CN116003195A - Non-isocyanate curing system for solid propellant and solid propellant - Google Patents
Non-isocyanate curing system for solid propellant and solid propellant Download PDFInfo
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- CN116003195A CN116003195A CN202211568878.6A CN202211568878A CN116003195A CN 116003195 A CN116003195 A CN 116003195A CN 202211568878 A CN202211568878 A CN 202211568878A CN 116003195 A CN116003195 A CN 116003195A
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- solid propellant
- curing system
- epoxy resin
- propellant
- maleic anhydride
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- 239000012948 isocyanate Substances 0.000 title claims abstract description 47
- 239000004449 solid propellant Substances 0.000 title claims abstract description 45
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 9
- 230000001070 adhesive effect Effects 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 238000004132 cross linking Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 30
- 239000003921 oil Substances 0.000 claims description 29
- 239000003822 epoxy resin Substances 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- NPCUWXDZFXSRLT-UHFFFAOYSA-N chromium;2-ethylhexanoic acid Chemical compound [Cr].CCCCC(CC)C(O)=O NPCUWXDZFXSRLT-UHFFFAOYSA-N 0.000 claims description 17
- DRQFBCMQBWNTNV-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;trifluoroborane Chemical compound FB(F)F.OCCN(CCO)CCO DRQFBCMQBWNTNV-UHFFFAOYSA-N 0.000 claims description 16
- -1 3, 5-diisopropyl salicylic acid chromium Chemical compound 0.000 claims description 8
- 229920002943 EPDM rubber Polymers 0.000 claims description 8
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 229920003049 isoprene rubber Polymers 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920001971 elastomer Polymers 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 5
- 229920001910 maleic anhydride grafted polyolefin Polymers 0.000 claims description 5
- 239000005060 rubber Substances 0.000 claims description 5
- KUTKUWZIKYFNCD-UHFFFAOYSA-K [Cr+3].CC(C)c1cc(C(C)C)c(O)c(c1)C(O)=O.CC(C)c1cc(C(C)C)c([O-])c(c1)C(O)=O.CC(C)c1cc(C(C)C)c([O-])c(c1)C([O-])=O Chemical compound [Cr+3].CC(C)c1cc(C(C)C)c(O)c(c1)C(O)=O.CC(C)c1cc(C(C)C)c([O-])c(c1)C(O)=O.CC(C)c1cc(C(C)C)c([O-])c(c1)C([O-])=O KUTKUWZIKYFNCD-UHFFFAOYSA-K 0.000 claims description 4
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000003380 propellant Substances 0.000 abstract description 52
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 230000007613 environmental effect Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000007246 mechanism Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 23
- 238000009472 formulation Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- UZGLIIJVICEWHF-UHFFFAOYSA-N octogen Chemical compound [O-][N+](=O)N1CN([N+]([O-])=O)CN([N+]([O-])=O)CN([N+]([O-])=O)C1 UZGLIIJVICEWHF-UHFFFAOYSA-N 0.000 description 6
- 239000000028 HMX Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 125000004069 aziridinyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- YNKVVRHAQCDJQM-UHFFFAOYSA-P diazanium dinitrate Chemical compound [NH4+].[NH4+].[O-][N+]([O-])=O.[O-][N+]([O-])=O YNKVVRHAQCDJQM-UHFFFAOYSA-P 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
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Abstract
The invention discloses a non-isocyanate curing system for a solid propellant and the solid propellant, which are composed of the following substances in percentage by mass: 16.5 to 22.8 percent of adhesive, 68.2 to 76.5 percent of plasticizer, 3.7 to 7.5 percent of curing agent, 0.6 to 1.2 percent of crosslinking network regulator and 0.4 to 0.9 percent of curing accelerator. The curing reaction mechanism of the curing system is not influenced by moisture, and the influence of environmental humidity and raw material moisture on the technological performance, mechanical performance and structural integrity of the propellant can be reduced. In addition, the non-isocyanate curing system provided by the invention has the advantages of high reactivity, good compatibility with propellant components, excellent mechanical properties and the like, and can meet the technical requirements of weapon equipment on high reliability and strong environmental adaptability of the propellant.
Description
Technical Field
The invention belongs to the technical field of solid propellants, and relates to a non-isocyanate curing system for a solid propellant and the solid propellant.
