CN112062926A - Cross-linking type fusible casting energetic polymer adhesive material - Google Patents
Cross-linking type fusible casting energetic polymer adhesive material Download PDFInfo
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- CN112062926A CN112062926A CN202010971424.8A CN202010971424A CN112062926A CN 112062926 A CN112062926 A CN 112062926A CN 202010971424 A CN202010971424 A CN 202010971424A CN 112062926 A CN112062926 A CN 112062926A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
- C06B45/105—The resin being a polymer bearing energetic groups or containing a soluble organic explosive
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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Abstract
The invention relates to a cross-linking type fusible casting energetic polymer adhesive material, belonging to the field of propellants. The raw materials of the invention comprise: energetic macromolecules, diisocyanate, disulfide and a crosslinking agent; the solvent comprises: tetrahydrofuran, dichloromethane, chloroform, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, and the like. The adhesive material prepared by the invention has the advantages of high viscosity, flowability, excellent mechanical property, high yield and cycle sustainability. At moderate temperatures (90 ℃), this crosslinked polymeric binder can be converted into a molten linear polymeric fluid, which effectively prevents the settling of the solid components in the propellant system, thereby producing a homogeneous propellant fuel.
Description
Technical Field
The invention relates to a cross-linking type fusible casting energetic polymer adhesive material, belonging to the field of propellants.
Background
The propellant is a main energy source required by launching of rocket and missile in recent years, a large amount of gas is generated instantly through combustion to push an aircraft to run, and in order to improve the energy characteristic of the propellant, the conventional propellant is generally composed of a plurality of components, namely a composite propellant. Conventional composite propellants mainly include: the energy-containing solid filler (oxidant and reducer), auxiliary agent (plasticizer, bonding agent, anti-aging agent, etc.), curing agent and adhesive are prepared by adding the four raw materials into a container in sequence according to a certain proportion, uniformly stirring, pouring into a mold, and curing and forming at a proper temperature.
This method has several disadvantages:
(1) the molecular weight of the adhesive is low (M)n1000-4000Da) and in smaller amounts (w%<20%). Therefore, the added solid filler is easy to settle in the curing process, so that the density of the propellant is uneven, the combustion is insufficient, and the thermal stability is poor;
(2) an additional curing agent is required. In order to form the propellant, a curing agent needs to be additionally added, so that the preparation process is increased, whether the curing reaction is completely carried out is difficult to determine, if the curing reaction is not completely carried out, the residual curing agent in the system can play a plasticizing role so as to reduce the mechanical property of the propellant, and if the curing reaction is excessively carried out, the propellant can be aged and the service life is shortened, so that the curing time and the curing temperature need to be carefully regulated and controlled, and the consumption of human resources is caused;
(3) in order to improve the energy property of the propellant, energy-containing adhesives have been paid much attention due to the properties of high energy, insensitivity, stability, no pollution and the like, but in general, energy-containing adhesives have bulky side groups, such as azide groups, nitrate groups, nitro groups and the like, which makes the intermolecular force weaker, resulting in extremely poor mechanical strength of the propellant;
(4) the solidified propellant needs to be prepared again once damaged, and the material can not repair the damage spontaneously, thereby causing great waste of high-energy materials such as the propellant.
Disclosure of Invention
The invention aims to overcome the defect that an adhesive in a propellant is not repairable on the premise of not damaging the energy property, the mechanical property and the bonding property of the propellant, prepare the adhesive containing energy and capable of being repaired and improve the recycling rate of a propellant material.
The purpose of the invention is realized by the following technical scheme.
A cross-linking type fusible casting energetic polymer adhesive material:
(1) the types of raw materials are as follows:
the cross-linking type fusible casting energetic polymer adhesive comprises the following raw materials: energetic polymer, diisocyanate, disulfide, cross-linking agent and catalyst; the solvent comprises: tetrahydrofuran, dichloromethane, chloroform, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, and the like.
