CN106336436B - Biferrocene hexacyanoferrate and preparation method thereof - Google Patents
Biferrocene hexacyanoferrate and preparation method thereof Download PDFInfo
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- CN106336436B CN106336436B CN201610709234.2A CN201610709234A CN106336436B CN 106336436 B CN106336436 B CN 106336436B CN 201610709234 A CN201610709234 A CN 201610709234A CN 106336436 B CN106336436 B CN 106336436B
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0202—Polynuclearity
- B01J2531/0205—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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Abstract
The invention discloses a kind of biferrocene hexacyanoferrate and preparation method thereof, the structural formula of the compound isIn formula
Description
Technical field
The invention belongs to solid propellant technical fields, and in particular to a kind of biferrocene hexacyanoferrate and its system
Preparation Method.
Background technique
Ferrocene and its derivative is because of its excellent burning regulatory function, as solid propellant (especially compound propulsion
Agent) most important burningrate catalyst, be widely used in strategy, in Tactical Weapon System, various ballistic missiles (including
Region of war, short distance, intermediate range, intercontinental ballistic missile etc.), airborne tactical missile, anti-ballistic high-speed circuit design and sea base submarine mine, torpedo etc.
Huge effect is played in weapon.
Ferrocene class burningrate catalyst due to applying at present has seriously affected me there are the problems such as easy to migrate, volatile
Storage life, use reliability and the environmental suitability of all kinds of missile propellant powder charges of state also virtually increase national defence basis
The funds expenditure of deposit.So researcher has done a large amount of research work and has been attempted to out that mechanical property is more preferable, anti-migration
Property and volatility is stronger, synthesis technology is easier and the higher ferrocene class burningrate catalyst of combustibility, to improve two
Luxuriant iron and its derivative there are the problem of.Alkyl is introduced into ferrocene molecule has obtained the bis- (second of 2,2- earliest by American Studies person
Base ferrocene)-propane (Catocene), it is at room temperature liquid that Catocene, which is the ferrocene class combustionregulator being commercialized at present,
Body, vapour pressure is lower, and iron content is high, can significantly improve the comprehensive performance of propellant.But there is also easy to migrate, easy by Catocene
The short problem of oxidation, propellant service life.The beginning of the seventies, Huskins et al. have synthesized liquid unit containing allyl alcohol structure
Ferrocene derivatives, the problem of overcoming migration and low temperature crystallization.Then, and someone has synthesized di-ferrocene isocyanic acid containing butyl
The combustionregulator of ester units, catalytic activity is high, but mechanical properties decrease.At present more common method first is that by ferrocene
Group is connected to polymer of the formation containing ferrocene on the side chain or main chain of macromolecular.What French explosive wastewater association developed
Butacene is exactly ferrocene derivatives and low molecular weight hydroxy-terminated polybutadiene graft copolymer, and when preparing propellant, it can
With the common adhesive (such as end hydroxy butadiene (HTPB)) in the alternative composite propellant of part, in propellant curing process
In, it can enter curing network, but this analog derivative manufacturing process is complicated, and sensitive to oxidant, iron content is few, and catalytic efficiency is not
Height, and the presence of iron can cause degradation reaction of fourth hydroxyl adhesive during storage, reduce the performance of fourth hydroxyl adhesive.
Li Fengsheng in 2008 et al. report in " solid-rocket technology " the 6th phase page 612~616 (2008) of volume 30 passes through ferrocene
Condensation reaction is grafted on SBA-15, is prepared for a kind of catalyst of low migration.But this catalyst iron-content is low, Er Qieyin
The Si oxide without energy is entered, catalytic effect is not very good.In addition, people introduce epoxy second in ferrocene-containing compound
Base, sulfydryl, azepine base etc. are easy to the active function groups polymerizeing, by finding to test of these compounds in solid propellant
They can partially solve the problems, such as migration, but can not all obtain the perfect combination of mechanical property, processing performance and combustibility.
