CN103566972B - A kind of Ferrocene oligomer and preparation method thereof - Google Patents
A kind of Ferrocene oligomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Ferrocene oligomer and preparation method thereof.With ethyl dicyclopentadienyl iron and triphosgene for raw material, by friedel-crafts acylation reaction preparation poly-(1-ethyl-1 '-formyl ferrocene), then through obtained poly-(1-ethyl-1 '-methylene radical ferrocene) oligopolymer of reduction reaction.The mixture of the tripolymer of 1-ethyl-1 '-methylene radical ferrocene, the tetramer and pentamer is comprised in oligopolymer, iron level reaches 25.22%, can be used as solid propellant combustion rate catalyzer, ensure under the lower level condition of addition, obtain the fast composite solidpropellant of high combustion.Ferrocene oligomer provided by the invention is when mixing with composite solidpropellant each component, and polymer chain is more easily gathered in polar oxygen agent ammoniumper chlorate surface, easily around oxygenant, forms combustion catalysis active centre, thus can effectively catalysis.Ferrocene oligomer preparation technology provided by the invention is easy, reaction conditions is gentle, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of Ferrocene oligomer and preparation method thereof, particularly a kind of solid propellant ferrocene burningrate catalyst and preparation method thereof.
Background technology
In the composite solidpropellant system being oxygenant with ammoniumper chlorate (AP), ferrocene deriv has obtained as the burningrate catalyst of high comprehensive performance and has applied widely, wherein, 2, the products such as 2 '-bis-(ethyl dicyclopentadienyl iron base)-propane (Kato is pungent, Catocene), octyl ferrocene and tertiary butyl ferrocene are the burningrate catalyst principal item used in current propelling agent.
These ferrocene class catalyzer there is different alkyl substituent structures, the consistencies of the physical property caused, catalytic efficiency, other component of propelling agent etc. are also incomplete same.The alkyl substituent introduced on luxuriant ring in more single ferrocene or bisferrocenylpropane finds during the affecting of its catalytic efficiency, ferrocene class presents slow downward trend to the Catalytic Thermal Decomposition efficiency of AP along with alkyl substituent carbochain increases, and this mainly to make in ferrocene deriv caused by iron level reduces because substituted alkyl extends.
Kato is pungent is current most widely used burningrate catalyst, and its preparation is raw material with ethyl dicyclopentadienyl iron, the biferrocene derivative (being commonly called as Kato pungent) obtained by Friedel-Crafts alkylation.Although Kato is pungent has that combustion catalysis is effective, consistency is fabulous, heat stable advantage, find in prolonged application that it is used as that burningrate catalyst is minimum deposits defect both ways.One, during preparation, ethyl dicyclopentadienyl iron raw material and product are not easily separated completely for unreacted, to such an extent as to residual a certain amount of ethyl dicyclopentadienyl iron in product.The latter may migrate to solid propellant surface in shaping composite solidpropellant, causes surface catalysis agent concentration greatly to increase, thus reduces propelling agent security; Secondly, the pungent iron level of Kato is lower than ferrocene due to the dilution of ethyl substituent and sec.-propyl abutment, is 23.83%.Because ferrocene class combustion catalysis is that the molecular state ferric oxide produced using its thermolysis decomposes as the further catalysis AP of active substance, therefore, the iron level that system catalytic activity is only improved ferrocene deriv be improved.This is particularly important for the fast solid propellant of the high combustion of development, because the fast solid propellant of the high combustion of development at present realizes mainly through the ferrocene class of adding more multiplex amount, sometimes for pursuing high combustion speed, adding the pungent amount of Kato and even reaching 4 ~ 5%.So high addition has significantly reduced solid content and the total energy level of system, and more disadvantageously, high addition has brought the more transport property ethyl dicyclopentadienyl iron of total amount into, and safety performance caused thus worsens and become the problem that can not be ignored.
Just because of this, seek more efficient, safer burningrate catalyst is all one of focus of propelling agent research field all the time.
Why prior art widely uses 2, and 2 '-bis-(ethyl dicyclopentadienyl iron base)-propane (Kato is pungent), as solid propellant combustion rate catalyzer, is that consistency is good because this product is liquid.But there is the defect of iron level still ethyl dicyclopentadienyl iron not easily Ex-all in lower, product in it.
