CN105713192A - 3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether and synthetic method - Google Patents
3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether and synthetic method Download PDFInfo
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- CN105713192A CN105713192A CN201610072759.XA CN201610072759A CN105713192A CN 105713192 A CN105713192 A CN 105713192A CN 201610072759 A CN201610072759 A CN 201610072759A CN 105713192 A CN105713192 A CN 105713192A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/16—Cyclic ethers having four or more ring atoms
- C08G65/20—Tetrahydrofuran
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
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Abstract
The invention discloses 3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether and a synthetic method and belongs to the field of organic synthesis.According to the method, bromoferrocene and sodium azide are used as raw materials, and 1-azidoferrocene is obtained by means of synthesis for use; dimethylformamide is used as a solvent, and pentaerythritol and thionyl chloride are used as raw materials for a reaction to obtain 2,2,2-tri (chloromethyl)-1-hydroxyethane, a sodium hydroxide aqueous solution is added for cyclization, distillation, extraction, drying, solvent steaming and crystallization are performed to obtain 3,3-bis (chloromethyl) oxetane, synthesized azidoferrocene is added, 3,3-bis (azidoferrocene) oxetane is obtained under the action of a catalyst, and 3,3-bis (azidoferrocene) epoxybutane/tetrahydrofuran polyether is obtained under the action of tetrahydrofuran/1,4-butanediol/boron trifluoride diethyl etherate.The process conditions are mild, the requirement on equipment is low, and mass synthesis is benefited.
Description
Technical field
The invention discloses double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-and synthetic method thereof.
Background technology
Ferrocene and its derivative is due to the catalytic performance of its uniqueness, by the extensive concern of research worker.In structure
Due to the existence of ferrum, the burning velocity of propellant as burningrate catalyst in solid propellant, can be regulated.Ferrocene connects simultaneously
Branch and other Organic substances form ferrocene derivatives, can be scattered in uniformly in solid propellant, make ferrum in solid propellant
Element dispersive property is more preferable.But due to ferrocene and dissociating property of small molecule derivative thereof, when being added in solid propellant, time long
Between storage cause the ferrocene in propellant to migrate, affect the combustibility of propellant.Therefore, develop one and do not migrate two
Cyclopentadienyl ferrum derivant or functional material become the Main way of development at present.
Azido compound refers to azido (-N3) compound, be a kind of containing can be higher compound, draw in Organic substance
Entering azido group, can increase substantially organic energy, introducing the groups containing energy such as nitrine in propellant component be solid propellant propulsion
The developing direction that agent is following.Nitrine amine is tired out compound and has carried out a series of research by SUN TIANTIAN, is that an alternative hydrazine of class advances
Agent novel containing can low toxicity liquid fuel (see document: the synthesis transitivity research of Azido Energetic fuel, Zhejiang University,
2013).Xu Ruoqian et al. develops the glycidyl azide polymer of a kind of three arm type Azido Energetic plasticizer azido end-blockings
(GAPA), this energetic plasticiser all shows excellence at aspects such as stability, plasticity energy, has preferable application prospect and (sees
Document: the synthesis of three arm type Azido Energetic plasticizer GAPA and performance, energetic material, Vol.17, No.6, December,
2009).Therefore, the introducing of azido group can improve propellant energy, reduces solid fuel volume, improves aircraft flight speed
Degree.
Comprehensive above 2 points, the present invention proposes a kind of novel containing energy self-catalysis binding agent, and chemical name is: 3,3-is double
(nitrine ferrocene) epoxy butane/tetrahydrofuran polyether, its structural formula is shown in, this product is polymer, containing two in each monomer
Ferrocene group, two azido groups, iron content is up to 18%.Ferrocene percent grafting is higher compared with Butacene, grafting is equal
Even, technique is easier to make for.
Summary of the invention
It is an object of the invention to invention one and contain energy height, the nonmigratory binding agent of ferrocene, solve ferrocene derivatives and make
For problems such as the ferrocene migrations of existence during solid propellant burningrate catalyst.And propose that a kind of technique is simple, yield is high,
It is prone to industrialized synthetic route.