Background
The solid propellant is a power source spring of strategic and tactical missile weapon equipment and directly determines the performance level of the missile weapon power system. With the change of battlefield environment and war form, higher technical requirements are put forward on the reliability of a weapon system, and the method has the important trend of higher environmental adaptability, more stable working performance and higher operation safety in the current and future solid propellant technical development.
The solid propellant is a composite material system composed of a high-energy oxidant, a metal fuel, a binder, a curing agent, a plasticizer and various functional materials. The polymer network structure formed by the adhesive and the curing agent is a basic skeleton of the solid propellant, and plays a decisive role in the processing performance, mechanical property and safety performance of the solid propellant. Of the active solid propellant curing systems, the most widely used are the hydroxyl/isocyanate curing systems, which are typically represented by HTPB, NEPE propellant systems. The reaction of hydroxyl and isocyanate has the advantages of mild process, no small molecule generation, excellent mechanical properties of the formed propellant, and the like, but isocyanate is sensitive to water and moisture, so that the isocyanate curing system has some problems. Firstly, isocyanate curing agent is easy to react with raw materials and moisture in air to generate carbon dioxide gas, so that propellant generates air holes and influences technological properties and mechanical properties; secondly, moisture can consume isocyanate components in a curing system, interfere curing reaction between hydroxyl and the isocyanate components, so that the mechanical properties of the propellant prepared in different humidity environments can be greatly fluctuated, and the stability and reliability of the performance are affected. In addition, for the novel high-energy propellant containing ADN, the application of ADN in the field of solid propellant is limited due to the poor compatibility of ADN with isocyanate. Therefore, designing a non-isocyanate curing system suitable for ADN-containing solid propellant formulations that is moisture insensitive and environmentally friendly is a very practical technical need in the field of solid propellants.
At present, the application of non-isocyanate curing systems at home and abroad is mature Ding Suo propellant, and the reaction principle is based on the reaction between carboxyl and epoxy or aziridine groups. Although the curing system is not affected by moisture, the mechanical property of the propellant is low, and the bulk viscosity of carboxyl-terminated polybutadiene is high, so that the solid content of the propellant is low to affect the improvement of the energy level of the propellant. In addition, the azide/alkynyl curing system and the nitrile oxide/alkenyl curing system have also made a certain research progress in preparing solid propellants by curing non-isocyanate, but all have the problem of insufficient mechanical properties of the propellants.
Disclosure of Invention
The invention aims to provide a non-isocyanate curing system for a solid propellant and the solid propellant, wherein the curing reaction mechanism of the curing system is not influenced by moisture, and the influence of environmental humidity and raw material moisture on the technological property, mechanical property and structural integrity of the propellant can be reduced. In addition, the non-isocyanate curing system provided by the invention has the advantages of high reactivity, good compatibility with propellant components, excellent mechanical properties and the like, and can meet the technical requirements of weapon equipment on high reliability and strong environmental adaptability of the propellant.
The technical scheme of the invention is as follows:
the non-isocyanate curing system for the solid propellant consists of the following substances in percentage by mass: 16.5 to 22.8 percent of adhesive, 68.2 to 76.5 percent of plasticizer, 3.7 to 7.5 percent of curing agent, 0.6 to 1.2 percent of crosslinking network regulator and 0.4 to 0.9 percent of curing accelerator.
Optionally, the adhesive is maleic anhydride grafted polyolefin rubber, the plasticizer is aliphatic hydrocarbon, the curing agent is difunctional or polyfunctional liquid epoxy resin, the crosslinking network regulator is trifunctional hydroxyl-containing liquid compound, and the curing accelerator is trivalent chromium complex.
Alternatively, the maleic anhydride grafted polyolefin rubber is selected from the group consisting of: at least one of maleic anhydride grafted ethylene propylene diene monomer rubber, maleic anhydride grafted butadiene rubber and maleic anhydride grafted isoprene rubber;
the aliphatic hydrocarbon is selected from the group consisting of: industrial white oil 1 # White industrial oil 2 # And technical white oil 3 # At least one of (a) and (b);
the difunctional or polyfunctional liquid epoxy resin is selected from the group consisting of: at least one of bisphenol a type epoxy resin E51, bisphenol a type epoxy resin E54, and bisphenol a type epoxy resin E44;
the trifunctional hydroxyl-containing liquid compound is selected from the group consisting of: at least one of trimethylolpropane, triethanolamine and triethanolamine boron trifluoride complex.
