2), temperature of reaction is-5～15 ℃, the reaction times is 4～6h;
(4) preparation of methyl cycle pentadiene dimer: the methyl cyclopentadiene mixture that step 3 is prepared reacts through heated polymerizable, normal pressure reclaims dichloromethane solvent, then concentrating under reduced pressure rectifying obtains methyl cycle pentadiene dimer; In heated polymerizable reaction process, polymeric reaction temperature is 30～120 ℃, and the reaction times is 4～6h.
2. the method for preparing methyl cycle pentadiene dimer as claimed in claim 1, is characterized in that: in step 1, Pintsch process temperature is preferably 280～300 ℃, by dropping mode, adds cycle pentadiene dimer.
3. the method for preparing methyl cycle pentadiene dimer as claimed in claim 1 or 2, is characterized in that: in step 2, the cyclopentadiene monomers adding and inferior amine salt mol ratio are preferably 1:1, and room temperature reaction is preferably 4h.
4. the method for preparing methyl cycle pentadiene dimer as described in claim 1 or 3, is characterized in that: in step 2, described inferior amine salt is one or more combinations in phthalic imidine salt, succsinic acid imide salt.
5. the method for preparing methyl cycle pentadiene dimer as claimed in claim 1 or 2, is characterized in that: in step 3, and the preferred 1:1 of the mol ratio of methylating reagent and cyclopentadiene, temperature of reaction is preferably 5 ℃, and the reaction times is preferably 5h.
6. the method for preparing methyl cycle pentadiene dimer as described in claim 1 or 5, it is characterized in that: described methylating reagent is a halomethane one or more combinations in methyl-sulfate, methylcarbonate, methanesulfonic methyl esters, trifluoromethanesulfonic acid methyl esters, dme, methylamine.
7. the method for preparing methyl cycle pentadiene dimer as claimed in claim 1 or 2, is characterized in that: in step 4, polymeric reaction temperature is preferably 30～120 ℃, and polymerization reaction time is preferably 4h.
8. the method for preparing methyl cycle pentadiene dimer as claimed in claim 1 or 2, is characterized in that: in step 4, concentrating under reduced pressure rectifying pressure is 10～1000Pa.
9. the method for preparing methyl cycle pentadiene dimer as claimed in claim 8, is characterized in that: in step 4, concentrating under reduced pressure rectifying pressure is preferably 100Pa.
10. the method for preparing methyl cyclopentadiene as claimed in claim 1, is characterized in that: in step 4, concentrating under reduced pressure rectification temperature is 80～100 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117105738A (en) * | 2023-10-24 | 2023-11-24 | 广东新华粤石化集团股份公司 | Preparation method of methylcyclopentadiene dimer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA820975A (en) * | 1969-08-19 | Ziegler Karl | Substitution products of cyclopentadiene and its alkyl and benzyl derivatives and the production thereof | |
| JP2001097896A (en) * | 1999-09-28 | 2001-04-10 | Asahi Kasei Corp | Method for producing alkylcyclopentadiene compound |
| CN1785942A (en) * | 2005-05-02 | 2006-06-14 | 宜兴市创新精细化工有限公司 | Synthesis method of methyl cycle pentadiene dimer |
-
2013
- 2013-11-01 CN CN201310528807.8A patent/CN103626622B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA820975A (en) * | 1969-08-19 | Ziegler Karl | Substitution products of cyclopentadiene and its alkyl and benzyl derivatives and the production thereof | |
| JP2001097896A (en) * | 1999-09-28 | 2001-04-10 | Asahi Kasei Corp | Method for producing alkylcyclopentadiene compound |
| CN1785942A (en) * | 2005-05-02 | 2006-06-14 | 宜兴市创新精细化工有限公司 | Synthesis method of methyl cycle pentadiene dimer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117105738A (en) * | 2023-10-24 | 2023-11-24 | 广东新华粤石化集团股份公司 | Preparation method of methylcyclopentadiene dimer |
| CN117105738B (en) * | 2023-10-24 | 2024-02-06 | 广东新华粤石化集团股份公司 | Preparation method of methylcyclopentadiene dimer |
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