Technical scheme: 3,3-double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether, its structural chemical formula
For:
The synthetic method of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of a kind of 3,3-, step is as follows: (1) folds
The synthesis of nitrogen ferrocene
In the second alcohol and water that mass ratio is 3:1, add bromo ferrocene, under 20 DEG C of temperature conditionss, add Azide
Sodium, second alcohol and water gross mass: bromo ferrocene: the mass ratio of Hydrazoic acid,sodium salt is 50-70:7-8:4-6, it is to slowly warm up to backflow,
React 5-8 hour；Above-mentioned mixed solution is washed twice with water after terminating by reaction, isolates organic facies, with anhydrous magnesium sulfate pair
Organic facies is deviate from solvent after being dried 2 hours and is obtained nitrine ferrocene；
(2) synthesis of 2,2,2-tri-(chloromethyl)-1-hydroxyl ethane
Using dimethylformamide as solvent, under 15 DEG C of temperature conditionss, it is slowly added dropwise the 60% of thionyl chloride total amount,
React 1-2 hour at a temperature of 20-30 DEG C；Keep 20-30 DEG C of temperature, be slow added into tetramethylolmethane, rise to 110-120 DEG C of reaction
4-5 hour；At a temperature of 110-120 DEG C, add the thionyl chloride of residue 40% mass, react 6 hours, obtain 2,2,2-tri-
(chloromethyl)-1-hydroxyl ethane；Wherein, dimethylformamide: thionyl chloride: the mass ratio of tetramethylolmethane is 2-3:6:7-8；
(3) synthesis of double (chloromethyl) oxetanes of 3,3-
Under 85 DEG C of temperature conditionss, by mass fraction be 30% sodium hydrate aqueous solution to 2,2,2-tri-(chloromethyl)-1-
In hydroxyl ethane, sodium hydrate aqueous solution and tetramethylolmethane mass ratio are 1:4-1:6, after completion of dropwise addition, continue reaction 3 hours；
After reaction terminates, distilling under 120-130 DEG C of temperature conditions, organic facies recovery obtained is separated, aqueous phase dichloromethane
Being extracted twice, the dichloromethane after extraction merges with organic facies, then is dried 2 hours with anhydrous magnesium sulfate, obtains with filter paper filtering
Filtrate；Filtrate is distilled in a rotary evaporator, temperature 80 DEG C, dichloromethane be evaporated after crude product, crude product crystallisation by cooling 36 hours,
Filtration under diminished pressure obtains double (chloromethyl) oxetanes of solid product 3,3-.
(4) synthesis of double (nitrine ferrocenyl) oxetanes of 3,3-
By 3, double (chloromethyl) oxetanes of 3-is dissolved in dichloromethane, adds catalyst BF3, at 120-130 DEG C
At a temperature of be slowly added in step (1) the nitrine ferrocene of synthesis, after be to slowly warm up to 90 DEG C, constant temperature 3 hours, obtain 3,3-is double
(nitrine ferrocenyl) oxetanes；Double (chloromethyl) oxetanes of 3,3-: dichloromethane: catalyst: nitrine ferrocene
Mass ratio be 2:6-8:0.5-1.5:1.6-2.8.
(5) synthesis of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-
Dichloromethane, oxolane, 1,4-butanediol and boron trifluoride diethyl etherate are according to mass ratio 4-5:1.5-2.5:0.02-
0.06:1 mixes, and stirring at normal temperature 0.5-1 hour is placed in ice bath, is slowly added in step (4) 3 obtained, the double (nitrine two of 3-
Cyclopentadienyl iron-based) oxetanes, boron trifluoride diethyl etherate: 3,3-double (nitrine ferrocenyl) oxetanes=1:4-1:6, insulation is anti-
Answer 24 hours；Close ice bath and be at room temperature slowly added to the carbon sodium hydride aqueous solution that mass fraction is 4%, stir 10-30 minute,
Being slowly added to dichloromethane, the mass ratio of dichloromethane and above-mentioned mixed solution is 0.5-2:1, stirs 20-50 minute, isolates
Lower floor's organic facies, washed once with carbon sodium hydride aqueous solution；Isolated organic facies addition anhydrous sodium sulfate is dried 2 hours,
By filtration, distillation obtains 3, double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3-.