The trivalent chromium complex is selected from the group consisting of: chromium 2-ethylhexanoate and chromium 3, 5-diisopropylsalicylate.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: maleic anhydride grafted butadiene rubber 18.9%, industrial white oil 2 # 75.6%, bisphenol A epoxy resin E51.8%, triethanolamine boron trifluoride complex 0.9% and chromium 2-ethylhexanoate 0.8%.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: 20.9% of maleic anhydride grafted ethylene propylene diene monomer rubber, 73.1% of industrial white oil 2#, 1.0% of bisphenol A epoxy resin E544.2%, 1.0% of triethanolamine boron trifluoride complex and 0.8% of 2-chromium ethylhexanoate.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: 20.5% of maleic anhydride grafted isoprene rubber, 71.6% of industrial white oil 1#71.6%, 516.1% of bisphenol A type epoxy resin E, 1.0% of trimethylolpropane and 0.8% of 3, 5-diisopropyl salicylic acid chromium.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: 22.8% of maleic anhydride grafted butadiene rubber, 68.3% of industrial white oil 2#, 516.8% of bisphenol A epoxy resin E516.8%, 1.2% of triethanolamine boron trifluoride complex and 0.9% of chromium 2-ethylhexanoate.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: 17.0% of maleic anhydride grafted ethylene propylene diene monomer, 76.4% of industrial white oil 2#, 445.1% of bisphenol A epoxy resin E, 0.8% of triethanolamine and 0.7% of chromium 2-ethylhexanoate.
The non-isocyanate curing system for the solid propellant comprises the following components in percentage by mass: 16.7% of maleic anhydride grafted isoprene rubber, 75.2% of industrial white oil 3#, 446.6% of bisphenol A type epoxy resin E, 0.8% of triethanolamine boron trifluoride complex and 0.7% of 3, 5-diisopropyl chromium salicylate.
A solid propellant comprising a non-isocyanate curing system for a solid propellant according to any one of the present invention; the content of the non-isocyanate curing system for the solid propellant in the solid propellant is 15-20%.
Compared with the prior art, the invention has the following beneficial effects:
(1) The curing reaction process of the non-isocyanate curing system is not influenced by environmental humidity and raw material moisture, the influence of moisture on the propellant curing process and the mechanical property of the propellant can be eliminated, and the environment for charging does not need to be dehumidified under the condition that the environmental humidity is more than 50%, so that the environmental adaptability of propellant charging is greatly improved.
(2) The curing system has high curing reaction activity and controllable reaction rate; the invention adopts the high-activity chromium-based complex to replace the traditional tertiary amine and quaternary ammonium salt compound as the curing accelerator, greatly improves the curing reaction rate and the curing degree, and can solve the problem of unstable mechanical property of the propellant caused by the post-curing reaction of the adhesive; the curing system can realize wide-temperature-range curing at 30-70 ℃, can improve the safety of the propellant in the curing process, and can solve the problem of component compatibility caused by high-temperature curing.
(3) The curing system can solve the engineering application problem of the energy-containing material ADN with strong hygroscopicity. The traditional isocyanate curing agent has poor compatibility with ADN, and simultaneously, the ADN has strong hygroscopicity, and the side reaction of moisture and isocyanate is enhanced after moisture absorption, so that the ADN propellant has poor patentability.
Drawings
FIG. 1 is a photograph of the appearance of an ADN-containing propellant prepared from a non-isocyanate curing system of the present invention;
FIG. 2 is a photograph of the appearance of an ADN-containing propellant prepared from an isocyanate curing system of the prior art.
Detailed Description
The present invention will be further described in detail with reference to examples.
Abbreviations interpretation:
AP: ammonium perchlorate;
HMX: octogen (cyclotetramethylene tetranitramine);
ADN: ammonium dinitrate;
the non-isocyanate curing system of the present invention comprises an adhesive, a plasticizer, a curing agent, a crosslinked network modifier, and a curing accelerator. The mass percentage of each component in the curing system is calculated by taking the total mass of the curing system as 100 percent: 16.5 to 22.8 percent of adhesive, 68.2 to 76.5 percent of plasticizer, 3.7 to 7.5 percent of curing agent, 0.6 to 1.2 percent of crosslinking network regulator and 0.4 to 0.9 percent of curing accelerator.