The energy-containing polymer includes: polyglycidyl ether azide (GAP), branched polyglycidyl ether azide (BGAP), 3-diazacyclomethyloxetane (BAMO), 3-Azidooxybutylene (AZOX), 3-azidomethyl-3-methyloxetane (AAMO), polyglycidyl nitrate (PGN), poly (1, 3-oxapropyl) -bis (2, 2-dinitriloylmethyl) -1, 3-malonate (PBBP), etc.;
the diisocyanate includes: dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), and the like;
the disulfides include: dimethylol disulfide, dihydroxyethyl disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, and the like;
the crosslinking agent comprises: trimethylolpropane, castor oil, pentaerythritol, and the like.
The catalyst is as follows: dibutyl tin dilaurate
(2) Relative content of raw materials
The addition parts of the substances are as follows: energy-containing polymer: 100 parts of (A); diisocyanate: 20-65 parts of a solvent; disulfide: 10-35 parts; polyhydroxy crosslinking agent: 0.5-2 parts; 0.1-0.3 part of catalyst.
Solvent: 35-50 parts (which is 0.25 times of the total mass part of the system).
The calculation formula of the feeding parts of the raw materials is as follows:
where a is the functionality of the crosslinking agent and b is the functionality of the disulfide, and furthermore, in the present adhesive system, there are three important parameters to calculate:
the parameter 1, the relative contents of isocyanato-NCO and hydroxy-OH, is indicated by R. Theoretically, the R value is 1, which represents that the isocyanic acid radical-NCO and the hydroxyl-OH in the system are completely reacted, however, the influence of the hydroxyl-OH in the environment and the moisture of the solvent is considered, in the actual operation process, the R value is generally 0.9-1.2, and the optimal R value needs to be determined in the experiment process according to the difference of the system;
The parameter 3, the percentage content of the hard segment, can be used for regulating and controlling the hardness and flexibility of the material, and is represented by a letter W. The larger the W value is, the higher the rigidity and toughness of the adhesive is, the smaller the W value is, the better the flexibility and elasticity of the adhesive is, and in order to avoid the adhesive from losing mechanical properties due to being too soft, the value range of W is generally between 20% and 60%.
(3) Preparation method of fusion-cast energetic polymer adhesive
Step one, end sealing. The energy-containing high polymer material is firstly vacuumized to remove the water in the system and prevent the interference reaction. Adding metered energetic polymer into a three-mouth bottle, and adding N at a certain speed at 90 DEG C2Under the atmosphere, the stirring speed is controlled at 200 r.s-1Dropwise and slowly adding metered diisocyanate dropwise, and then under the action of a proper amount of catalyst (dibutyltin dilaurate)And reacting for 4 hours, wherein in the process, the hydroxyl of the energetic polymer completely reacts with the isocyanic acid radical of the diisocyanate, and the reaction of the hydroxyl of the energetic polymer is characterized to be complete by the disappearance of the peak position of the hydroxyl of the energetic polymer in an infrared test, namely blocking reaction.
Step two, chain scraping. Cooling the system to room temperature, adding a chain extender disulfide and a solvent to react for six hours, wherein in the process, the room temperature aims at slowing down the reactivity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; then dropwise adding the solution dissolved with the cross-linking agent into a three-neck flask, stirring until the viscosity of the system is obviously increased, and then quickly pouring the solution into a polytetrafluoroethylene mold, wherein in the step, the quick increase of the viscosity of the system represents that a polyhydroxy cross-linking agent reacts violently with isocyanate in the system, which is a key step for changing the whole system from a linear state to a cross-linking state.