Summary of the invention
Technical problem to be solved by the present invention lies in overcome existing ferrocene class burningrate catalyst to push away as complex solid
Into disadvantage present in agent addition agent, provide a kind of not volatile under field conditions (factors), resistance to migration is strong, and catalytic performance is adjustable
The biferrocene hexacyanoferrate of control, and a kind of easy to operate, cost is provided for the biferrocene hexacyanoferrate
Lower preparation method.
Solve above-mentioned technical problem used by technical solution be the structural formula of the biferrocene hexacyanoferrate such as
Shown in lower:
In formulaRepresent the biferrocene methyl quaternary ammonium cation or biferrocene methyl of two unit positive charges of band
Alkylimidazolium cation.
The structural formula of the biferrocene methyl quaternary ammonium cation of above-mentioned two unit positive charges of band are as follows:
The integer that m is 3~10 in formula.
The structural formula of the biferrocene methyl alkyl glyoxaline cation of above-mentioned two unit positive charges of band are as follows:
The integer that n is 4~10 in formula.
Biferrocene hexacyanoferrate of the present invention the preparation method comprises the following steps: by biferrocene methyl quaternary ammonium iodide or
Biferrocene methyl alkyl imidazolium iodide is dissolved in methanol, and Hexacyanoferrate aqueous solutions of potassium is then added dropwise, is stirred at room temperature
Reaction 3~4 hours, isolates and purifies product, obtains biferrocene hexacyanoferrate.
Above-mentioned Hexacyanoferrate potassium and biferrocene methyl quaternary ammonium iodide or biferrocene methyl alkyl imidazoles
The molar ratio of iodide is 0.8:1, and wherein the structural formula of biferrocene methyl quaternary ammonium iodide is as follows:
The structural formula of biferrocene methyl alkyl imidazolium iodide is as follows:
The integer that n is 3~10 in formula, the integer that m is 4~10,Represent I-。
Biferrocene hexacyanoferrate of the invention is not volatile under field conditions (factors), and resistance to migration is strong, thermostabilization
Property is good, and the catalytic performance of the compound is controllable, can meet the recipe requirements of different type solid propellant, and increases
Iron content, catalytic performance are expected to improve.The preparation method of the compounds of this invention is easy to operate, synthesis cost is low, overcomes two cyclopentadienyls
The disadvantages of iron and its complicated, expensive, at high cost derivative synthesis technology.
Detailed description of the invention
Fig. 1 is the differential of the biferrocene hexacyanoferrate of the Examples 1 to 8 preparation of addition 3% in ammonium perchlorate
Scanning amount thermal analysis curve.
Fig. 2 is the differential of biferrocene hexacyanoferrate prepared by the embodiment 9~15 of addition 3% in ammonium perchlorate
Scanning amount thermal analysis curve.
Fig. 3 is that the differential of the biferrocene hexacyanoferrate of the Examples 1 to 8 preparation of addition 4% in hexogen is swept
Retouch thermometric analysis curve.
Fig. 4 is that the differential of biferrocene hexacyanoferrate prepared by the embodiment 9~15 of addition 5% in hexogen is swept
Retouch thermometric analysis curve.
Fig. 5 is the differential of the biferrocene hexacyanoferrate of the Examples 1 to 8 preparation of addition 1% in octogen
Scanning amount thermal analysis curve.
Fig. 6 is the differential of biferrocene hexacyanoferrate prepared by the embodiment 9~15 of addition 2% in octogen
Scanning amount thermal analysis curve.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
Following 1, the 3- propylidene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.478g (1mmol) 1,3- propylidene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is dark blue precipitate generation immediately, reaction 4 is stirred at room temperature
Hour, filtering, filter cake distillation washing 3 times is subsequently placed in 45 DEG C drying 48 hours in vacuum oven, obtains blue solid
Powder 1,3- propylidene bis- [the hexacyanoferrate 0.566g of (1- ferrocenyl methyl) dimethyl ammonium, yields 85%.