The adhesive is maleic anhydride grafted polyolefin rubber, preferably one or a mixture of more of maleic anhydride grafted Ethylene Propylene Diene Monomer (EPDM) -G-MAH, maleic anhydride grafted butadiene rubber (BR-G-MAH) and maleic anhydride grafted isoprene rubber (IR-G-MAH);
the plasticizer is aliphatic hydrocarbon, preferably industrial white oil 1 # White industrial oil 2 # Or technical white oil 3 # One or a mixture of several of the above;
the curing agent is a liquid epoxy resin with two or more functionalities, preferably one or a mixture of bisphenol A type epoxy resin E51, bisphenol A type epoxy resin E54 and bisphenol A type epoxy resin E44;
the network regulator is a trifunctional hydroxyl-containing liquid compound, preferably one or a mixture of a plurality of trimethylolpropane, triethanolamine and triethanolamine boron trifluoride complex;
the curing accelerator is a trivalent chromium complex, preferably one of chromium 2-ethylhexanoate or chromium 3, 5-diisopropylsalicylate.
Chromium 2-ethylhexanoate is a complex of the formula:
a process for the preparation of chromium 2-ethylhexanoate, the process comprising the steps of:
(1) Adding 24g of sodium hydroxide and 100mL of distilled water into a three-necked flask, stirring and dissolving, adding 95g of 2-ethylhexanoic acid, and stirring and reacting for 30min to obtain colorless and transparent solution;
(2) 40g of chromium nitrate is dissolved in 100mL of distilled water, added into the colorless transparent solution obtained in the step (1) and stirred for reaction for 1h;
(3) Adding 100mL of n-hexane into the reaction mixture obtained in the step (2), and stirring for 10min;
(4) Transferring the solution obtained in the step (3) into a separating funnel, standing for layering, separating a water layer, neutralizing excessive 2-ethylhexanoic acid with a sodium hydroxide dilute solution, washing divalent metal ions with a sodium carbonate dilute solution, washing impurities such as sodium ions and nitrate ions with distilled water, and drying with anhydrous magnesium sulfate to constant weight;
(5) Evaporating n-hexane under reduced pressure to obtain a blue viscous substance;
(6) And (3) placing the blue sticky substance obtained in the step (5) into a ground triangular flask, heating the ground triangular flask to 180 ℃ in a constant temperature box, and keeping the constant temperature for 2 hours to obtain a dark green sticky substance, namely the chromium 2-ethylhexanoate.
The 3, 5-diisopropyl salicylic acid chromium is a complex with the following structural formula:
the preparation of chromium 3, 5-diisopropylsalicylate was carried out according to invention patent CN 1097487666. A.
The propellant prepared by the non-isocyanate curing system (such as example 3 of the invention) can solve the problem of propellant air holes caused by the compatibility of moisture and components, and the propellant prepared by the conventional isocyanate system has air hole defects; the propellant prepared by the non-isocyanate system has a continuous and compact internal structure and no air hole defect, and is shown in figures 1 and 2.
The following examples are given as preferred examples, and are mainly used for understanding the present invention, but the present invention is not limited to these examples. The mechanical property test is carried out according to GJB770B-2005 "explosive test method".
Example 1:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
| Component (A) | Content/wt.% |
| BR-G-MAH | 18.9 |
| Industrial white oil 2 # | 75.6 |
| Bisphenol A type epoxy resin E51 | 3.8 |
| Triethanolamine boron trifluoride complex | 0.9 |
| 2-Ethylhexanoic acid chromium | 0.8 |
Propellant formulation
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 168h, curing temperature is 50 ℃.
Mechanical properties of the propellant: maximum tensile strength at 20 ℃ is 0.71MPa, and maximum elongation is 51.5%; maximum elongation at 50 ℃ is 60.4%, and maximum elongation at-40 ℃ is 42.3%.
Example 2:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
| Component (A) | Content/wt.% |
| EPDM-G-MAH | 20.9 |
| Industrial white oil 2 # | 73.1 |
| Bisphenol A type epoxy resin E54 | 4.2 |
| Triethanolamine boron trifluoride complex | 1.0 |
| 2-Ethylhexanoic acid chromium | 0.8 |
Propellant formulation
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 144h, curing temperature is 60 ℃.
Mechanical properties of the propellant: the maximum tensile strength at 20 ℃ is 0.66MPa, and the maximum elongation is 57.3%; maximum elongation at 50 ℃ is 64.2%, and maximum elongation at-40 ℃ is 43.6%.
