CN112694606A - Poly-heptafluoro-butyl glycidyl ether, preparation method and application - Google Patents
Poly-heptafluoro-butyl glycidyl ether, preparation method and application Download PDFInfo
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- CN112694606A CN112694606A CN201911010188.7A CN201911010188A CN112694606A CN 112694606 A CN112694606 A CN 112694606A CN 201911010188 A CN201911010188 A CN 201911010188A CN 112694606 A CN112694606 A CN 112694606A
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- glycidyl ether
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- boron trifluoride
- butyl glycidyl
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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
- C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
- C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/001—Fillers, gelling and thickening agents (e.g. fibres), absorbents for nitroglycerine
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
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Abstract
The invention discloses a poly heptafluoro butyl glycidyl ether, a preparation method and application thereof, wherein the main chain of the poly heptafluoro butyl glycidyl ether contains a large amount of carbon-oxygen bonds, and the flexibility of the poly heptafluoro butyl glycidyl ether is superior to that of polybutadiene; the introduction of fluorine-containing groups into the side chains improves the density and oxygen balance on one hand, and on the other hand, fluorine can interact with high-energy metal powder (such as aluminum, boron and the like) in the explosive to further improve the energy of the explosive. The explosive has excellent mechanical properties and good stability, and can improve the oxygen balance and energy level of aluminum-containing and boron-containing explosives. Compared with the difluoroammonia polymer, the difluoroammonia polymer has better thermal stability and safer use. The product of the invention has simple and convenient preparation method, easy separation and purification and high yield, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of fluorine-containing polymers, in particular to poly (heptafluorobutyl glycidyl ether), a preparation method and application thereof.
Background
The energy-containing binder is used as an important component of the energy-containing material, provides a basic framework for the energy-containing material, enables the energy-containing material to have a certain shape and bear certain stress, and is widely applied to solid propellants and explosives. In recent years, polyaziridine glycidyl ether and polynitrate glycidyl ether have received extensive attention from researchers, and synthetic processes and mechanical properties of binders based on the two polymers have been developed. However, the former has poor mechanical properties and adhesive properties, while the latter has low sensitivity, so that the application prospects of the former are greatly limited. At present, hydroxyl-terminated polybutadiene is most widely used, and has the defects of excellent mechanical property and compatibility with energetic materials and low energy. Thus, fluorine-containing adhesives have been developed, and the fluorine-containing adhesives studied for the first time are difluoroammonia polymers, which have the advantages of high density, high energy and the like, but have limited applications and developments because of the disadvantages of high explosiveness, high toxicity and the like.
Disclosure of Invention
The present invention aims to solve the above problems and provide a novel binder and a method for preparing the same, namely, a poly (heptafluorobutyl glycidyl ether), a method for preparing the same, and use of the same.
The invention realizes the purpose through the following technical scheme:
a polyheptafluorobutyl glycidyl ether having the following structural formula:
in the formula: n is 4 to 20.
The other aspect of the application also provides a preparation method of the poly-heptafluorobutyl glycidyl ether, which comprises the steps of taking heptafluorobutoxy propylene oxide as a raw material, taking alcohol as an initiator and boron trifluoride diethyl etherate as a catalyst, and polymerizing the heptafluorobutoxy propylene oxide to generate the poly-heptafluorobutyl glycidyl ether.
In a further embodiment, the alcohol used as the initiator may be ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, pentaerythritol.
The method comprises the specific steps of dissolving alcohol and boron trifluoride diethyl etherate in dichloromethane, stirring uniformly at room temperature, then cooling to 0 ℃, slowly dropwise adding monomer heptafluorobutoxy epoxypropane in protective gas atmosphere, washing with distilled water after full reaction, and removing the solvent by reduced pressure distillation to obtain viscous liquid, namely the poly-heptafluorobutyl glycidyl ether.
The volume ratio of the addition amount of the alcohol to the boron trifluoride ethyl ether is 1.5-2.5: 1, and the volume ratio of the addition amount of the dichloromethane to the boron trifluoride ethyl ether is 90-150: 1.