And step three, volatilizing the solvent. Removing the solvent from the adhesive poured into the tetrafluoro plate in a fume hood or an oven to obtain a transparent foamless self-repairing cross-linking type energy-containing adhesive film material;
advantageous effects
A flowable type cross-linked polymer adhesive has the following advantages:
(1) high viscosity and flowability. At moderate temperature (90 ℃), the cross-linked polymer adhesive can be converted into a molten linear polymer fluid, and the solid components can be effectively prevented from settling in a propellant system, so that uniform propellant fuel can be prepared;
(2) the preparation process of the propellant is simplified. The adhesive and the solid filler are mixed, melted and injected at 80 ℃ and cooled to form the product without complex curing process;
(3) the mechanical property is excellent. The binder component can be crosslinked again in its linear network after cooling, thus improving the mechanical strength of the propellant. The mechanical strength of the common energetic adhesive is in the range of 0.5-1Mpa, but in the invention, the mechanical strength of the adhesive is enhanced by 2-5 times, and the compression resistance of the propellant can be greatly improved;
(5) the yield is high. In the preparation process of the adhesive, all raw materials are converted into products, and no by-products such as precipitates, gases, compounds and the like are generated;
(6) the raw materials are cheap and easy to obtain. The raw materials used are all industrially produced at present;
(8) the cycle can be continued. The adhesive prepared by the method can be recycled, the damaged material can be repaired by only slightly heating, and the obtained propellant can also be used for repairing cracks by the same method, so that the waste of energy materials is greatly reduced.
Drawings
FIG. 1 is a flow chart of the synthesis of a cross-linking type castable energetic polymeric binder;
FIG. 2 Infrared characterization of the product adhesive;
FIG. 3 stress-strain curves before and after adhesive repair;
FIG. 4 is a schematic representation of the high temperature flow of a cross-linked castable energetic polymeric binder;
FIG. 5 is a flow diagram of the preparation of a melt-cast propellant.
Detailed Description
The invention is further described with reference to the following figures and examples.
Example 1:
preparation of polyazide glycidyl ether (GAP) type fusible casting energy-containing high-molecular adhesive:
raw materials: 100 parts of polyazidyl glycidyl ether (GAP), 44.9 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 20.5 parts of dihydroxyethyl disulfide (HEDS), 1.2 parts of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 40 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced by castor oil, pentaerythritol, etc.; tetrahydrofuran may be replaced with dichloromethane, chloroform, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, etc.
The preparation method comprises the following steps:
first, prepolymerization. The polyaziridin glycidyl ether is firstly subjected to vacuum pumping treatment to remove water in the system and prevent interference with the reaction. Adding metered poly azide glycidyl ether into a three-neck flask, and adding N at a certain speed at 90 DEG C2Under the atmosphere, the stirring speed is controlled at 200 r.s-1Dropwise and slowly adding metered 4,4 '-dicyclohexylmethane diisocyanate dropwise, and then reacting for 4 hours under the action of a proper amount of catalyst (dibutyltin dilaurate), wherein in the process, hydroxyl in polyazidine glycidyl ether and isocyanato in 4,4' -dicyclohexylmethane diisocyanate completely react, namely blocking reaction.
And step two, chain scraping. Cooling the system to room temperature, adding metered chain extender dihydroxyethyl disulfide and solvent tetrahydrofuran to react for six hours, wherein in the process, the room temperature aims at slowing down the reaction activity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; and then dropwise adding the solution in which the trimethylolpropane is dissolved into a three-neck bottle, stirring until the viscosity of the system is obviously increased, and then quickly pouring the system into a polytetrafluoroethylene mold.
And thirdly, volatilizing the solvent. The adhesive poured into the tetrafluoro plate is put in a fume hood or an oven to remove the solvent, and the transparent foamless self-repairing crosslinking type energy-containing adhesive film material can be obtained
And (4) conclusion:
FIG. 1 is a flow chart of a cross-linking type fusible cast energetic polymer adhesive prepared by using polyazide glycidyl ether (GAP), dicyclohexylmethane diisocyanate (HMDI), dihydroxyethyl disulfide (HEDS) and Trimethylolpropane (TMP) as raw materials.
