CN101165065A - Method for producing alkylated cyclopentadiene tricarbonyl manganese - Google Patents
Method for producing alkylated cyclopentadiene tricarbonyl manganese Download PDFInfo
- Publication number
- CN101165065A CN101165065A CNA2006101374110A CN200610137411A CN101165065A CN 101165065 A CN101165065 A CN 101165065A CN A2006101374110 A CNA2006101374110 A CN A2006101374110A CN 200610137411 A CN200610137411 A CN 200610137411A CN 101165065 A CN101165065 A CN 101165065A
- Authority
- CN
- China
- Prior art keywords
- cyclopentadiene
- alkylating
- tricarbonyl manganese
- production method
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to synthesis process of organic metal compound, and is especially process of producing alkylated methyl cyclopentadienyl tricarbonyl manganese, which is applied as the antiknock additive for engine fuel.
Description
Technical field
The present invention relates to a kind of production method of alkylating cyclopentadiene tricarbonyl manganese.Relate to a kind of metal-organic synthesis technique specifically, the method for especially producing methylated cyclopentadiene tricarbonyl manganese.Alkylating cyclopentadiene tricarbonyl manganese is a kind of antiknock dope that is used for motor spirit.
Background technology
Alkylating cyclopentadiene tricarbonyl manganese is a kind of antiknock dope, with methyl cyclopentyl-dialkyl-tricarbon manganium (MMT) widespread use the most.Registered 97122153 the Chinese patent of being numbered has disclosed a kind of method of producing cyclopentadiene tricarbonyl manganese.But the cyclopentadiene tricarbonyl manganese that this method is produced is a kind of crystalline salt.Crystalline salt is used in the liquid antiknock dope uses that certain difficulty, its dissolving in solvent are arranged is a problem that must solve in the technology.
In addition, in the process of producing alkylating cyclopentadiene tricarbonyl manganese, often unavoidably produce by product such as cyclopentadiene tricarbonyl manganese (CMT).Remove the CMT by product and need more equipment and cost.But alkylating its characteristics of cyclopentadiene tricarbonyl manganese production method that the present invention relates to are need not remove the CMT by product of production.The mixture of a spot of CMT and alkylating cyclopentadiene tricarbonyl manganese has produced beyond thought synergy.
Summary of the invention
The present invention discloses a kind of simple, effectively, the method for the alkyl cyclopentadiene manganese tricarbonyl of practical production.Specifically, the present invention relates to a kind of production method of fuel oil antiknock dope, described additive is alkylating cyclopentadiene tricarbonyl manganese.Preferably, alkylation of the present invention is meant alkyl list or the polysubstituted cyclopentadiene group with a branch or the unbranched 1-4 of a containing carbon atom.More preferably, alkylating cyclopentadiene of the present invention is selected from methyl cyclopentadiene, the dimethyl cyclopentadiene, the trimethylammonium cyclopentadiene, tetramethyl-ring pentadiene, ethyl cyclopentadiene, the diethyl cyclopentadiene, triethyl cyclopentadiene, tetraethyl-cyclopentadiene, the propyl group cyclopentadiene, dipropyl cyclopentadiene, tripropyl cyclopentadiene, the tetrapropyl cyclopentadiene, butyl cyclopentadiene, dibutyl cyclopentadiene, tributyl cyclopentadiene, tetrabutyl cyclopentadiene and their mixture.Especially excellently, the present invention relates to the production method of a kind of production methyl cyclopentyl-dialkyl-tricarbon manganium (MMT).
Description of drawings:
Fig. 1: octane value response curve figure shows the influence of the MMT/CMT mixture of different ratios to the octane value generation.
Fig. 2: the octane value change curve shows that the MMT/CMT mixture of different ratios changes the influence that produces to octane value.
