CN103566972A - Ferrocene oligomer and preparation method thereof - Google Patents
Ferrocene oligomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ferrocene oligomer and a preparation method thereof. With ethyl ferrocene and triphosgene as raw materials, poly(1-ethyl-1'-formyl ferrocene) is prepared through a Friedel-Crafts acylation reaction; a poly(1-ethyl-1'-methylene ferrocene) oligomer is prepared through a reduction reaction. The ferrocene oligomer contains mixtures of tripolymer, tetramer and pentamer of 1-ethyl-1'-methylene ferrocene; the iron content reaches 25.22%. The ferrocene oligomer can be used as a catalyst for the burning speed of a solid propellant, so that high-burning-rate compound solid propellant can be obtained under the condition of small adding quantity. When the ferrocene oligomer provided by the invention is mixed with each component of the compound solid propellant, the polymer chains are easy gather on the surface of a polar oxidizing agent ammonium perchlorate, and a burning catalytic activity center is easy to form around the oxidizing agent, so that effective catalysis can be achieved. The ferrocene oligomer provided by the invention has the advantages of simple preparation technique and mild reaction conditions, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of ferrocene oligomer and preparation method thereof, particularly ferrocene burningrate catalyst and preparation method thereof for a kind of solid propellant.
Background technology
Take in the composite solidpropellant system that ammonium perchlorate (AP) is oxidant, ferrocene derivatives has obtained application widely as the burningrate catalyst of high comprehensive performance, wherein, 2, (Kato is pungent, Catocene), the product such as octyl ferrocene and tert-butyl group ferrocene is the burningrate catalyst principal item of using in current propellant for 2 '-bis-(ethyl dicyclopentadienyl iron base)-propane.
These ferrocene class catalyst there is different alkyl substituent structures, the compatibilities of the physical property causing, catalytic efficiency, other component of propellant etc. are also incomplete same.The alkyl substituent of introducing on luxuriant ring in more single ferrocene or bisferrocenylpropane is found during on the affecting of its catalytic efficiency, ferrocene class is to the Catalytic Thermal Decomposition efficiency of AP along with alkyl substituent carbon chain growth presents the trend of slow decreasing, and this is mainly to make in ferrocene derivatives due to iron content reduces because substituted alkyl extends.
Kato is pungent is current most widely used burningrate catalyst, and its preparation is to take ethyl dicyclopentadienyl iron as raw material, the biferrocene derivative (being commonly called as Kato pungent) obtaining by Fu-Ke alkylated reaction.Although Kato is pungent has that combustion catalysis is effective, compatibility is fabulous, heat stable advantage,, in prolonged application, find that it is used as the minimum defect both ways of depositing of burningrate catalyst.One, during preparation unreacted completely ethyl dicyclopentadienyl iron raw material and product not easily separated, 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 the composite solidpropellant of moulding, causes surface catalysis agent concentration greatly to increase, thereby reduces propellant security; Secondly, the pungent iron content of Kato is lower than ferrocene due to the dilution of ethyl substituting group and isopropyl abutment, is 23.83%.Because ferrocene class combustion catalysis is to using the molecular state oxidation iron that its thermal decomposition produces to decompose as the further catalysis AP of active material, therefore, improve the iron content that system catalytic activity is only improved ferrocene derivatives.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 is mainly realized by adding the ferrocene class of more multiplex amount, sometimes, for pursuing high combustion speed, adds the pungent amount of Kato and has even reached 4～5%.So high addition has greatly reduced solid content and the total energy level of system, and more disadvantageously, high addition has been brought the more animal migration ethyl dicyclopentadienyl iron of total amount into, and the security performance that caused thus worsens has become the problem can not be ignored.
Just because of this, seek more efficient, safer burningrate catalyst is all one of focus of propellant research field all the time.
Summary of the invention
Why prior art is widely used 2,2 '-bis-(ethyl dicyclopentadienyl iron base)-propane (Kato is pungent) as solid propellant combustion rate catalyst, is that compatibility is good because this product is liquid.But its exist iron content still in lower, product ethyl dicyclopentadienyl iron be difficult for the defect of Ex-all.