Similar polyazidyl glycidyl ethers may be exchanged for branched polyazidyl glycidyl ether (BGAP), 3-diazacycloxybutyl ring (BAMO), 3-azidooxybutyl ring (AZOX), 3-azidomethyl-3-methyloxybutyl ring (AAMO), polyglycidyl nitrate (PGN), poly (1, 3-oxapropyl) -bis (2, 2-dinitratomethyl) -1, 3-malonate (PBBP), etc.;
dicyclohexylmethane diisocyanate may be replaced with Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI), etc.;
dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.;
trimethylolpropane may be replaced with castor oil, pentaerythritol, etc.
FIG. 2 is an infrared diagram of a cross-linking type castable polymer binder prepared from poly azide glycidyl ether (GAP), dicyclohexylmethane diisocyanate (HMDI), dihydroxyethyl disulfide (HEDS) and Trimethylolpropane (TMP) as raw materials and a main raw material. At 2250cm-1Where represents an-NCO group, the peak position in the product disappeared, indicating that the HMDI had fully participated in the reaction, 3345cm-1And 1500cm-1Where (d) represents the peak of N-H stretching vibration and bending vibration in urethane at 1700cm-1Wherein represents C ═ 0cm in the carbamate-12100cm of the peak of stretching vibration-1Is a characteristic peak of-N3, 2850cm-1The vicinity is the symmetric and asymmetric stretching vibration peaks of C-H, indicating the successful preparation of the energetic binder containing urethane structures.
Fig. 3 is a stress-strain curve for the original and repaired splines. The original sample bar is subjected to stress of 5.3MPa and elongation of 780% when being broken, the broken stress of the restored sample bar is 4.8MPa and elongation of 680%, and restoration efficiency is eta (4.8/5.3) × 100% ═ 91% when being subjected to mechanical testing, wherein the notches with the depth of 1/2 are manufactured on the sample bar and the sample bar is restored for 6 hours at 80 ℃. For the energy-containing polyurethane elastomer, the mechanical property of the adhesive is obviously higher than that of the currently reported energy-containing material (generally 0.1-1Mpa), and the adhesive also has an excellent repairing effect, thereby laying a foundation for the preparation of the high-strength self-repairing propellant.
FIG. 4 is a schematic view of the high temperature flow of a cross-linked melt-castable energetic polymer binder at 80 deg.C, the cross-linked structure in the system is broken into segments that can flow and bond with each other to form a cross-linked network at room temperature.
TABLE 1 feed ratio of raw materials
Example 2:
preparation of branched polyazide glycidyl ether (BGAP) type fusible casting energetic polymer adhesive:
raw materials: 100 parts of branched polyazide glycidyl ether (BGAP), 45 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 21 parts of dihydroxyethyl disulfide (HEDS), 1.3 parts of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 35-50 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced by castor oil, pentaerythritol, etc.; tetrahydrofuran may be replaced with dichloromethane, chloroform, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, etc.
The preparation method comprises the following steps:
a one-step method: the branched polyaziridine glycidyl ether is firstly vacuumized to remove water in the system and prevent interference with the reaction. Adding metered poly azide glycidyl ether, 4' -dicyclohexyl methane diisocyanate, dihydroxyethyl disulfide and trimethylolpropane dissolved in tetrahydrofuran into a three-necked bottle, stirring at 25 ℃ for 1h, pouring into a tetrafluoro plate, putting into an oven at 80 ℃ for curing for 2 days, and preparing the branched poly azide glycidyl ether fusion-casting energy-containing high-molecular adhesive.
Example 3:
preparing a poly (3, 3-di-azomethionyl) oxetane (PBAMO) type fusible casting energy-containing high polymer adhesive:
raw materials: 100 parts of poly (3, 3-diazomethyloxybutylene) (PBAMO), 48 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 24 parts of dihydroxyethyl disulfide (HEDS), 1.1 parts of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 40 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced with castor oil, pentaerythritol, etc.