The spectral data of product are as follows: IR (cm-1): 3012 (C=C-H), 2998 (- CH3), 2864 (- CH2), 2057 (C ≡
N), 1692 (C=C).Elemental analysis (being calculated value in bracket): C%59.24 (59.37), H%5.99 (5.74), N%
12.45(12.59)。
The 1,3- propylidene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
Its specific synthetic method are as follows: 0.291g (1.2mmol) dimethylamine methyl ferrocene is dissolved completely in and fills 10mL
In the 50mL round-bottomed flask of acetone, then 0.201g (1mmol) 1,3- diiodo propane is added dropwise, there is yellow mercury oxide generation immediately,
Reaction 8 hours, filtering is stirred at room temperature, filter cake is washed 2~3 times with ether, is placed in a vacuum drying oven 45 DEG C of dryings 48 hours, obtains
Bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,3- propylidene.
Embodiment 2
Following Isosorbide-5-Nitrae-the butylidenebis of preparation structure formula [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.492g (1mmol) Isosorbide-5-Nitrae-butylidenebis
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is black precipitate generation immediately, it is small that reaction 4 is stirred at room temperature
When, filtering, filter cake distillation washing 3 times is subsequently placed in 45 DEG C drying 48 hours in vacuum oven, obtains black solid powder
Isosorbide-5-Nitrae-butylidenebis [the hexacyanoferrate 0.592g of (1- ferrocenyl methyl) dimethyl ammonium, yield 87%.
The spectral data of product are as follows: IR (cm-1): 3063 (C=C-H), 2919 (- CH3), 2874 (- CH2), 2071 (C ≡
N), 1686 (C=C).Elemental analysis (being calculated value in bracket): C%59.41 (59.55), H%5.98 (5.80), N%
12.37(12.50)。
The present embodiment 1,4- butylidenebis [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar-two iodobutane of Isosorbide-5-Nitrae, other steps and reality
It is identical to apply example 1, Isosorbide-5-Nitrae-butylidenebis [(1- ferrocenyl methyl) Eschenmoser's salt can be obtained.
Embodiment 3
Following 1, the 5- pentylidene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.506g (1mmol) 1,5- pentylidene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is yellow-green precipitate generation immediately, other steps and implementation
Example 1 is identical, obtains greenish yellow solid powder 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 5- pentylidene
0.597g, yield 86%.
The spectral data of product are as follows: IR (cm-1): 3057 (C=C-H), 2966 (- CH3), 2881 (- CH2), 2112 (C ≡
N), 1632 (C=C).Elemental analysis (being calculated value in bracket): C%59.58 (59.73), H%6.02 (5.86), N%
12.27(12.41)。
The 1,5- pentylidene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,5-, bis- iodopentane, other steps and reality
It is identical to apply example 1, bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,5- pentylidene can be obtained.
Embodiment 4
Following 1, the 6- hexylidene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.520g (1mmol) 1,6- hexylidene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is green precipitate generation immediately, other steps and embodiment
1 is identical, obtains green solid powder 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 6- hexylidene
0.631g, yield 89%.
The spectral data of product are as follows: IR (cm-1): 3071 (C=C-H), 2983 (- CH3), 2850 (- CH2), 2028 (C ≡
N), 1641 (C=C).Elemental analysis (being calculated value in bracket): C%59.77 (59.91), H%6.17 (5.91), N%
12.20(12.33)。
The 1,6- hexylidene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,6-, bis- iodohexane, other steps and reality
It is identical to apply example 1, bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,6- hexylidene can be obtained.
Embodiment 5
Following 1, the 7- heptamethylene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.534g (1mmol) 1,7- heptamethylene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is green precipitate generation immediately.Other steps and embodiment
1 is identical, obtains green solid powder 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 7- heptamethylene
0.635g, yield 88%.
The spectral data of product are as follows: IR (cm-1): 3063 (C=C-H), 2967 (- CH3), 2870 (- CH2), 2079 (C ≡
N), 1642 (C=C).Elemental analysis (being calculated value in bracket): C%59.92 (60.09), H%6.14 (5.97), N%
12.11(12.25)。
The 1,7- heptamethylene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,7- diiodo- heptane, other steps and reality
It is identical to apply example 1, bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,7- heptamethylene can be obtained.