The object of the invention is to overcome the deficiency that prior art exists, provide that a kind of iron content 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 ferrocene) oligomer, the mixture that comprises tripolymer, the tetramer and the pentamer of 1-ethyl-1 '-methylene ferrocene in oligomer, 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, in reactor, drop into 10 parts of ethyl dicyclopentadienyl irons, 3～10 parts of lewis acid catalysts and 5～20 parts of solvents, under nitrogen protection, drip and be dissolved in 5 parts of formed solution of organic solvent by 2～10 parts of triphosgenes, acylation reaction at ambient temperature after dripping off in 1 hour, the reaction time is 2～24 hours;
2. hydrolysis: after acylation reaction completes, add 10～50 parts of water, stirring at room Water Under solution reaction is after 1～5 hour, the separated organic phase of removing, extract through washing, dry, steam after desolventizing and obtain crude product;
3. column chromatography: take volume ratio=1: 1 acetone: benzinum is eluent, and crude product is carried out to separation by column chromatography, and the chromatographic solution obtaining is processed through rotary evaporation in vacuo, obtains acyl group product;
(2) Clemensen reduction reaction
1. reduction reaction: by weight, in reactor, drop into the acyl group product obtaining in 10 parts of steps 1,10～150 parts of organic solvents, 10～60 parts of isopropyl alcohols, 50～100 parts of zinc amalgams, be warming up to after 65 ℃～95 ℃, drip 50～100 parts of hydrochloric acid, drip off follow-up continuous insulation reaction and when reactant mixture color becomes brown color, stop reaction;
2. post processing: after reduction reaction completes, separate organic phase, by the water organic solvent extraction obtaining, extract, through washing, dry, steams and desolventizes to obtain reduction crude product;
3. carry and heat up in a steamer processing: reduction crude product is that under 120 ℃～160 ℃, the vacuum condition that is 1mmHg～2mmHg, decompression is carried and distillated low-boiling-point substance in temperature, and 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 alchlor or boron trifluoride etherate; Described organic solvent is the mixture of a kind of in carrene, dichloroethanes, chloroform and carbon tetrachloride 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 processing time be 1～2 hour.
Mechanism of the present invention is: adopting ethyl dicyclopentadienyl iron and triphosgene is raw material, by friedel-crafts acylation reaction, prepares poly-(1-ethyl-1 '-formyl ferrocene), restores and makes poly-(1-ethyl-1 '-methylene ferrocene), and reaction equation 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 ferrocene) iron content of ferrocene oligomer type burningrate catalyst is high, is 25.22%, the pungent product that waits of Kato as burningrate catalyst catalytic effect higher than existing extensive use.
2, poly-(1-ethyl-1 '-methylene ferrocene) burningrate catalyst comprises 1-ethyl-1 '-methylene ferrocene tripolymer, the tetramer and pentamer, for oligomer, in solid propellant propulsion agent prescription, animal migration is very little, and this is conducive to guarantee the security performance of propellant.
3, adopt solid phosgene triphosgene as Fu-Ke acylation agent preparation poly-(1-ethyl-1 '-formyl ferrocene); again formoxyl is reduced into poly-(1-ethyl-1 '-methylene ferrocene) with iron powder/watery hydrochloric acid; the reaction process that obtains ferrocene oligomer type burningrate catalyst is easy, reaction condition is gentle, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the high-efficient liquid phase chromatogram that gathers (1-ethyl-1 '-methylene ferrocene) of preparing by the embodiment of the present invention 1 technical scheme.
The specific embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
1, poly-(1-ethyl-1 '-formyl ferrocene) is synthetic
Electromagnetic agitation is being housed; reflux condensing tube; in the four-hole boiling flask of thermometer and charging hopper; add 12.9 grams of ethyl dicyclopentadienyl irons; 6.0 grams of aluminum trichloride (anhydrous)s and 150 grams of carrene; then open and stir, pass into nitrogen protection, under room temperature, drip 3.6 grams of triphosgenes (solid phosgene) and be dissolved in the solution forming in 50 grams of carrene.Within 1 hour, dropwise, add rear room temperature and continue reaction 6 hours.
After having reacted, add 30 grams of water, stirring at room hydrolysis 2 hours, after hydrolysis finishes, separate organic phase, water extracts for 50 grams * 3 times with carrene, merges oil phase, washes 50 grams * 3 times, add 0.5 gram of anhydrous sodium sulfate drying, after filtering drier, filtrate is steamed except carrene, obtains 10.9 grams of crude products.Column chromatography for separation, eluent is acetone: benzinum=1: 1, obtain 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 ferrocene) preparation
In being equipped with the four-hole boiling flask of mechanical agitation, reflux condensing tube, thermometer and charging hopper, add 11 grams poly-(1-ethyl-1 '-formyl ferrocene), 200 grams of dichloroethanes and 50 grams of isopropyl alcohols, open and stir, add again 150 grams of zinc amalgams, when temperature of reaction system rises to 75 ℃, drip at a slow speed 150 grams of hydrochloric acid, within approximately 2 hours, dropwise, after drip finishing, continue reaction 6 hours, when the color of solution becomes brown color, stop reaction.