The preparation method comprises the following steps:
first, prepolymerization. The poly-3, 3-diazacycloxybutylene is firstly vacuumized to remove the water in the system and prevent the interference of the reaction. Adding the metered poly-3, 3-di-azidomethyloxybutylene into a three-necked flask, and adding N at a certain speed at 90 DEG C2Under the atmosphere, the stirring speed is controlled at 200 r.s-1Dropwise and slowly adding metered 4,4 '-dicyclohexylmethane diisocyanate dropwise, and then reacting for 4 hours under the action of a proper amount of catalyst (dibutyltin dilaurate), wherein in the process, hydroxyl in the poly-3, 3-diazacyclooxybutylene and isocyanato in the 4,4' -dicyclohexylmethane diisocyanate completely react, namely blocking reaction.
And step two, chain scraping. Cooling the system to room temperature, adding metered chain extender dihydroxyethyl disulfide and solvent tetrahydrofuran to react for six hours, wherein in the process, the room temperature aims at slowing down the reaction activity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; and then dropwise adding the solution in which the trimethylolpropane is dissolved into a three-neck bottle, stirring until the viscosity of the system is obviously increased, and then quickly pouring the system into a polytetrafluoroethylene mold.
And thirdly, volatilizing the solvent. The adhesive poured into the tetrafluoro plate is put in a fume hood or an oven to remove the solvent, and the transparent foamless self-repairing crosslinking type energy-containing adhesive film material can be obtained
Example 4:
preparation of poly 3-azidooxybutylene (PAZOX) type fusible cast energetic polymer adhesive:
raw materials: 100 parts of poly (3-azidooxybutylene) (PAZOX), 50 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 25 parts of dihydroxyethyl disulfide (HEDS), 1.6 parts of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 40 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced with castor oil, pentaerythritol, etc.
The preparation method comprises the following steps:
first, prepolymerization. The poly-3-azido oxybutylene firstly carries out vacuum pumping treatment to remove the water in the system and prevent the interference reaction. Adding metered poly-3-azidooxybutylene into a three-mouth bottle, controlling the stirring rate at 200 r.s < -1 > under the atmosphere of N2 at a certain speed at 90 ℃, dropwise and slowly adding metered 4,4 '-dicyclohexylmethane diisocyanate, and then reacting for 4 hours under the action of a proper amount of catalyst (dibutyltin dilaurate), wherein in the process, hydroxyl in the poly-3, 3-azidomethyloxybutylene and isocyanate in the 4,4' -dicyclohexylmethane diisocyanate completely react and are called blocking reaction.
And step two, chain scraping. Cooling the system to room temperature, adding metered chain extender dihydroxyethyl disulfide and solvent tetrahydrofuran to react for six hours, wherein in the process, the room temperature aims at slowing down the reaction activity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; and then dropwise adding the solution in which the trimethylolpropane is dissolved into a three-neck bottle, stirring until the viscosity of the system is obviously increased, and then quickly pouring the system into a polytetrafluoroethylene mold.
And thirdly, volatilizing the solvent. The adhesive poured into the tetrafluoro plate is put in a fume hood or an oven to remove the solvent, and the transparent foamless self-repairing crosslinking type energy-containing adhesive film material can be obtained
Example 5:
preparation of a poly (3-azidomethyl-3-methyloxybutylene) (PAAMO) based castable energetic polymer adhesive:
raw materials: 100 parts of poly (3-azidomethyl-3-methyloxybutylene) (PAAMO), 60 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 27 parts of dihydroxyethyl disulfide (HEDS), 1.4 parts of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 40 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced with castor oil, pentaerythritol, etc.