Describe in detail：
The present invention relates to a kind of method of producing alkylating cyclopentadiene tricarbonyl manganese, its feature exists Single or polysubstituted cyclopentadiene in raw materials, wherein each substituting group be branch or regardless of The alkyl that contains 1-4 carbon atom that props up. Especially, alkylating cyclopentadiene of the present invention Be selected from methyl cyclopentadiene, dimethyl cyclopentadiene, trimethyl cyclopentadiene, tetramethyl-ring penta 2 Alkene, the ethyl cyclopentadiene, the diethyl cyclopentadiene, the triethyl group cyclopentadiene, the tetraethyl cyclopentadiene, The propyl group cyclopentadiene, dipropyl cyclopentadiene, tripropyl cyclopentadiene, tetrapropyl cyclopentadiene, fourth The basic ring pentadiene, the dibutyl cyclopentadiene, the tributyl cyclopentadiene, tetrabutyl cyclopentadiene, with And their mixture. Particularly preferably, alkylating cyclopentadiene of the present invention is first Basic ring pentadiene, the alkylating cyclopentadiene tricarbonyl manganese that produces are methyl cyclopentadiene three carbonyls Base manganese (MMT).
According to one embodiment of the invention, alkylating cyclopentadiene tricarbonyl manganese produces by the following method:
(1) selection has the reactor of whipping appts and medium heating jacket, in this reactor and in inert atmosphere, react,
(2) medium and the sodium Metal 99.5 with institute's requested number injects in the still, and then, its production process is carried out in inert atmosphere,
(3) subsequently reaction-ure mixture is stirred, add alkylating cyclopentadiene, when stopping to decompose hydrogen, the proved response process stops, and generates alkylating cyclopentadiene sodium,
(4) at ambient temperature, add Manganous chloride tetrahydrate and sulfuration dicarbapentaborane iron or phosphatization dicarbapentaborane iron, stir and heat, add CO to reactor then, and reactor is no less than the 80-100 normal atmosphere being full of to be forced under the CO condition, reaction medium is heated to enough can finishes the temperature of reaction and accelerate stirring velocity
(5) when CO no longer is absorbed, the end of expression reaction process stops heating, continuing to be cooled to room temperature under the stirring condition, with reactive material discharging from reactor, gets thick product.Wherein the cyclopentadiene tricarbonyl manganese content of by-products is about 1.5-15%.
According to the described step 4 of above invention embodiment, after adding Manganous chloride tetrahydrate and sulfuration dicarbapentaborane iron (or Manganous chloride tetrahydrate and phosphatization dicarbapentaborane iron) at ambient temperature, add CO to reactor, reaction mixture is stirred and is heated to the temperature that enough can finish reaction, wherein the outlet temperature of reaction medium is preferably between 200 to 500 degree Celsius, between the 240-300 degree more preferably Celsius, 250-260 degree most preferably Celsius.For stirring velocity, the solid phase of described reaction medium should be not less than 10 meter per seconds with the relative stirring velocity of liquid phase, and perhaps, total stirring velocity of reaction mixture is changeed for per minute 50-400.
According to another embodiment of the invention, the method for the alkylating cyclopentadiene tricarbonyl manganese of above-mentioned production further comprises mode in 30-80 ℃ temperature under the purified step of coarse fodder product by vacuum distilling.
Being applicable to that the medium among the present invention can be tetrahydrofuran (THF) or diethylene glycol dimethyl ether, also can be that well known to those skilled in the art other is applicable to the medium of producing the organic octane promoter of metal.Being applicable to that equipment of the present invention can be the registered equipment that 97122153 Chinese patent discloses that is numbered, also can be that other is applicable to and produces the organic octane promoter of metal, has the equipment of whipping appts and medium heating jacket.The full content that is incorporated herein Chinese patent 97122153 with to the present invention as supporting and explanation.
An advantage of the present invention is that it provides a kind of production method of alkylating cyclopentadiene tricarbonyl manganese, and its carbonylation processes is fast, and the rate of recovery height of product is with short production cycle, and the whipping step of the processing of product and machinery makes moderate progress.