Further, the protective gas is nitrogen or argon.
The further scheme is that the molecular weight of the poly heptafluorobutane glycidyl ether is between 1000-5000.
In another aspect, the application also provides the application of the poly-heptafluoro-butyl glycidyl ether and the poly-heptafluoro-butyl glycidyl ether obtained by the preparation method as an energetic polymer in the fields of explosives, propellants and initiating explosive devices.
The invention has the beneficial effects that:
the main chain of the poly (heptafluoro-butyl glycidyl ether) contains a large number of carbon-oxygen bonds, so that the flexibility of the poly (heptafluoro-butyl glycidyl ether) is superior to that of polybutadiene; the introduction of fluorine-containing groups into the side chains improves the density and oxygen balance on one hand, and on the other hand, fluorine can interact with high-energy metal powder (such as aluminum, boron and the like) in the explosive to further improve the energy of the explosive. The explosive has excellent mechanical properties and good stability, and can improve the oxygen balance and energy level of aluminum-containing and boron-containing explosives. Compared with the difluoroammonia polymer, the difluoroammonia polymer has better thermal stability and safer use. The product of the invention has simple and convenient preparation method, easy separation and purification and high yield, and is suitable for industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the embodiments or the drawings needed to be practical in the prior art description, and obviously, the drawings in the following description are only some embodiments of the embodiments, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows a hydrogen nuclear magnetic resonance spectrum (a) and a carbon nuclear magnetic resonance spectrum (b) of poly (heptafluorobutane glycidyl ether).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1:
375. mu.L of butanediol, 215. mu.L of boron trifluoride diethyl etherate and 22mL of methylene chloride were placed in a 100mL single-neck flask and stirred at room temperature for 30 min. Then, the temperature was decreased to 0 ℃ and the nitrogen atmosphere was replaced, and 35g of heptafluorobutoxypropylene oxide was added dropwise over about 4 hours. After the dropwise addition, the temperature is kept at 0 ℃ for reaction for 6h, and then the temperature is raised to room temperature for reaction for 12 h. After the reaction is finished, 400mL of distilled water is used for washing away the residual initiator and catalyst, then dichloromethane is removed by reduced pressure distillation, and vacuum drying is carried out at 50 ℃ until the weight is constant, so that 22g of poly heptafluorobutane glycidyl ether is obtained, the molecular weight is 2732g/mol, the dispersion coefficient is 1.32, and the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum are shown in FIG. 1.
Example 2:
535. mu.L of propylene glycol, 215. mu.L of boron trifluoride diethyl etherate and 22mL of methylene chloride were put into a 100mL single-neck flask, and stirred at room temperature for 30 min. Then, the temperature was decreased to 0 ℃ and the nitrogen atmosphere was replaced, and 30g of heptafluorobutoxypropylene oxide was added dropwise over about 4 hours. After the dropwise addition, the temperature is kept at 0 ℃ for reaction for 6h, and then the temperature is raised to room temperature for reaction for 8 h. After the reaction, the residual initiator and catalyst were washed with 400mL of distilled water, then the dichloromethane was distilled off under reduced pressure, and dried under vacuum at 50 ℃ to constant weight to give 21g of polyheptafluorobutane glycidyl ether with a molecular weight of 1827g/mol and a dispersion coefficient of 1.32.
Example 3:
535. mu.L of hexanediol, 215. mu.L of boron trifluoride diethyl etherate and 30mL of methylene chloride were placed in a 100mL single-neck flask, and stirred at room temperature for 30 min. Then, the temperature was decreased to 0 ℃ and the nitrogen atmosphere was replaced, and 30g of heptafluorobutoxypropylene oxide was added dropwise over about 4 hours. After the dropwise addition, the temperature is kept at 0 ℃ for reaction for 6h, and then the temperature is raised to room temperature for reaction for 12 h. After the reaction, the residual initiator and catalyst were washed with 400mL of distilled water, and then the dichloromethane was distilled off under reduced pressure, and dried under vacuum at 50 ℃ to constant weight to give 21g of polyheptafluorobutane glycidyl ether having a molecular weight of 3327g/mol and a dispersion coefficient of 1.4.