Synthetic route is schematically as follows
Beneficial effects of the present invention: the 3 of present invention proposition, double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3-,
Ferrocene content is high, has good catalytic performance, can be applicable in solid propellant；Ferrocene does not migrates, and uniformly divides
Dissipate in solid propellant；Monomer contains two azido groups, and binding agent has higher energy；The reaction bar that the present invention proposes
Part is the gentleest controlled, is suitable for industrialized production.Double (nitrine ferrocene) the new solid propellant of tetrahydrofuran polyether of 3,3-is used
Adhesive, the iron content in product is up to 18%, it is possible to increase the performance during propellant combustion, the azido group in structure
Binding agent energy is made to increase substantially.
Detailed description of the invention
The present invention is expanded on further below by embodiment, but embodiment will not limit the invention.In the present invention
The bound value of technological parameter enumerated of technical scheme, interval can realize the product of application claims.
Embodiment 1
The synthesis of nitrine ferrocene:
In 50g ethanol/water (ethanol: water=3:1), add 7g bromo ferrocene, under the conditions of temperature 20 DEG C, add nitrine
Change sodium 4g, be to slowly warm up to backflow, react and mixed solution was washed twice with water in 6 hours, separate organic facies, use anhydrous magnesium sulfate
Deviate from solvent after being dried 2 hours and obtain nitrine ferrocene 6.9g.
The synthesis of 2,2,2-tri-(chloromethyl)-1-hydroxyl ethane:
Using 55g dimethylformamide as solvent, under the conditions of 15 DEG C, it is slowly added dropwise 65g thionyl chloride, reaction temperature control
System is reacted 2 hours at a temperature of 25 DEG C.In reactor, it is slowly added to 75g tetramethylolmethane at a temperature of latter 25 DEG C, rises to 115 DEG C instead
Answer 4 hours.At a temperature of 115 DEG C, add 43g thionyl chloride, react 6 hours.
The synthesis of double (chloromethyl) oxetanes of 3,3-:
Under the conditions of 85 DEG C, in dropping sodium hydrate aqueous solution (9g water 4g sodium hydroxide) to reactor, after completion of dropwise addition
Continue reaction 3 hours.Distilling at a temperature of 125 DEG C, organic facies recovery obtained separates, and aqueous phase 50ml dichloromethane extracts two
Secondary, organic facies merging 5g anhydrous magnesium sulfate is dried 2 hours, obtains filtrate with filter paper filtering.Filtrate is steamed in a rotary evaporator
Evaporating, temperature 80 DEG C, dichloromethane obtains crude product 58g, crude product crystallisation by cooling 24 hours after being evaporated, and filtration under diminished pressure obtains 6.8g solid and produces
Double (chloromethyl) oxetanes of product 3,3-.
The synthesis of double (nitrine ferrocenyl) oxetanes of 3,3-:
By 3, double (chloromethyl) oxetanes of 3-is dissolved in 30g dichloromethane, adds 4g catalyst BF3, at 130 DEG C
At a temperature of be slowly added in (1) nitrine ferrocene of synthesis, after be to slowly warm up to 90 DEG C, constant temperature 3 hours.Obtain 3,3-double (folded
Nitrogen ferrocenyl) oxetanes.
The synthesis of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-:
Weighing dichloromethane 100g, 1,4-butanediol 0.35g, boron trifluoride diethyl etherate 22g, oxolane 45g add reaction
In device, stirring at normal temperature 1 hour.Obtain reaction mass to be placed in ice bath, at a temperature of 0 DEG C, be slowly added to material in (4) step,
Rear insulation reaction 20 hours.Close ice bath and be at room temperature slowly added to 100g 4% carbon sodium hydride aqueous solution, stir 10 minutes, slow
Slow addition 100g dichloromethane, stirs 30 minutes, isolates lower floor's organic facies and repeats to wash one with 100g carbon sodium hydride aqueous solution
Secondary.Isolating organic facies addition 10g anhydrous sodium sulfate to be dried 2 hours, by filtration, distillation obtains 3, and 3-is double (nitrine ferrocene)
Epoxy butane/tetrahydrofuran polyether 8.2g.