Example 3:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
| Component (A) | Content/wt.% |
| IR-G-MAH | 20.5 |
| Industrial white oil 1 # | 71.6 |
| Bisphenol A type epoxy resin E51 | 6.1 |
| Trimethylolpropane | 1.0 |
| 3, 5-Diisopropyl salicylic acid chromium | 0.8 |
Propellant formulation
| Component (A) | Content/wt.% |
| IR-G-MAH | 4.09 |
| Industrial white oil 1 # | 14.32 |
| Bisphenol A type epoxy resin E51 | 1.23 |
| Trimethylolpropane | 0.2 |
| 3, 5-Diisopropyl salicylic acid chromium | 0.16 |
| AP | 19.48 |
| HMX | 42.06 |
| Al | 18.46 |
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 120h, curing temperature is 70 ℃.
Mechanical properties of the propellant: the maximum tensile strength at 20 ℃ is 0.69MPa, and the maximum elongation is 53.2%; maximum elongation at 50 ℃ is 62.5%, and maximum elongation at-40 ℃ is 45.7%.
Example 4:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
| Component (A) | Content/wt.% |
| BR-G-MAH | 22.8 |
| Industrial white oil 2 # | 68.3 |
| Bisphenol A type epoxy resin E51 | 6.8 |
| Triethanolamine boron trifluoride complex | 1.2 |
| 2-Ethylhexanoic acid chromium | 0.9 |
Propellant formulation
| Component (A) | Content/wt.% |
| BR-G-MAH | 4.56 |
| Industrial white oil 2 # | 13.67 |
| Bisphenol A type epoxy resin E51 | 1.36 |
| Triethanolamine boron trifluoride complex | 0.23 |
| 2-Ethylhexanoic acid chromium | 0.18 |
| ADN | 15.67 |
| AP | 15.67 |
| HMX | 14.84 |
| Al | 33.82 |
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 336h, curing temperature is 30 ℃.
Mechanical properties of the propellant: the maximum tensile strength at 20 ℃ is 0.58MPa, and the maximum elongation is 68.3%; maximum elongation at 50 ℃ is 71.2 percent, and maximum elongation at-40 ℃ is 51.7 percent.
Example 5:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
Propellant formulation
| Component (A) | Content/wt.% |
| EPDM-G-MAH | 2.54 |
| Industrial white oil 2 # | 11.46 |
| Bisphenol A type epoxy resin E44 | 0.76 |
| Triethanolamine salt | 0.14 |
| 2-Ethylhexanoic acid chromium | 0.10 |
| ADN | 21.91 |
| AP | 15.77 |
| HMX | 34.18 |
| Al | 13.14 |
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 336h, curing temperature is 40 ℃.
Mechanical properties of the propellant: the maximum tensile strength at 20 ℃ is 0.62MPa, and the maximum elongation is 63.3%; 50% elongation at 50℃and 50.7% elongation at 40 ℃.
Example 6:
(1) The curing system and the propellant formulation (mass%) are implemented:
composition of curing system formula
| Component (A) | Content/wt.% |
| IR-G-MAH | 16.7 |
| Industrial white oil 3 # | 75.2 |
| Bisphenol A type epoxy resin E44 | 6.6 |
| Triethanolamine boron trifluoride complex | 0.8 |
| 3, 5-Diisopropyl salicylic acid chromium | 0.7 |
Propellant formulation
(2) Curing conditions and propellant mechanical Properties
Curing conditions: curing time is 120h, curing temperature is 70 ℃.
Mechanical properties of the propellant: the maximum tensile strength at 20 ℃ is 0.55MPa, and the maximum elongation is 62.3%; maximum elongation at 50 ℃ is 70.5%, and maximum elongation at-40 ℃ is 51.2%.
Sponge-like structure integral g-C3N4 composite material, preparation method and application
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (10)
1. The non-isocyanate curing system for the solid propellant is characterized by comprising the following substances in percentage by mass:
16.5 to 22.8 percent of adhesive, 68.2 to 76.5 percent of plasticizer, 3.7 to 7.5 percent of curing agent, 0.6 to 1.2 percent of crosslinking network regulator and 0.4 to 0.9 percent of curing accelerator.
2. The non-isocyanate curing system for a solid propellant of claim 1 wherein the binder is a maleic anhydride grafted polyolefin rubber, the plasticizer is an aliphatic hydrocarbon, the curing agent is a difunctional or polyfunctional liquid epoxy resin, the crosslinked network modifier is a trifunctional hydroxyl-containing liquid compound, and the curing accelerator is a trivalent chromium complex.