The preparation method comprises the following steps:
first, prepolymerization. The poly-3-azidomethyl-3-methyloxybutylene is firstly vacuumized to remove the moisture in the system and prevent the interference with the reaction. Adding the metered poly-3-azidomethyl-3-methyloxybutylene into a three-necked bottle, and adding N at a certain speed at 90 DEG C2Under the atmosphere, the stirring speed is controlled at 200 r.s-1Dropwise and slowly adding metered 4,4 '-dicyclohexylmethane diisocyanate, and reacting for 4 hours under the action of a proper amount of catalyst (dibutyltin dilaurate), wherein in the process, hydroxyl in poly (3, 3-diazacyclomethyloxybutylene) and 4,4' -dicyclohexylThe isocyanate group in the methane diisocyanate is completely reacted, and is called blocking reaction.
And step two, chain scraping. Cooling the system to room temperature, adding metered chain extender dihydroxyethyl disulfide and solvent tetrahydrofuran to react for six hours, wherein in the process, the room temperature aims at slowing down the reaction activity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; and then dropwise adding the solution in which the trimethylolpropane is dissolved into a three-neck bottle, stirring until the viscosity of the system is obviously increased, and then quickly pouring the system into a polytetrafluoroethylene mold.
And thirdly, volatilizing the solvent. The adhesive poured into the tetrafluoro plate is put in a fume hood or an oven to remove the solvent, and the transparent foamless self-repairing crosslinking type energy-containing adhesive film material can be obtained
Example 6:
preparation of a polyglycidyl nitrate (PGN) -based castable energetic polymeric binder:
raw materials: 100 parts of polyglycidyl nitrate (PGN), 53 parts of 4,4' -dicyclohexylmethane diisocyanate (HMDI), 23 parts of dihydroxyethyl disulfide (HEDS), 0.9 part of Trimethylolpropane (TMP), 0.4 part of catalyst (T12) and 40 parts of tetrahydrofuran.
Wherein 4,4' -dicyclohexylmethane diisocyanate can be replaced by toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, etc.; dihydroxyethyl disulfide may be replaced with dimethylol disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-aminophenyl) disulfide, etc.; trimethylolpropane may be replaced with castor oil, pentaerythritol, etc.
The preparation method comprises the following steps:
first, prepolymerization. The polyglycidyl nitrate is first vacuumized to remove water in the system and prevent interference with the reaction. Adding the measured polyglycidyl nitrate into a three-mouth bottle, and adding N at a certain speed at 90 DEG C2Under the atmosphere, the stirring speed is controlled at 200 r.s-1Slowly dropping the mixture dropwiseAdding a metered amount of 4,4 '-dicyclohexylmethane diisocyanate, and then reacting for 4 hours under the action of a proper amount of catalyst (dibutyltin dilaurate), wherein in the process, hydroxyl in poly (3, 3-diazacyclooxybutylene) and isocyanate in 4,4' -dicyclohexylmethane diisocyanate completely react, namely blocking reaction.
And step two, chain scraping. Cooling the system to room temperature, adding metered chain extender dihydroxyethyl disulfide and solvent tetrahydrofuran to react for six hours, wherein in the process, the room temperature aims at slowing down the reaction activity of the disulfide and the isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a polymer chain of the system, increase the collision probability of hydroxyl-OH and the isocyanic acid radical-NCO and improve the reaction efficiency; and then dropwise adding the solution in which the trimethylolpropane is dissolved into a three-neck bottle, stirring until the viscosity of the system is obviously increased, and then quickly pouring the system into a polytetrafluoroethylene mold.
And thirdly, volatilizing the solvent. The adhesive poured into the tetrafluoro plate is put in a fume hood or an oven to remove the solvent, and the transparent foamless self-repairing crosslinking type energy-containing adhesive film material can be obtained
Example 7:
preparing the fusible cast self-repairing propellant.
Raw materials: 14 parts of the prepared energy-containing self-repairing adhesive, 6 parts of plasticizer, 20 parts of aluminum powder, 50 parts of ammonium perchlorate and 10 parts of octogen.