Another advantage of the present invention is that the alkylating cyclopentadiene tricarbonyl manganese that is produced is liquid, has increased it as antiknock dope and other solubility of additive and Combination, makes product convenient easy-to-use.The finished product cyclopentadiene tricarbonyl manganese that technology produced of existing production cyclopentadiene tricarbonyl manganese is a kind of crystalline salt, it must be dissolved in the machine solvent can use.The alkylating cyclopentadiene tricarbonyl manganese of product of finishing of the present invention then is a liquid, and it all is better than cyclopentadiene tricarbonyl manganese as solubility of additive and Combination.Therefore, the invention solves cyclopentadiene three carbonyls and be difficult to direct applied problem as crystalline salt.
Another advantage of the present invention is that it can produce the burning stiffeners mixture of a kind of alkylating cyclopentadiene tricarbonyl manganese and cyclopentadiene tricarbonyl manganese, and this mixture has beyond thought effect to the octane value that improves fuel.Specifically, in the process of producing alkylating cyclopentadiene tricarbonyl manganese, tend to inevasible generation cyclopentadiene tricarbonyl manganese, and the place to go cyclopentadiene tricarbonyl manganese needs extra operation and equipment, has increased production time and spending.The present invention finds that alkylating cyclopentadiene tricarbonyl manganese mixes with a certain proportion of cyclopentadiene tricarbonyl manganese and can produce beyond thought combustion-supporting effect, that is, the combustion-supporting effect of mixture is also better than single alkylating cyclopentadiene tricarbonyl manganese or single cyclopentadiene tricarbonyl manganese.And, because alkylating cyclopentadiene tricarbonyl manganese can effectively dissolve the cyclopentadiene tricarbonyl manganese by product that produces in the production process, need not provide other solvent with the dissolving cyclopentadiene tricarbonyl manganese again, therefore, described production method produced according to the invention can produce the mixture of alkylating cyclopentadiene tricarbonyl manganese and cyclopentadiene tricarbonyl manganese once.That is, the present invention neither needs to use more equipment and cost to remove cyclopentadiene tricarbonyl manganese, does not also need to provide another kind of solvent with the dissolving cyclopentadiene tricarbonyl manganese, makes that the present invention can more economic and effective application in industry.
Embodiment
Embodiment 1:
(1) selects for use 6 liters to be provided with whipping appts and medium heating jacket reactor, and in this still, react.
(2) with rare gas element CO reactor is carried out purge earlier, and add 3.3 liters of tetrahydrofuran (THF)s and 253 gram sodium Metal 99.5s, and be suspended state in the tetrahydrochysene medium.Repeat purge with rare gas element.
(3) (solid phase, liquid phase stirring velocity in reaction medium is 0.01 meter per second) slowly stirred in beginning, under less than 10 ℃ of conditions of temperature, adds 780 gram methyl cyclopentadienes, and when stopping to decompose hydrogen, the proved response process stops, and generates methyl cyclopentadiene sodium.
(4) at ambient temperature, in solvents tetrahydrofurane, add 7000 gram Manganous chloride tetrahydrates and 10.3 gram (0.1 mole) sulfuration dicarbapentaborane iron mixtures, stir, be heated to 60 ℃, add CO to reactor then, make it to be forced into 80 atmospheric pressures with suspended state.Be warming up to 250-260 ℃.Reaction stirred.Its solid phase and liquid phase stir speed of relative movement and are not less than 10 seconds/meter.Stop through reactor internal drop in 15 minutes.The proved response material is drawn CO and is stopped, and proves that simultaneously carbonyl reaction stops.
(5) lower the temperature and stop to stir, reactant is cooled to room temperature, and reactive material is discharging from reactor, promptly gets the thick product of methyl cyclopentyl-dialkyl-tricarbon manganium of the present invention.
The thick product of methyl cyclopentyl-dialkyl-tricarbon manganium is separated out purified product by vacuum distilling in temperature 80-95 ℃, obtain the methyl cyclopentyl-dialkyl-tricarbon manganium crystalline powder.