The object of the invention is to the deficiency overcoming prior art existence, there is provided that a kind of iron level is higher, to fire fast catalytic efficiency better, safer Ferrocene oligomer burningrate catalyst, and a kind of simple process is provided, be suitable for the burningrate catalyst preparation method of suitability for industrialized production.
To achieve the above object of the invention, the technical solution adopted in the present invention is to provide a kind of Ferrocene oligomer, it is poly-(1-ethyl-1 '-methylene radical ferrocene) oligopolymer, comprise the mixture of the tripolymer of 1-ethyl-1 '-methylene radical ferrocene, the tetramer and pentamer in oligopolymer, the structure of described Ferrocene oligomer is as follows:
，
Wherein, n is 1 ~ 3.
Technical solution of the present invention provides a kind of preparation method of Ferrocene oligomer, comprises the steps:
(1) friedel-crafts acylation reaction
1. acylation reaction: by weight, drop into 10 parts of ethyl dicyclopentadienyl irons in the reactor, 3 ~ 10 parts of lewis acid catalysts and 5 ~ 20 parts of solvents, drip under nitrogen protection and be dissolved in by 2 ~ 10 parts of triphosgene the solution that 5 parts of organic solvents are formed, acylation reaction at ambient temperature after dripping off in 1 hour, the reaction times is 2 ~ 24 hours;
2. hydrolysis: after acylation reaction completes, add 10 ~ 50 parts of water, stirring at room temperature Water Under solution is reacted after 1 ~ 5 hour, is separated and removes organic phase, and extraction liquid obtains crude product through washing, drying, steaming after desolventizing;
3. column chromatography: with volume ratio=1: the acetone of 1: sherwood oil is eluent, is separated by crude product by column chromatography, the chromatographic solution obtained, through rotary evaporation in vacuo process, obtains acylated product;
(2) Clemmensen reduction reaction
1. reduction reaction: by weight, drop into the acylated product obtained in 10 parts of steps 1 in the reactor, 10 ~ 150 parts of organic solvents, 10 ~ 60 parts of Virahols, 50 ~ 100 parts of zinc amalgams, after being warming up to 65 DEG C ~ 95 DEG C, drip 50 ~ 100 parts of hydrochloric acid, drip off stopped reaction when follow-up continuous insulation reaction to reaction mixture color becomes brown color;
2. aftertreatment: after reduction reaction completes, separates organic phase, and by the aqueous phase organic solvent extraction obtained, extraction liquid is through washing, drying, and steaming desolventizes and to obtain reduction crude product;
3. carry and heat up in a steamer process: reduction crude product temperature be 120 DEG C ~ 160 DEG C, vacuum tightness be the condition of 1mmHg ~ 2mmHg under decompression carry and distillate low-boiling-point substance, carrying the time of heating up in a steamer is 0.5 ~ 10 hour, obtains brown color thick liquid nano Ferrocene oligomer.
In technical solution of the present invention, described Lewis acid is any one in aluminum chloride or boron trifluoride ethyl ether complex; Described organic solvent is the mixture of a kind of in methylene dichloride, ethylene dichloride, chloroform and tetracol phenixin or any two kinds.
In preparation process, the described acylation reaction time is 3 ~ 8 hours.The described reduction reaction time is 3 ~ 8 hours.Described carry that to heat up in a steamer the treatment time be 1 ~ 2 hour.
Mechanism of the present invention is: adopt ethyl dicyclopentadienyl iron and triphosgene to be raw material, and by friedel-crafts acylation reaction preparation poly-(1-ethyl-1 '-formyl ferrocene), restore obtained poly-(1-ethyl-1 '-methylene radical ferrocene), reaction formula is as follows:
Wherein, n=1 ~ 3.
Compared with prior art, its beneficial effect of technical scheme provided by the invention is:
1, poly-(1-ethyl-1 '-methylene radical ferrocene) iron level of Ferrocene oligomer type burningrate catalyst is high, is 25.22%, as the Kato pungent grade product of burningrate catalyst catalytic effect higher than existing widespread use.
2, poly-(1-ethyl-1 '-methylene radical ferrocene) burningrate catalyst comprises the tripolymer of 1-ethyl-1 '-methylene radical ferrocene, the tetramer and pentamer, for oligopolymer, in solid propellant propulsion agent prescription, transport property is very little, and this is conducive to the safety performance ensureing propelling agent.