The preparation method comprises the following steps:
FIG. 5 is a flow chart of preparation of a casting propellant, wherein 14 parts of prepared adhesive is firstly taken to be melted at 80 ℃, 6 parts of plasticizer (generally accounting for 1% -3% of the total mass of the system) is added to promote the fluidity of the system, then 20 parts of aluminum powder, 50 parts of ammonium perchlorate and 10 parts of octogen are added as solid fillers, and after being mixed and stirred uniformly, the mixture is cast into a mold under the action of external pressure, and the mold can be formed after cooling, so that the high-strength, high-energy and self-repairable solid propellant is prepared.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A cross-linking type fusible casting energetic polymer adhesive material is characterized in that: the method comprises the following steps: energetic polymer, diisocyanate, disulfide, cross-linking agent and catalyst; the solvent comprises: tetrahydrofuran, dichloromethane, trichloromethane, acetone, butanone, N-dimethylformamide and N, N-dimethylacetamide; the addition parts of the substances are as follows: energy-containing polymer: 100 parts of (A); diisocyanate: 20-65 parts of a solvent; disulfide: 10-35 parts; polyhydroxy crosslinking agent: 0.5-2 parts; 0.1-0.3 part of catalyst.
2. A cross-linked, castable, energetic polymeric binder material according to claim 1, wherein: the energy-containing polymer comprises: polyazidoglycidyl ether (GAP), branched polyglycidyl ether (BGAP), 3-diazacyclomethyloxetane (BAMO), 3-Azidooxybutylene (AZOX), 3-azidomethyl-3-methyloxetane (AAMO), polyglycidyl nitrate (PGN) or poly bis (1, 3-oxapropyl) -bis (2, 2-dinitriloylmethyl) -1, 3-malonate (PBBP).
3. A cross-linked, castable, energetic polymeric binder material according to claim 1, wherein: the diisocyanate comprises: dicyclohexylmethane diisocyanate (HMDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), Hexamethylene Diisocyanate (HDI) or Lysine Diisocyanate (LDI).
4. A cross-linked, castable, energetic polymeric binder material according to claim 1, wherein: the disulfide includes: dimethylol disulfide, dihydroxyethyl disulfide, dihydroxypropyl disulfide, bis (4-hydroxyphenyl) disulfide or bis (2-aminophenyl) disulfide.
5. A cross-linked, castable, energetic polymeric binder material according to claim 1, wherein: the crosslinking agent comprises: trimethylolpropane, castor oil or pentaerythritol.
6. A cross-linked, castable, energetic polymeric binder material according to claim 1, wherein: the catalyst comprises: dibutyltin dilaurate.
7. A process for preparing a cross-linked castable energetic polymeric binder material according to any one of claims 1 to 6, characterized in that: the method comprises the following steps:
step one, end sealing; dripping diisocyanate into the energetic polymer material after vacuum treatment under the protection of inert gas and stirring at 90 ℃; adding a catalyst, and fully reacting; obtaining a system;
step two, chain scraping; cooling the system obtained in the step one to room temperature, and then adding a chain extender disulfide and a solvent for reaction; at the moment, the room temperature aims at slowing down the reactivity of disulfide and isocyanic acid radical and preventing crosslinking, and the solvent is added to spread a macromolecular chain of a system, increase the probability of collision of hydroxyl-OH and isocyanic acid radical-NCO and improve the reaction efficiency; then dropwise adding the solution dissolved with the cross-linking agent into a container, stirring until the viscosity is obviously increased, and then quickly pouring into a polytetrafluoroethylene mold;
step three, volatilizing the solvent; the binder poured into the tetrafluoro plate is subjected to solvent removal in a fume hood or an oven to obtain a cross-linking type energy-soluble polymer binder material.
8. The method of claim 7, wherein: and step two, adding the chain extender disulfide and the solvent for reaction for six hours.
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