Embodiment 6
Following 1, the 8- octamethylene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.548g (1mmol) 1,8- octamethylene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is bottle green precipitating to generate immediately.Other steps and implementation
Example 1 is identical, obtains dark green solid powder 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 8- octamethylene
0.626g, yield 85%.
The spectral data of product are as follows: IR (cm-1): 3050 (C=C-H), 2943 (- CH3), 2875 (- CH2), 2105 (C ≡
N), 1688 (C=C).Elemental analysis (being calculated value in bracket): C%60.05 (60.26), H%6.19 (6.03), N%
12.01(12.16)。
The 1,8- octamethylene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,8- diiodo-octane, other steps and reality
It is identical to apply example 1, bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,8- octamethylene can be obtained.
Embodiment 7
Following 1, the 9- nonylene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.562g (1mmol) 1,9- nonylene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is green precipitate generation immediately.Other steps and embodiment
1 is identical, obtains green solid powder 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 9- nonylene
0.751g, yield 88%.
The spectral data of product are as follows: IR (cm-1): 3035 (C=C-H), 2984 (- CH3), 2820 (- CH2), 2112 (C ≡
N), 1641 (C=C).Elemental analysis (being calculated value in bracket): C%60.30 (60.43), H%6.27 (6.09), N%
11.92(12.08)。
The 1,9- nonylene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,9-, bis- iodononane, other steps and reality
It is identical to apply example 1, bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,9- nonylene can be obtained.
Embodiment 8
Following 1, the 10- decylene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) dimethyl ammonium,
It is specific the preparation method comprises the following steps:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.576g (1mmol) 1,10- decylene pair
[in the methanol solution of (1- ferrocenyl methyl) Eschenmoser's salt, there is the generation of dark oil object immediately.Other steps and implementation
Example 1 is identical, obtains dark oil object 1, the bis- [hexacyanoferrates of (1- ferrocenyl methyl) dimethyl ammonium of 10- decylene
0.635g, yield 83%.
The spectral data of product are as follows: IR (cm-1): 3034 (C=C-H), 2952 (- CH3), 2874 (- CH2), 2074 (C ≡
N), 1647 (C=C).Elemental analysis (being calculated value in bracket): C%60.45 (60.60), H%6.29 (6.14), N%
11.84(12.00)。
The 1,10- decylene of the present embodiment it is bis- [structural formula of (1- ferrocenyl methyl) Eschenmoser's salt is as follows:
In embodiment 1,1,3- diiodo propane used is replaced with equimolar 1,10- diiodo- decane, other steps with
Embodiment 1 is identical, and bis- [(the 1- ferrocenyl methyl) Eschenmoser's salts of 1,10- decylene can be obtained.
Embodiment 9
Following Isosorbide-5-Nitrae-the butylidenebis of preparation structure formula [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tool
Preparation are as follows:
0.076g (0.8mmol) Hexacyanoferrate potassium is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water
In, it is fully transparent to solution, then the clear solution is added dropwise to 5mL dissolved with 0.844g (1mmol) Isosorbide-5-Nitrae-butylidenebis
[in the methanol solution of (1- ferrocenyl methyl) -3- imidazolium iodide, there is dark brown oil generation immediately, be stirred at room temperature anti-
It answers 4 hours, is spin-dried for Rotary Evaporators, then with distillation washing 3 times, recrystallized 3 times with methanol/distilled water, again with methanol/second
Ether recrystallizes 3 times, is finally placed in a vacuum drying oven 45 DEG C of dryings 48 hours, obtains dark brown oil Isosorbide-5-Nitrae-butylidenebis
[the hexacyanoferrate 0.564g of (1- ferrocenyl methyl) -3- imidazoles, yield 77%.
The spectral data of product are as follows: IR (cm-1): 3039 (C=C-H), 2911 (- CH3), 2857 (- CH2), 2051 (C ≡
N), 1625 (C=C).Elemental analysis (being calculated value in bracket): C%56.37 (56.56), H%6.04 (5.81), N%
15.99(16.15)。
The present embodiment 1,4- butylidenebis [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
Its specific synthetic method are as follows: dissolve 1.48g (0.01mol) compound A and 7.16g (0.021mol) compound B
In the round-bottomed flask for filling 40mL acetonitrile, after back flow reaction 36 hours, filtrate is spin-dried for by heat filtering, and 1mL methanol is added, and uses
Distilled water recrystallize 3 times after, 45 DEG C drying 48 hours, obtain [(1- ferrocenyl the methyl) -3- imidazoles iodate of Isosorbide-5-Nitrae-butylidenebis
Object, yield 70%.