Example 4:
535. mu.L of glycerol, 215. mu.L of boron trifluoride diethyl etherate and 30mL of methylene chloride were put into a 100mL single-neck flask, and stirred at room temperature for 30 min. Then, the temperature was decreased to 0 ℃ and the nitrogen atmosphere was replaced, and 30g of heptafluorobutoxypropylene oxide was added dropwise over about 4 hours. After the dropwise addition, the temperature of 0 ℃ is kept for reaction for 4h, and then the temperature is raised to room temperature for reaction for 16 h. After the reaction, 400mL of distilled water was used to wash off the residual initiator and catalyst, the dichloromethane was distilled off under reduced pressure, and the product was dried under vacuum at 50 ℃ to constant weight to give 20g of polyheptafluorobutane glycidyl ether having a molecular weight of 4527g/mol and a dispersion coefficient of 1.31.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims. It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (8)
1. A polyheptafluorobutyl glycidyl ether having the following structural formula:
in the formula: n is 4 to 20.
2. The method of producing polypeptafluorobutyl glycidyl ether as claimed in claim 1, characterized in that heptafluorobutoxy propylene oxide is polymerized to produce polypeptafluorobutyl glycidyl ether using heptafluorobutoxy propylene oxide as a raw material, alcohol as an initiator, and boron trifluoride ethyl ether as a catalyst.
3. The method of claim 2, wherein the alcohol used as the initiator is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerol, and pentaerythritol.
4. The method for preparing poly (heptafluorobutyl glycidyl ether) according to claim 2, wherein the method comprises the specific steps of dissolving alcohol and boron trifluoride diethyl etherate in dichloromethane, stirring the mixture uniformly at room temperature, cooling the mixture to 0 ℃, slowly adding monomer heptafluorobutoxy propylene oxide dropwise in a protective gas atmosphere, washing the mixture with distilled water after sufficient reaction, and removing the solvent by distillation under reduced pressure to obtain viscous liquid, namely poly (heptafluorobutyl glycidyl ether).
5. The method of claim 2, wherein the shielding gas is nitrogen or argon.
6. The method of claim 2, wherein the molecular weight of the poly (heptafluorobutyl) glycidyl ether is between 1000-5000.
7. The process for producing polypeptafluorobutyl glycidyl ether as set forth in claim 4, wherein the volume ratio of the alcohol to the boron trifluoride etherate added is 1.5-2.5: 1, and the volume ratio of the dichloromethane to the boron trifluoride etherate added is 90-150: 1.
8. Use of the polyheptafluorobutyl glycidyl ether of claim 1 and the polyheptafluorobutyl glycidyl ether obtained by the preparation method of claims 2 to 7 as an energy-containing polymer in the fields of explosives, propellants and initiating explosive devices.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824130A (en) * | 2009-12-31 | 2010-09-08 | 广东银洋树脂有限公司 | Preparation method of soft segment lateral chain fluorine-containing waterborne polyurethane |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
| CN106084204A (en) * | 2016-08-23 | 2016-11-09 | 西安近代化学研究所 | A kind of trifluoromethyl replaces azide polymer and preparation method thereof |
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- 2019-10-22 CN CN201911010188.7A patent/CN112694606A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824130A (en) * | 2009-12-31 | 2010-09-08 | 广东银洋树脂有限公司 | Preparation method of soft segment lateral chain fluorine-containing waterborne polyurethane |
| CN103772692A (en) * | 2013-12-27 | 2014-05-07 | 南京信息工程大学 | Copolymerized glycol of perfluoroalkyl glycidyl ethers and cyclic ether and preparation method of copolymerized glycol |
| CN106084204A (en) * | 2016-08-23 | 2016-11-09 | 西安近代化学研究所 | A kind of trifluoromethyl replaces azide polymer and preparation method thereof |
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Application publication date: 20210423 |