Embodiment 2:
According to ASTM D2699 international standard, adopt the ASTM-CFR testing engine, the mixture of blended methyl cyclopentyl-dialkyl-tricarbon manganium (MMT) and cyclopentadiene tricarbonyl manganese (CMT) is in varing proportions tested.Under the manganese content of par, write down different mixtures to conventional white gasoline (Regular Unleaded Gasoline, the effect of burning octane value RUL).
Fig. 1 shows the influence that in each manganese interpolation level (Treat Rate) octane value (Octane Number) is produced with the MMT/CMT mixture of different mixed.Fig. 2 shows with respect to the basic fuel oil that does not add any octane promoter, and the MMT/CMT mixture of different ratios adds level at each manganese octane value is changed the influence that (Delta Octane Number) produced.As shown in the figure, the mixture that contains about 10%CMT and about 90%MMT has produced beat all synergy in the interpolation level of 8mg Mn/L, and its octane value is changed to 1.4 (Fig. 2).For the octane value variation that the independent use numerical value that MMT produced is 0.9, this has represented 56% reinforced effects.
Claims (10)
1. method of producing alkylating cyclopentadiene tricarbonyl manganese is characterized in that:
(1) selection has the reactor of whipping appts and medium heating jacket, in this reactor and in inert atmosphere, react,
(2) medium and the sodium Metal 99.5 with institute's requested number injects in the still, and then, its production process is carried out in inert atmosphere,
(3) subsequently reaction-ure mixture is stirred, add alkylating cyclopentadiene, when stopping to decompose hydrogen, the proved response process stops, and generates alkylating cyclopentadiene sodium,
(4) at ambient temperature, add Manganous chloride tetrahydrate and sulfuration dicarbapentaborane iron or phosphatization dicarbapentaborane iron, stir and heat, add CO to reactor then, and reactor is no less than the 80-100 normal atmosphere being full of to be forced under the CO condition, reaction medium is heated to enough finishing the temperature of reaction and accelerating stirring velocity
(5) when CO no longer is absorbed, the end of expression reaction process stops heating, continuing to be cooled to room temperature under the stirring condition, with reactive material discharging from reactor, gets thick product.
2. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1 further comprises mode in 30-80 ℃ temperature under the purified step of described thick product by vacuum distilling.
3. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1, it is characterized in that described alkylating cyclopentadiene is selected from: methyl cyclopentadiene, the dimethyl cyclopentadiene, the trimethylammonium cyclopentadiene, tetramethyl-ring pentadiene, ethyl cyclopentadiene, the diethyl cyclopentadiene, the triethyl cyclopentadiene, tetraethyl-cyclopentadiene, propyl group cyclopentadiene, the dipropyl cyclopentadiene, the tripropyl cyclopentadiene, tetrapropyl cyclopentadiene, butyl cyclopentadiene, the dibutyl cyclopentadiene, the tributyl cyclopentadiene, tetrabutyl cyclopentadiene, and their mixture.
4. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1 is characterized in that described alkylating cyclopentadiene is a methyl cyclopentadiene.
5. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1, its feature also is: described medium is tetrahydrofuran (THF) or diethylene glycol dimethyl ether.
6. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1 is characterized in that the solid phase of described reaction medium should be not less than 10 meter per seconds with the relative stirring velocity of liquid phase.
7. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1, the total stirring velocity that it is characterized in that described reaction medium is between 50-400 rev/min.
8. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 1 is characterized in that described reaction medium is heated to 200 to 500 degree Celsius.
9. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 8 is characterized in that described reaction medium is heated to 240 to 300 degree Celsius.