Embodiment 2
The synthesis of nitrine ferrocene:
In 60g ethanol/water (ethanol: water=3:1), add 8g bromo ferrocene, under the conditions of temperature 20 DEG C, add nitrine
Change sodium 4g and be to slowly warm up to backflow, react and mixed solution was washed twice with water in 8 hours, separate organic facies, use anhydrous magnesium sulfate
Deviate from solvent after being dried 2 hours and obtain nitrine ferrocene 6.5g.
The synthesis of 2,2,2-tri-(chloromethyl)-1-hydroxyl ethane:
Using 40g dimethylformamide as solvent, under the conditions of 15 DEG C, it is slowly added dropwise 60g thionyl chloride, reaction temperature control
System is reacted 1-2 hour at a temperature of 20-30 DEG C.In reactor, it is slowly added to 73g tetramethylolmethane at a temperature of latter 20-30 DEG C, rises
React 4-5 hour to 110-120 DEG C.At a temperature of 110-120 DEG C, add 40g thionyl chloride, react 6 hours.
The synthesis of double (chloromethyl) oxetanes of 3,3-:
Under the conditions of 85 DEG C, in dropping sodium hydrate aqueous solution (9g water 4g sodium hydroxide) to reactor, after completion of dropwise addition
Continue reaction 3 hours.Distilling at a temperature of 130 DEG C, organic facies recovery obtained separates, and aqueous phase 50ml dichloromethane extracts two
Secondary, organic facies merging 5g anhydrous magnesium sulfate is dried 2 hours, obtains filtrate with filter paper filtering.Filtrate is steamed in a rotary evaporator
Evaporating, temperature 80 DEG C, dichloromethane obtains crude product 51g, crude product crystallisation by cooling 24 hours after being evaporated, and filtration under diminished pressure obtains 6.9g solid and produces
Double (chloromethyl) oxetanes of product 3,3-.The synthesis of double (nitrine ferrocenyl) oxetanes of 3,3-:
By 3, double (chloromethyl) oxetanes of 3-is dissolved in 25g dichloromethane, adds 4g catalyst BF3, 126
Be slowly added in (1) nitrine ferrocene of synthesis at a temperature of DEG C, after be to slowly warm up to 90 DEG C, constant temperature 3 hours.Obtain 3,3-double
(nitrine ferrocenyl) oxetanes.
The synthesis of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-:
Weighing dichloromethane 90g, 1,4-butanediol 0.4g, boron trifluoride diethyl etherate 20g, oxolane 45g add reactor
In, stirring at normal temperature 1 hour.Obtain reaction mass to be placed in ice bath, at a temperature of 0 DEG C, be slowly added to material in (4) step, after
Insulation reaction 20 hours.Close ice bath and be at room temperature slowly added to 100g 4% carbon sodium hydride aqueous solution, stir 10 minutes, slowly
Add 100g dichloromethane, stir 30 minutes, isolate lower floor's organic facies and repeat to washed once with 100g carbon sodium hydride aqueous solution.
Isolating organic facies addition 10g anhydrous sodium sulfate to be dried 2 hours, by filtration, distillation obtains 3, double (nitrine ferrocene) ring of 3-
Oxygen butane/tetrahydrofuran polyether 8g.
Embodiment 3
The synthesis of nitrine ferrocene:
In 50g ethanol/water (ethanol: water=3:1), add 7.5g bromo ferrocene, under the conditions of temperature 20 DEG C, add folded
Sodium nitride 4g, is to slowly warm up to backflow, reacts and be washed twice with water by mixed solution for 6 hours, separate organic facies, use anhydrous slufuric acid
Magnesium is deviate from solvent after being dried 2 hours and is obtained nitrine ferrocene 6.5g.
The synthesis of 2,2,2-tri-(chloromethyl)-1-hydroxyl ethane:
Using 40g dimethylformamide as solvent, under the conditions of 15 DEG C, it is slowly added dropwise 65g thionyl chloride, reaction temperature control
System is reacted 1 hour at a temperature of 20 DEG C.In reactor, it is slowly added to 73g tetramethylolmethane at a temperature of latter 20-30 DEG C, rises to 110
DEG C reaction 4 hours.At a temperature of 110-120 DEG C, add 42g thionyl chloride, react 6 hours.