3, adopt solid phosgene triphosgene as Fu-Ke acylation agent preparation poly-(1-ethyl-1 '-formyl ferrocene); again formyl radical is reduced into poly-(1-ethyl-1 '-methylene radical ferrocene) with iron powder/dilute hydrochloric acid; the reaction process obtaining Ferrocene oligomer type burningrate catalyst is easy, reaction conditions is gentle, is applicable to suitability for industrialized production.
Summary of the invention
Accompanying drawing explanation
Fig. 1 is the high-efficient liquid phase chromatogram gathering (1-ethyl-1 '-methylene radical ferrocene) prepared by the embodiment of the present invention 1 technical scheme.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
1, poly-(1-ethyl-1 '-formyl ferrocene) synthesis
Induction stirring is being housed; reflux condensing tube; in the four-hole boiling flask of thermometer and feed hopper; add 12.9 grams of ethyl dicyclopentadienyl irons; 6.0 grams of aluminum trichloride (anhydrous)s and 150 grams of methylene dichloride; then open stirring, pass into nitrogen protection, under room temperature, drip 3.6 grams of triphosgene (solid phosgene) be dissolved in the solution formed in 50 grams of methylene dichloride.Within 1 hour, dropwise, add rear room temperature and continue reaction 6 hours.
After having reacted, add 30 grams of water, stirring at room temperature is hydrolyzed 2 hours, after hydrolysis reaction terminates, separate organic phase, aqueous phase methylene dichloride extracts for 50 grams × 3 times, merges oil phase, washes 50 grams × 3 times, add 0.5 gram of anhydrous sodium sulfate drying, after filtering siccative, filtrate is steamed except methylene dichloride, obtains 10.9 grams of crude products.Column chromatography for separation, eluent is acetone: sherwood oil=1: 1, obtains 11.1 grams of black solid products poly-(1-ethyl-1 '-formyl ferrocene), productive rate 79.2 %.Product
1h NMR (chloroform-d
6): δ 7.32 (8H), δ 4.19 (10H), δ 2.11 (4H ,-CH
2), δ 1.51 (6H ,-CH
3).IR(KBr compressing tablet, cm
-1): 3092 (Fc, ν C-H), 1708 (ν C=O).
2, poly-(1-ethyl-1 '-methylene radical ferrocene) preparation
In the four-hole boiling flask being equipped with mechanical stirring, reflux condensing tube, thermometer and feed hopper, add 11 grams poly-(1-ethyl-1 '-formyl ferrocene), 200 grams of ethylene dichloride and 50 grams of Virahols, open and stir, add 150 grams of zinc amalgams again, when temperature of reaction system rises to 75 DEG C, drip 150 grams of hydrochloric acid at a slow speed, within about 2 hours, dropwise, drip after finishing, continue reaction 6 hours, when the color of solution becomes brown color, stopped reaction.
After having reacted, separate organic phase, aqueous phase ethylene dichloride extracts for 50 grams × 3 times, and merge oil phase, wash 50 grams × 3 times, add 4 grams of anhydrous sodium sulfate dryings, after filtering siccative, filtrate steaming removal solvent, obtains 16 grams of crude products.Crude product reduces pressure to carry and distillates low-boiling-point substance under temperature 150 DEG C, vacuum tightness 2mmHg, carries the 1 hour time of heating up in a steamer, obtains brown color thick liquid nano Ferrocene oligomer, productive rate 62.0%.Product
1h NMR (chloroform-d
6): δ 7.29 (8H), δ 4.09 (8H), δ 1.51 (2H ,-CH
2-), δ 1.20 (4H ,-CH
2), δ 0.91 (6H ,-CH
3).IR(KBr compressing tablet, cm
-1): 3090 (Fc, ν C-H).Ultimate analysis (%): Fe
2c
25h
28measured value (calculated value) Fe 25.22(25.35).
Product is with liquid chromatography test oligopolymer composition, and result is see accompanying drawing 1.In Fig. 1, be respectively 17.15min, 25.25min, 25.65min and 25.96min place in the residence time and occur four components respectively, four component concentrations are respectively 18.6%, 22.1%, 42.3 and 14.4%, corresponding poly-(1-ethyl-1 '-methylene radical ferrocene) dimer, tripolymer, the tetramer and pentamer respectively, wherein based on the tetramer.
3, to the thermolysis catalysis of oxygenant in propelling agent
2.75 grams of ammoniumper chlorate (AP) are mixed with 0.03 gram poly-(1-ethyl-1 '-methylene radical ferrocene), 5min is ground with agate mortar, TG-DTA is utilized to carry out thermal analyses test to sample, heat-up rate is 10 DEG C/min, atmosphere is High Purity Nitrogen, gas flow 100ml/min, Range of measuring temp is 50 DEG C ~ 500 DEG C, and sample crucible is alumina crucible.