10. the production method of alkylating cyclopentadiene tricarbonyl manganese as claimed in claim 9 is characterized in that described reaction medium is heated to 250 to 260 degree Celsius.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101374110A CN101165065A (en) | 2006-10-18 | 2006-10-18 | Method for producing alkylated cyclopentadiene tricarbonyl manganese |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101374110A CN101165065A (en) | 2006-10-18 | 2006-10-18 | Method for producing alkylated cyclopentadiene tricarbonyl manganese |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101165065A true CN101165065A (en) | 2008-04-23 |
Family
ID=39333934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006101374110A Pending CN101165065A (en) | 2006-10-18 | 2006-10-18 | Method for producing alkylated cyclopentadiene tricarbonyl manganese |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101165065A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570769A (en) * | 2013-11-22 | 2014-02-12 | 辽宁石油化工大学 | Method for synthesizing methyl cyclopentadienyl manganese tricarbonyl |
| CN111518144A (en) * | 2020-05-26 | 2020-08-11 | 开封泓盈化工发展有限公司 | Process for extracting cyclopentadiene tricarbonyl manganese by reduced pressure distillation |
-
2006
- 2006-10-18 CN CNA2006101374110A patent/CN101165065A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570769A (en) * | 2013-11-22 | 2014-02-12 | 辽宁石油化工大学 | Method for synthesizing methyl cyclopentadienyl manganese tricarbonyl |
| CN111518144A (en) * | 2020-05-26 | 2020-08-11 | 开封泓盈化工发展有限公司 | Process for extracting cyclopentadiene tricarbonyl manganese by reduced pressure distillation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0025702B1 (en) | Process for producing ethylidenediacetate | |
| CN1190410A (en) | Addition polymers of polycycloolefines containing functional substituents | |
| EP2684940B1 (en) | Additives for fuels and oils comprising functionalised diblock copolymers | |
| CN1100087A (en) | Process for the preparation of carboxylic acids or corresponding esters in the presence of a catalyst based on reodium and iridium | |
| CN101165065A (en) | Method for producing alkylated cyclopentadiene tricarbonyl manganese | |
| JP4612547B2 (en) | Method for producing ester condensate | |
| JP5349450B2 (en) | Iron-containing polymer suitable for diesel exhaust particle trap regeneration | |
| RU2005138788A (en) | METHOD OF CARBONILATION USING CATALYSTS WITH METAL-POLYPENTENT LIGANDS | |
| KR102008546B1 (en) | Process for making hybrid polyester-polyether polyols | |
| US7256303B1 (en) | Method for producing alkylated cyclopentadienyl manganese tricarbonyls | |
| CN114989405B (en) | Titanium catalyst for synthesizing polyester by DMT method and preparation method and application thereof | |
| CN107286187B (en) | Alkyl aluminum complex containing N, N, N, N-tetradentate chelating penta-coordination, preparation method thereof and method for catalyzing ring-opening polymerization of lactide | |
| CN102173447B (en) | Method for directly synthesizing metal (tungsten or molybdenum) carbonyl complex from tungsten oxide or molybdenum oxide | |
| CN103282329B (en) | The manufacture method of alkene | |
| CN111875637B (en) | Phosphine ligand and synthesis method and application thereof | |
| CN1042034C (en) | Catalyst synthesis | |
| CN100999689A (en) | Preparation process of methyl cyclopent diene manganese tricarbonyl (MMT) antiexplosive agent | |
| CN112831357B (en) | High-environmental-protection fuel oil capable of replacing gasoline and preparation method thereof | |
| JP3031572B2 (en) | Hydrocarbon oil composition | |
| EP0784044B1 (en) | Process for producing monocarboxylic and/or dicarboxylic acids | |
| CN107848942B (en) | Process for preparing vinyl esters of higher carboxylic acids | |
| CN113336620B (en) | Preparation method of bicyclobutane and application of bicyclobutane as aerospace high-energy fuel | |
| CN104549523B (en) | Catalyst for ethylidene diacetate synthesis | |
| CN1242029C (en) | Diesel combustion-supporting agent and preparation method thereof | |
| JP6726329B2 (en) | Method for producing polybutadiene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20080423 |