After having reacted, separate organic phase, water extracts for 50 grams * 3 times with dichloroethanes, merges oil phase, washes 50 grams * 3 times, adds 4 grams of anhydrous sodium sulfate dryings, and after filtering drier, filtrate steaming removal solvent, obtains 16 grams of crude products.Crude product reduces pressure to carry and distillates low-boiling-point substance under 150 ℃ of temperature, vacuum 2mmHg, carries the 1 hour time of heating up in a steamer, and 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).Elementary analysis (%): Fe
2c
25h
28measured value (calculated value) Fe 25.22(25.35).
Product forms with liquid chromatogram test oligomer, and result is referring to accompanying drawing 1.In Fig. 1, in the time of staying, be respectively 17.15min, 25.25min, 25.65min and 25.96min place and occur respectively four components, four constituent contents are respectively 18.6%, 22.1%, 42.3 and 14.4%, corresponding poly-(1-ethyl-1 '-methylene ferrocene) dimer, tripolymer, the tetramer and pentamer, wherein take the tetramer as main respectively.
3, the thermal decomposition catalysis to oxidant in propellant
2.75 grams of ammonium perchlorate (AP) are mixed with 0.03 gram poly-(1-ethyl-1 '-methylene ferrocene), with agate mortar, grind 5min, utilize TG-DTA to carry out hot analytical test to sample, programming rate is 10 ℃/min, atmosphere is High Purity Nitrogen, gas flow 100ml/min, Range of measuring temp is 50 ℃～500 ℃, sample crucible is alumina crucible.
Test result shows, the ammonium perchlorate of addition polymerization (1-ethyl-1 '-methylene ferrocene) does not have respectively a heat absorption and release decomposition peak at 252.2 ℃ and 320.8 ℃, add the ammonium perchlorate of poly-(1-ethyl-1 '-methylene ferrocene) at 251.8 ℃ and 303.3 ℃, to occur respectively heat absorption and release peak, 17.5 ℃ in advance, exothermic decomposition peak, visible poly-(1-ethyl-1 '-methylene ferrocene) thermal decomposition has good catalytic effect to AP.
1, poly-(1-ethyl-1 '-formyl ferrocene) is synthetic
Electromagnetic agitation is being housed; reflux condensing tube; in the four-hole boiling flask of thermometer and charging hopper; add 10.7 grams of ethyl dicyclopentadienyl irons; 1.5 grams of boron trifluoride etherates and 120 grams of dichloroethanes; after reinforced, open and stir, pass into nitrogen protection, under room temperature, drip 3.6 grams of triphosgenes (solid phosgene) and be dissolved in the solution forming in 50 grams of dichloroethanes.Within 2 hours, dropwise, add rear room temperature and continue reaction 4 hours.
After having reacted, add 20 grams of water, stirring at room hydrolysis 2 hours, after hydrolysis finishes, separate organic phase, water extracts for 50 grams * 3 times with dichloroethanes, merges oil phase, washes 50 grams * 3 times, add 0.5 part of anhydrous sodium sulfate drying, after filtering drier, filtrate steaming removal solvent dichloroethanes, obtains 11.2 grams of crude products.Column chromatography for separation, eluent is acetone: benzinum=1: 1, obtain 9.5 grams of black solid products poly-(1-ethyl-1 '-formyl ferrocene), productive rate 84.3 %.
2, poly-(1-ethyl-1 '-methylene ferrocene) preparation
In being equipped with the four-hole boiling flask of mechanical agitation, reflux condensing tube, thermometer and charging hopper, add 11 grams poly-(1-ethyl-1 '-formyl ferrocene), 80 grams of dichloroethanes and 30 grams of isopropyl alcohols, open and stir, add again 80 grams of zinc amalgams, when temperature of reaction system rises to 75 ℃, drip at a slow speed 80 grams of hydrochloric acid, within approximately 2 hours, dropwise, after drip finishing, continue reaction 5 hours, when the color of solution becomes brown color, reaction finishes.