The structural formula of above compound A is as follows:
Its synthetic method are as follows: 30g imidazoles and 18.509g sodium hydroxide are added in three-necked flask, under nitrogen protection
130 DEG C are reacted 4 hours, and dry powdered imidazole natrium is generated；3g imidazole natrium and 4.5g 1,4- dibromobutane are added to and are filled
In the round-bottomed flask of 40mL ethyl alcohol, back flow reaction 4 hours, filtering, filtrate was spin-dried for Rotary Evaporators, and distilled water is added to dissolve, and was used
Chloroform extraction three times, takes subnatant to be spin-dried for, and obtains compound A, yield 80%.
The structural formula of above compound B is as follows:
Its synthetic method are as follows: 2.430g (10mmol) dimethylamine methyl ferrocene is dissolved completely in and fills 10mL acetone
In 250mL round-bottomed flask, then 1.970g (14mmol) iodomethane is added dropwise, has yellow mercury oxide generation immediately, be passed through N2, room temperature
It is stirred to react 2 hours, filters, filter cake is washed 2~3 times with ether, is placed in a vacuum drying oven 45 DEG C of dryings 48 hours, obtains chemical combination
Object B, yield 85%.
Embodiment 10
Following 1, the 5- pentylidene of preparation structure formula bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tools
Preparation are as follows:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- bis- of 0.858g (1mmol) 1,5- pentylidene
The iron-based methyl of cyclopentadienyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark brown oil 1,
5- pentylidene bis- [the hexacyanoferrate 0.582g of (1- ferrocenyl methyl) -3- imidazoles, yields 78%.
The spectral data of product are as follows: IR (cm-1): 3074 (C=C-H), 2917 (- CH3), 2886 (- CH2), 2043 (C ≡
N), 1636 (C=C).Elemental analysis (being calculated value in bracket): C%56.52 (56.76), H%6.14 (5.87), N%
15.81(16.05)。
The present embodiment 1,5- pentylidene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is with equimolar 1, pentamethylene bromide replacement, other steps and reality
It is identical to apply example 9, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,5- pentylidene.
Embodiment 10
Following 1, the 6- hexylidene of preparation structure formula bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tools
Preparation are as follows:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- bis- of 0.872g (1mmol) 1,6- hexylidene
The iron-based methyl of cyclopentadienyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark brown oil 1,
6- hexylidene bis- [the hexacyanoferrate 0.571g of (1- ferrocenyl methyl) -3- imidazoles, yields 75%.
The spectral data of product are as follows: IR (cm-1): 3056 (C=C-H), 2955 (- CH3), 2843 (- CH2), 2051 (C ≡
N), 1619 (C=C).Elemental analysis (being calculated value in bracket): C%56.78 (56.96), H%6.27 (5.93), N%
15.79(15.94)。
The present embodiment 1,6- hexylidene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar 1,6- dibromo-hexane, other steps and reality
It is identical to apply example 9, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,6- hexylidene.
Embodiment 11
Following 1, the 7- heptamethylene of preparation structure formula bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tools
Preparation are as follows:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- bis- of 0.886g (1mmol) 1,7- heptamethylene
The iron-based methyl of cyclopentadienyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark brown oil 1,
7- heptamethylene bis- [the hexacyanoferrate 0.604g of (1- ferrocenyl methyl) -3- imidazoles, yields 78%.
The spectral data of product are as follows: IR (cm-1): 3025 (C=C-H), 2937 (- CH3), 2871 (- CH2), 2043 (C ≡
N), 1673 (C=C).Elemental analysis (being calculated value in bracket): C%56.98 (57.14), H%6.29 (5.98), N%
15.69(15.83)。
The present embodiment 1,7- heptamethylene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar 1,7- dibromo-heptane, other steps and reality
It is identical to apply example 9, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,7- heptamethylene.