Test result shows, the ammoniumper chlorate of non-addition polymerization (1-ethyl-1 '-methylene radical ferrocene) has a heat absorption and release decomposition peak respectively 252.2 DEG C and 320.8 DEG C, then there is heat absorption and release peak respectively 251.8 DEG C and 303.3 DEG C in the ammoniumper chlorate adding poly-(1-ethyl-1 '-methylene radical ferrocene), exothermic decomposition peak shifts to an earlier date 17.5 DEG C, and visible poly-(1-ethyl-1 '-methylene radical ferrocene) has good catalytic effect to AP thermolysis.
Embodiment 2
1, poly-(1-ethyl-1 '-formyl ferrocene) synthesis
Induction stirring is being housed; reflux condensing tube; in the four-hole boiling flask of thermometer and feed hopper; add 10.7 grams of ethyl dicyclopentadienyl irons; 1.5 grams of boron trifluoride ethyl ether complexs and 120 grams of ethylene dichloride; open after reinforced and stir, pass into nitrogen protection, under room temperature, drip 3.6 grams of triphosgene (solid phosgene) be dissolved in the solution formed in 50 grams of ethylene dichloride.Within 2 hours, dropwise, add rear room temperature and continue reaction 4 hours.
After having reacted, add 20 grams of water, stirring at room temperature is hydrolyzed 2 hours, after hydrolysis reaction terminates, separate organic phase, aqueous phase ethylene dichloride extracts for 50 grams × 3 times, merges oil phase, washes 50 grams × 3 times, add 0.5 part of anhydrous sodium sulfate drying, after filtering siccative, filtrate steaming removal solvent ethylene dichloride, obtains 11.2 grams of crude products.Column chromatography for separation, eluent is acetone: sherwood oil=1: 1, obtains 9.5 grams of black solid products poly-(1-ethyl-1 '-formyl ferrocene), productive rate 84.3 %.
2, poly-(1-ethyl-1 '-methylene radical ferrocene) preparation
In the four-hole boiling flask being equipped with mechanical stirring, reflux condensing tube, thermometer and feed hopper, add 11 grams poly-(1-ethyl-1 '-formyl ferrocene), 80 grams of ethylene dichloride and 30 grams of Virahols, open and stir, add 80 grams of zinc amalgams again, when temperature of reaction system rises to 75 DEG C, drip 80 grams of hydrochloric acid at a slow speed, within about 2 hours, dropwise, drip after finishing, continue reaction 5 hours, when the color of solution becomes brown color, reaction terminates.
After having reacted, separate organic phase, aqueous phase ethylene dichloride extracts for 30 grams × 3 times, merge oil phase, wash 20 grams × 3 times, add 4 grams of anhydrous sodium sulfate dryings, after filtering siccative, filtrate steaming removal solvent, obtain 9.2 grams of crude products, crude product reduces pressure to carry and distillates low-boiling-point substance under temperature 150 DEG C, vacuum tightness 2mmHg, carries the 1 hour time of heating up in a steamer, obtain brown color thick liquid nano Ferrocene oligomer 6.8, productive rate 69.2%.Product elemental analyzes (%): Fe
2c
25h
28measured value (calculated value) Fe 25.09(25.35).
3, to the thermolysis catalysis of oxygenant in propelling agent
The Ferrocene oligomer of synthesizing according to method test in embodiment 1 is to the thermolysis catalytic effect of oxygenant ammoniumper chlorate (AP) in propelling agent, result shows, heat absorption and release peak is there is respectively in the ammoniumper chlorate adding poly-(1-ethyl-1 '-methylene radical ferrocene) 253.6 DEG C and 301.1 DEG C, shift to an earlier date 19.7 DEG C than the AP exothermic decomposition peak not adding catalyzer, visible poly-(1-ethyl-1 '-methylene radical ferrocene) has good catalytic effect to AP thermolysis.
Claims (6)
1. a Ferrocene oligomer, it is characterized in that it is poly-(1-ethyl-1 '-methylene radical ferrocene) oligopolymer, comprise the mixture of the tripolymer of 1-ethyl-1 '-methylene radical ferrocene, the tetramer and pentamer in oligopolymer, the structure of described Ferrocene oligomer is as follows:
，
Wherein, n is 1 ~ 3.