3. The non-isocyanate curing system for a solid propellant of claim 2 wherein the maleic anhydride grafted polyolefin rubber is selected from the group consisting of: at least one of maleic anhydride grafted ethylene propylene diene monomer rubber, maleic anhydride grafted butadiene rubber and maleic anhydride grafted isoprene rubber;
the aliphatic hydrocarbon is selected from the group consisting of: industrial white oil 1 # White industrial oil 2 # And technical white oil 3 # At least one of (a) and (b);
the difunctional or polyfunctional liquid epoxy resin is selected from the group consisting of: at least one of bisphenol a type epoxy resin E51, bisphenol a type epoxy resin E54, and bisphenol a type epoxy resin E44;
the trifunctional hydroxyl-containing liquid compound is selected from the group consisting of: at least one of trimethylolpropane, triethanolamine and triethanolamine boron trifluoride complex.
The trivalent chromium complex is selected from the group consisting of: chromium 2-ethylhexanoate and chromium 3, 5-diisopropylsalicylate.
4. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: maleic anhydride grafted butadiene rubber 18.9%, industrial white oil 2 # 75.6%, bisphenol A epoxy resin E51.8%, triethanolamine boron trifluoride complex 0.9% and chromium 2-ethylhexanoate 0.8%.
5. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: 20.9% of maleic anhydride grafted ethylene propylene diene monomer rubber, 73.1% of industrial white oil 2#, 1.0% of bisphenol A epoxy resin E544.2%, 1.0% of triethanolamine boron trifluoride complex and 0.8% of 2-chromium ethylhexanoate.
6. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: 20.5% of maleic anhydride grafted isoprene rubber, 71.6% of industrial white oil 1#71.6%, 516.1% of bisphenol A type epoxy resin E, 1.0% of trimethylolpropane and 0.8% of 3, 5-diisopropyl salicylic acid chromium.
7. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: 22.8% of maleic anhydride grafted butadiene rubber, 68.3% of industrial white oil 2#, 516.8% of bisphenol A epoxy resin E516.8%, 1.2% of triethanolamine boron trifluoride complex and 0.9% of chromium 2-ethylhexanoate.
8. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: 17.0% of maleic anhydride grafted ethylene propylene diene monomer, 76.4% of industrial white oil 2#, 445.1% of bisphenol A epoxy resin E, 0.8% of triethanolamine and 0.7% of chromium 2-ethylhexanoate.
9. The non-isocyanate curing system for the solid propellant is characterized by comprising the following components in percentage by mass: 16.7% of maleic anhydride grafted isoprene rubber, 75.2% of industrial white oil 3#, 446.6% of bisphenol A type epoxy resin E, 0.8% of triethanolamine boron trifluoride complex and 0.7% of 3, 5-diisopropyl chromium salicylate.
10. A solid propellant comprising the non-isocyanate curing system for a solid propellant according to any one of claims 1 to 9;
the content of the non-isocyanate curing system for the solid propellant in the solid propellant is 15-20%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211568878.6A CN116003195A (en) | 2022-12-08 | 2022-12-08 | Non-isocyanate curing system for solid propellant and solid propellant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211568878.6A CN116003195A (en) | 2022-12-08 | 2022-12-08 | Non-isocyanate curing system for solid propellant and solid propellant |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211568878.6A Pending CN116003195A (en) | 2022-12-08 | 2022-12-08 | Non-isocyanate curing system for solid propellant and solid propellant |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948698A (en) * | 1967-09-06 | 1976-04-06 | Hercules Incorporated | Solid propellant compositions having epoxy cured, carboxy-terminated rubber binder |
| CN107879868A (en) * | 2017-10-25 | 2018-04-06 | 湖北航天化学技术研究所 | A kind of nitrine class solid propellant and its preparation technology |
| CN109748766A (en) * | 2019-02-28 | 2019-05-14 | 湖北航天化学技术研究所 | A kind of curing system and solid propellant and preparation method containing the curing system |
-
2022
- 2022-12-08 CN CN202211568878.6A patent/CN116003195A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3948698A (en) * | 1967-09-06 | 1976-04-06 | Hercules Incorporated | Solid propellant compositions having epoxy cured, carboxy-terminated rubber binder |
| CN107879868A (en) * | 2017-10-25 | 2018-04-06 | 湖北航天化学技术研究所 | A kind of nitrine class solid propellant and its preparation technology |
| CN109748766A (en) * | 2019-02-28 | 2019-05-14 | 湖北航天化学技术研究所 | A kind of curing system and solid propellant and preparation method containing the curing system |
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