Embodiment 13
Following 1, the 8- octamethylene of preparation structure formula bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tools
Preparation are as follows:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- bis- of 0.900g (1mmol) 1,8- octamethylene
The iron-based methyl of cyclopentadienyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark brown oil 1,
8- octamethylene bis- [the hexacyanoferrate 0.599g of (1- ferrocenyl methyl) -3- imidazoles, yields 76%.
The spectral data of product are as follows: IR (cm-1): 3063 (C=C-H), 2929 (- CH3), 2819 (- CH2), 2013 (C ≡
N), 1633 (C=C).Elemental analysis (being calculated value in bracket): C%57.08 (57.33), H%6.37 (6.04), N%
15.57(15.73)。
The present embodiment 1,8- octamethylene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar 1,8-, bis- bromooctane, other steps and reality
It is identical to apply example 9, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,8- octamethylene.
Embodiment 14
Following 1, the 9- nonylene of preparation structure formula bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles, tools
Preparation are as follows:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- bis- of 0.914g (1mmol) 1,9- nonylene
The iron-based methyl of cyclopentadienyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark brown oil 1,
9- nonylene bis- [the hexacyanoferrate 0.578g of (1- ferrocenyl methyl) -3- imidazoles, yields 72%.
The spectral data of product are as follows: IR (cm-1): 3012 (C=C-H), 2916 (- CH3), 2887 (- CH2), 2034 (C ≡
N), 1655 (C=C).Elemental analysis (being calculated value in bracket): C%57.35 (57.51), H%6.38 (6.09), N%
15.44(15.63)。
The present embodiment 1,9- nonylene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar 1,9- dibromo nonane, other steps and reality
It is identical to apply example 9, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,9- nonylene.
Embodiment 15
Following 1, the 10- decylene of preparation structure formula it is bis- [hexacyanoferrate of (1- ferrocenyl methyl) -3- imidazoles,
It is specific the preparation method comprises the following steps:
Six cyanogen of 0.076g (0.8mmol) conjunction iron is dissolved completely in the 50mL round-bottomed flask for filling 20mL distilled water, to
Solution is fully transparent, then the clear solution is added dropwise to 5mL dissolved with the bis- [(1- of 0.928g (1mmol) 1,10- decylene
Ferrocenyl methyl) -3- imidazolium iodide methanol solution in, other steps are same as Example 9, obtain dark-brown oily oil
Shape object 1,10- decylene bis- [the hexacyanoferrate 0.604g of (1- ferrocenyl methyl) -3- imidazoles, yields 79%.
The spectral data of product are as follows: IR (cm-1): 3023 (C=C-H), 2921 (- CH3), 2886 (- CH2), 2063 (C ≡
N), 1616 (C=C).Elemental analysis (being calculated value in bracket): C%57.48 (57.69), H%6.44 (6.15), N%
15.37(15.53)。
The present embodiment 1,10- decylene it is bis- [structural formula of (1- ferrocenyl methyl) -3- imidazolium iodide is as follows:
In embodiment 9, Isosorbide-5-Nitrae-dibromobutane used is replaced with equimolar 1,10- dibromo-decane, other steps with
Embodiment 9 is identical, obtains bis- [(1- ferrocenyl the methyl) -3- imidazolium iodides of 1,10- decylene.
In order to prove that the present invention has apparent facilitation effect to the thermal decomposition of solid propellant major constituent, inventor is with high chlorine
For sour ammonium, hexogen and octogen, to the catalytic performance of biferrocene hexacyanoferrate prepared by embodiment 1~15
It is tested, specific experiment situation is as follows:
Compound 3mg, powdered ammonium perchlorate 97mg prepared by Example 1~15, ground and mixed is uniform, using difference
Scanning calorimeter instrument tests its catalytic performance, and experimental result is shown in Fig. 1 and Fig. 2.
Compound 4mg, powdered hexogen 96mg prepared by Example 1~8, ground and mixed is uniform, using differential
Scanning calorimeter tests its catalytic performance, and experimental result is shown in Fig. 3.