After having reacted, separate organic phase, water extracts for 30 grams * 3 times with dichloroethanes, merge oil phase, wash 20 grams * 3 times, add 4 grams of anhydrous sodium sulfate dryings, after filtering drier, filtrate steaming removal solvent, obtain 9.2 grams of crude products, crude product reduces pressure to carry and distillates low-boiling-point substance under 150 ℃ of temperature, vacuum 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 elementary analysis (%): Fe
2c
25h
28measured value (calculated value) Fe 25.09(25.35).
3, the thermal decomposition catalysis to oxidant in propellant
According to method in embodiment 1, test the thermal decomposition catalytic effect of synthetic ferrocene oligomer to oxidant ammonium perchlorate (AP) in propellant, result shows, add the ammonium perchlorate of poly-(1-ethyl-1 '-methylene ferrocene) to occur respectively heat absorption and release peak at 253.6 ℃ and 301.1 ℃, than the AP exothermic decomposition peak that does not add catalyst, shift to an earlier date 19.7 ℃, visible poly-(1-ethyl-1 '-methylene ferrocene) thermal decomposition has good catalytic effect to AP.
Claims (7)
1. a ferrocene oligomer, it is characterized in that it is poly-(1-ethyl-1 '-methylene ferrocene) oligomer, the mixture that comprises tripolymer, the tetramer and the pentamer of 1-ethyl-1 '-methylene ferrocene in oligomer, 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, in reactor, drop into 10 parts of ethyl dicyclopentadienyl irons, 3～10 parts of lewis acid catalysts and 5～20 parts of solvents, under nitrogen protection, drip and be dissolved in 5 parts of formed solution of organic solvent by 2～10 parts of triphosgenes, acylation reaction at ambient temperature after dripping off in 1 hour, the reaction time is 2～24 hours;
2. hydrolysis: after acylation reaction completes, add 10～50 parts of water, stirring at room Water Under solution reaction is after 1～5 hour, the separated organic phase of removing, extract through washing, dry, steam after desolventizing and obtain crude product;
3. column chromatography: take volume ratio=1: 1 acetone: benzinum is eluent, and crude product is carried out to separation by column chromatography, and the chromatographic solution obtaining is processed through rotary evaporation in vacuo, obtains acyl group product;
(2) Clemensen reduction reaction
1. reduction reaction: by weight, in reactor, drop into the acyl group product obtaining in 10 parts of steps 1,10～150 parts of organic solvents, 10～60 parts of isopropyl alcohols, 50～100 parts of zinc amalgams, be warming up to after 65 ℃～95 ℃, drip 50～100 parts of hydrochloric acid, drip off follow-up continuous insulation reaction and when reactant mixture color becomes brown color, stop reaction;
2. post processing: after reduction reaction completes, separate organic phase, by the water organic solvent extraction obtaining, extract, through washing, dry, steams and desolventizes to obtain reduction crude product;
3. carry and heat up in a steamer processing: reduction crude product is that under 120 ℃～160 ℃, the vacuum condition that is 1mmHg～2mmHg, decompression is carried and distillated low-boiling-point substance in temperature, and 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 alchlor or boron trifluoride etherate.
4. the preparation method of a kind of ferrocene oligomer according to claim 2, is characterized in that: described organic solvent is the mixture of a kind of in carrene, dichloroethanes, chloroform and carbon tetrachloride or any two kinds.
5. 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.
6. 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.
7. the preparation method of a kind of ferrocene oligomer according to claim 2, is characterized in that: it is 1～2 hour that the processing time is heated up in a steamer in described carrying.
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Cited By (3)
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| CN104004195A (en) * | 2014-05-09 | 2014-08-27 | 中南大学 | Ferrocenyl polymer and porous material thereof, and preparation methods and application thereof |
| CN105348043A (en) * | 2015-11-27 | 2016-02-24 | 河北工业大学 | Separating and recycling method and device for solvent-water mixture containing impurities prone to scale formation |
| CN105817263A (en) * | 2016-04-12 | 2016-08-03 | 中国科学院上海有机化学研究所 | Vinylferrocene oligomer catalyst for catalyzing decomposition of ammonium perchlorate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105817263A (en) * | 2016-04-12 | 2016-08-03 | 中国科学院上海有机化学研究所 | Vinylferrocene oligomer catalyst for catalyzing decomposition of ammonium perchlorate |
| 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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Effective date of registration: 20190411 Address after: 215228 North Ring Road, Shengze Town, Wujiang District, Suzhou City, Jiangsu Province, 1988 Patentee after: Jiangsu Hua Hao silk Limited by Share Ltd Address before: 215123 199 Ren Yan Road, Suzhou Industrial Park, Suzhou, Jiangsu Patentee before: Soochow University |
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