The synthesis of double (chloromethyl) oxetanes of 3,3-:
Under the conditions of 85 DEG C, in dropping sodium hydrate aqueous solution (9g water 4g sodium hydroxide) to reactor, after completion of dropwise addition
Continue reaction 3 hours.Distilling at a temperature of 120 DEG C, organic facies recovery obtained separates, and aqueous phase 50ml dichloromethane extracts
Twice, organic facies merging 5g anhydrous magnesium sulfate is dried 2 hours, obtains filtrate with filter paper filtering.Filtrate is in a rotary evaporator
Distillation, temperature 80 DEG C, dichloromethane obtains crude product 55g, crude product crystallisation by cooling 24 hours after being evaporated, filtration under diminished pressure obtains 7g solid and produces
Double (chloromethyl) oxetanes of product 3,3-.
The synthesis of double (nitrine ferrocenyl) oxetanes of 3,3-:
By 3, double (chloromethyl) oxetanes of 3-is dissolved in 25g dichloromethane, adds 4g catalyst BF3, at 120 DEG C
At a temperature of be slowly added in (1) nitrine ferrocene of synthesis, after be to slowly warm up to 90 DEG C, constant temperature 3 hours.Obtain 3,3-double (folded
Nitrogen ferrocenyl) oxetanes.
The synthesis of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-:
Weighing dichloromethane 100g, 1,4-butanediol 0.35g, boron trifluoride diethyl etherate 20g, oxolane 40g add reaction
In device, stirring at normal temperature 1 hour.Obtain reaction mass to be placed in ice bath, at a temperature of 0 DEG C, be slowly added to material in (4) step,
Rear insulation reaction 20 hours.Close ice bath and be at room temperature slowly added to 120g 4% carbon sodium hydride aqueous solution, stir 10 minutes, slow
Slow addition 100g dichloromethane, stirs 30 minutes, isolates lower floor's organic facies and repeats to wash one with 100g carbon sodium hydride aqueous solution
Secondary.Isolating organic facies addition 10g anhydrous sodium sulfate to be dried 3 hours, by filtration, distillation obtains 3, and 3-is double (nitrine ferrocene)
Epoxy butane/tetrahydrofuran polyether 7.9g.
Embodiment result table
Claims (2)
1.3,3-double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether, it is characterised in that its structural chemical formula is:
2. one kind 3, the synthetic method of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3-, it is characterised in that step is such as
Under:
(1) synthesis of nitrine ferrocene
In the second alcohol and water that mass ratio is 3:1, add bromo ferrocene, under 20 DEG C of temperature conditionss, add Hydrazoic acid,sodium salt, second
Alcohol and water gross mass: bromo ferrocene: the mass ratio of Hydrazoic acid,sodium salt is 50-70:7-8:4-6, is to slowly warm up to backflow, reacts 5-
8 hours；Above-mentioned mixed solution is washed twice with water after terminating by reaction, isolates organic facies, with anhydrous magnesium sulfate to organic facies
Deviate from solvent after being dried 2 hours and obtain nitrine ferrocene；
(2) synthesis of 2,2,2-tri-(chloromethyl)-1-hydroxyl ethane
Using dimethylformamide as solvent, under 15 DEG C of temperature conditionss, it is slowly added dropwise the 60% of thionyl chloride total amount, 20-30
React 1-2 hour at a temperature of DEG C；Keep 20-30 DEG C of temperature, be slow added into tetramethylolmethane, rise to 110-120 DEG C of reaction 4-5 little
Time；At a temperature of 110-120 DEG C, add the thionyl chloride of residue 40% mass, react 6 hours, obtain 2,2,2-tri-(chloromethanes
Base)-1-hydroxyl ethane；Wherein, dimethylformamide: thionyl chloride: the mass ratio of tetramethylolmethane is 2-3:6:7-8；
(3) synthesis of double (chloromethyl) oxetanes of 3,3-