Compound 5mg, powdered hexogen 95mg prepared by Example 9~15, ground and mixed is uniform, using differential
Scanning calorimeter tests its catalytic performance, and experimental result is shown in Fig. 4.
Compound 1mg, powdered octogen 99mg prepared by Example 1~8, ground and mixed is uniform, using difference
Scanning calorimeter instrument tests its catalytic performance, and experimental result is shown in Fig. 5.
Compound 2mg, powdered octogen 98mg prepared by Example 9~15, ground and mixed is uniform, using difference
Scanning calorimeter instrument tests its catalytic performance, and experimental result is shown in Fig. 6.
By Fig. 1 and Fig. 2 as it can be seen that pure ammonium perchlorate is most strongly exothermic peak temperature at 304.4 DEG C, thermal discharge is smaller, works as height
After adding 3% 1~15 compound of embodiment in ammonium chlorate respectively, the heat that system is released is than the warm of pure ammonium perchlorate releasing
Amount significantly increases, and is advanced by the exothermic peak temperature of ammonium perchlorate, illustrates thermal decomposition of the compounds of this invention to ammonium perchlorate
With good combustion catalysis.
By Fig. 3 and 4 as it can be seen that pure hexogen is most strongly exothermic peak temperature at 229.7 DEG C, thermal discharge 788.11J/g, when
After adding 4% 7 compound of embodiment or 10~14 compound of embodiment of addition 5% in hexogen, hexogen can be made
Peak temperature drop is low, and thermal discharge increases, and illustrates that these compounds have good combustion catalysis to the thermal decomposition of hexogen.
By Fig. 5 and Fig. 6 as it can be seen that pure octogen is most strongly exothermic peak temperature at 284.1 DEG C, thermal discharge is
1022.31J/g, when the compound of embodiment 6 and 8 for adding 1% in octogen respectively or respectively 9 He of embodiment of addition 2%
After 15 compounds, the peak temperature drop of octogen can be made low, thermal discharge increases, and illustrates these compounds to the heat point of octogen
Solution has good combustion catalysis.
Claims (2)
1. a kind of biferrocene hexacyanoferrate, it is characterised in that the structural formula of the compound is as follows:
In formulaRepresent the biferrocene methyl alkyl glyoxaline cation of two unit positive charges of band；
The structural formula of the biferrocene methyl alkyl glyoxaline cation of two unit positive charges of above-mentioned band are as follows:
The integer that n is 4~10 in formula.
2. the preparation method of biferrocene hexacyanoferrate described in claim 1, it is characterised in that: by biferrocene
Methyl alkyl imidazolium iodide is dissolved in methanol, and Hexacyanoferrate aqueous solutions of potassium is then added dropwise, it is small that reaction 3~4 is stirred at room temperature
When, product is isolated and purified, biferrocene hexacyanoferrate is obtained；
The molar ratio of above-mentioned Hexacyanoferrate potassium and biferrocene methyl alkyl imidazolium iodide is 0.8:1, wherein double-core
The structural formula of ferrocenylmethyl alkyl imidazole iodide is as follows:
The integer that n is 4~10 in formula,Represent I-。
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| CN103288886A (en) * | 2013-06-17 | 2013-09-11 | 陕西师范大学 | Double-core ferrocene high-nitrogen energetic ion compound and preparation method thereof |
| CN104876974A (en) * | 2015-05-07 | 2015-09-02 | 陕西师范大学 | Ferrocene tetrazole ionic compounds and preparation method thereof |
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| CN103288886A (en) * | 2013-06-17 | 2013-09-11 | 陕西师范大学 | Double-core ferrocene high-nitrogen energetic ion compound and preparation method thereof |
| CN104876974A (en) * | 2015-05-07 | 2015-09-02 | 陕西师范大学 | Ferrocene tetrazole ionic compounds and preparation method thereof |
| CN104876975A (en) * | 2015-05-07 | 2015-09-02 | 陕西师范大学 | High-iron-content ferrocenyl tetrazole ionic compound and preparation method thereof |
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