2. a preparation method for Ferrocene oligomer as claimed in claim 1, is characterized in that comprising the steps:
(1) friedel-crafts acylation reaction
1. acylation reaction: by weight, drop into 10 parts of ethyl dicyclopentadienyl irons in the reactor, 3 ~ 10 parts of lewis acid catalysts and 5 ~ 20 parts of solvents, drip under nitrogen protection and be dissolved in by 2 ~ 10 parts of triphosgene the solution that 5 parts of organic solvents are formed, acylation reaction at ambient temperature after dripping off in 1 hour, the reaction times is 2 ~ 24 hours;
2. hydrolysis: after acylation reaction completes, add 10 ~ 50 parts of water, stirring at room temperature Water Under solution is reacted after 1 ~ 5 hour, is separated and removes organic phase, and extraction liquid obtains crude product through washing, drying, steaming after desolventizing;
3. column chromatography: with volume ratio=1: the acetone of 1: sherwood oil is eluent, is separated by crude product by column chromatography, the chromatographic solution obtained, through rotary evaporation in vacuo process, obtains acylated product;
(2) Clemmensen reduction reaction
1. reduction reaction: by weight, drop into the acylated product obtained in 10 parts of steps 1 in the reactor, 10 ~ 150 parts of organic solvents, described organic solvent is the mixture of a kind of in methylene dichloride, ethylene dichloride, chloroform and tetracol phenixin or any two kinds, 10 ~ 60 parts of Virahols, 50 ~ 100 parts of zinc amalgams, after being warming up to 65 DEG C ~ 95 DEG C, drip 50 ~ 100 parts of hydrochloric acid, drip off stopped reaction when follow-up continuous insulation reaction to reaction mixture color becomes brown color;
2. aftertreatment: after reduction reaction completes, separates organic phase, and by the aqueous phase organic solvent extraction obtained, extraction liquid is through washing, drying, and steaming desolventizes and to obtain reduction crude product;
3. carry and heat up in a steamer process: reduction crude product temperature be 120 DEG C ~ 160 DEG C, vacuum tightness be the condition of 1mmHg ~ 2mmHg under decompression carry and distillate low-boiling-point substance, carrying the time of heating up in a steamer is 0.5 ~ 10 hour, obtains brown color thick liquid nano Ferrocene oligomer.
3. the preparation method of a kind of Ferrocene oligomer according to claim 2, is characterized in that: described Lewis acid is any one in aluminum chloride or boron trifluoride ethyl ether complex.
4. the preparation method of a kind of Ferrocene oligomer according to claim 2, is characterized in that: the described acylation reaction time is 3 ~ 8 hours.
5. the preparation method of a kind of Ferrocene oligomer according to claim 2, is characterized in that: the described reduction reaction time is 3 ~ 8 hours.
6. the preparation method of a kind of Ferrocene oligomer according to claim 2, is characterized in that: it is 1 ~ 2 hour that the treatment time is heated up in a steamer in described carrying.
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| CN104004195B (en) * | 2014-05-09 | 2016-08-24 | 中南大学 | Ferrocene-based polymer and porous material thereof and their preparation method and application |
| CN105348043B (en) * | 2015-11-27 | 2018-05-04 | 河北工业大学 | The separation and recovery method and device of solvent-water mixture containing easy fouling impurity |
| CN105817263B (en) * | 2016-04-12 | 2019-05-17 | 中国科学院上海有机化学研究所 | A kind of vinyl ferrocene oligomer catalyst being catalyzed ammonium perchlorate decomposition |
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| US3867213A (en) * | 1969-07-31 | 1975-02-18 | Us Army | Ferrocene-containing monomers and copolymers |
| CN101186625B (en) * | 2007-12-18 | 2010-09-15 | 吕德斌 | Ethylene group diferrocene derivative and synthetic method thereof |
| CN103242377B (en) * | 2013-04-22 | 2016-02-10 | 苏州志向纺织科研股份有限公司 | A kind of α, ω-di-ferrocene hydrocarbon and preparation method thereof |
| CN103288884A (en) * | 2013-05-28 | 2013-09-11 | 陕西科技大学 | Preparation method of alpha-bromoacetyl ferrocene |
| CN103288886B (en) * | 2013-06-17 | 2015-05-20 | 陕西师范大学 | Double-core ferrocene high-nitrogen energetic ion compound and preparation method thereof |
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