Under 85 DEG C of temperature conditionss, by mass fraction be 30% sodium hydrate aqueous solution to 2,2,2-tri-(chloromethyl)-1-hydroxyl
In ethane, sodium hydrate aqueous solution and tetramethylolmethane mass ratio are 1:4-1:6, after completion of dropwise addition, continue reaction 3 hours；Reaction
After end, distilling under 120-130 DEG C of temperature conditions, organic facies recovery obtained is separated, and aqueous phase dichloromethane extracts
Twice, the dichloromethane after extraction merges with organic facies, then is dried 2 hours with anhydrous magnesium sulfate, obtains filtrate with filter paper filtering；
Filtrate is distilled in a rotary evaporator, temperature 80 DEG C, and dichloromethane obtains crude product, crude product crystallisation by cooling 36 hours, decompression after being evaporated
It is filtrated to get double (chloromethyl) oxetanes of solid product 3,3-；
(4) synthesis of double (nitrine ferrocenyl) oxetanes of 3,3-
By 3, double (chloromethyl) oxetanes of 3-is dissolved in dichloromethane, adds catalyst BF3, at a temperature of 120-130 DEG C
Be slowly added in step (1) the nitrine ferrocene of synthesis, after be to slowly warm up to 90 DEG C, constant temperature 3 hours, obtain 3, the double (nitrine of 3-
Ferrocenyl) oxetanes；Double (chloromethyl) oxetanes of 3,3-: dichloromethane: catalyst: the quality of nitrine ferrocene
Ratio is 2:6-8:0.5-1.5:1.6-2.8；
(5) synthesis of double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3,3-
Dichloromethane, oxolane, 1,4-butanediol and boron trifluoride diethyl etherate are according to mass ratio 4-5:1.5-2.5:0.02-
0.06:1 mixes, and stirring at normal temperature 0.5-1 hour is placed in ice bath, is slowly added in step (4) 3 obtained, the double (nitrine two of 3-
Cyclopentadienyl iron-based) oxetanes, boron trifluoride diethyl etherate: 3,3-double (nitrine ferrocenyl) oxetanes=1:4-1:6, insulation is anti-
Answer 24 hours；Close ice bath and be at room temperature slowly added to the carbon sodium hydride aqueous solution that mass fraction is 4%, stir 10-30 minute,
Being slowly added to dichloromethane, the mass ratio of dichloromethane and above-mentioned mixed solution is 0.5-2:1, stirs 20-50 minute, isolates
Lower floor's organic facies, washed once with carbon sodium hydride aqueous solution；Isolated organic facies addition anhydrous sodium sulfate is dried 2 hours,
By filtration, distillation obtains 3, double (nitrine ferrocene) epoxy butane/tetrahydrofuran polyether of 3-.
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| CN106316729A (en) * | 2016-08-24 | 2017-01-11 | 湖北航天化学技术研究所 | Wide adaptive azide polyether propellant |
| CN109837053A (en) * | 2019-03-06 | 2019-06-04 | 西安近代化学研究所 | A kind of polyene-based polytetrahydrofuran adhesive and its synthetic method |
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| KR20140125017A (en) * | 2013-04-17 | 2014-10-28 | 한양대학교 에리카산학협력단 | Oxirane prepolymer binder, oxirane prepolymer binder containing ferrocene derivatives, and method for preparing the same |
| KR20140126859A (en) * | 2013-04-23 | 2014-11-03 | 한양대학교 에리카산학협력단 | Oxetane prepolymer binder, oxetane prepolymer binder containing ferrocene derivatives, and method for preparing the same |
| CN104650338A (en) * | 2014-12-03 | 2015-05-27 | 营口天元化工研究所股份有限公司 | Preparation method of 3,3-bi(nitrine methyl) epoxybutane and tetrahydrofuran copolymer |
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| CN109837053A (en) * | 2019-03-06 | 2019-06-04 | 西安近代化学研究所 | A kind of polyene-based polytetrahydrofuran adhesive and its synthetic method |
| CN109837053B (en) * | 2019-03-06 | 2021-02-26 | 西安近代化学研究所 | Polyene polytetrahydrofuran adhesive and synthesis method thereof |
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