CN114105718B - Coated fine-grained ammonium perchlorate and preparation method and application thereof - Google Patents
Coated fine-grained ammonium perchlorate and preparation method and application thereof Download PDFInfo
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- CN114105718B CN114105718B CN202111580849.7A CN202111580849A CN114105718B CN 114105718 B CN114105718 B CN 114105718B CN 202111580849 A CN202111580849 A CN 202111580849A CN 114105718 B CN114105718 B CN 114105718B
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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
- C06B23/005—Desensitisers, phlegmatisers
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0083—Treatment of solid structures, e.g. for coating or impregnating with a modifier
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B31/00—Compositions containing an inorganic nitrogen-oxygen salt
- C06B31/28—Compositions containing an inorganic nitrogen-oxygen salt the salt being ammonium nitrate
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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
- C06B45/18—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component
- C06B45/30—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component
- C06B45/32—Compositions or products which are defined by structure or arrangement of component of product comprising a coated component the component base containing an inorganic explosive or an inorganic thermic component the coating containing an organic compound
Abstract
The invention discloses coated fine-grained ammonium perchlorate and a preparation method and application thereof, and the coated fine-grained ammonium perchlorate is a core-shell structure formed by the fine-grained ammonium perchlorate and a bonded phase-change coating agent coated on the surface of the fine-grained ammonium perchlorate, wherein the bonded phase-change coating agent has a structural formula
Wherein: r 1 ＝‑CH 3 or-H, R 2 An aliphatic group, an alicyclic group or an aromatic group, wherein n is an integer between 18 and 34; the fine-grained ammonium perchlorate is particles with the average grain size of 2-10 mu m; the coated fine-grained ammonium perchlorate has the characteristics of low sensitivity and strong interface action due to the molecular structure of the bonding type phase-change coating agent and the combination mode of the bonding type phase-change coating agent and has good application prospect in a high-combustion-rate butylated hydroxytoluene propellant.
Description
Technical Field
The invention relates to the technical field of preparation of composite energetic materials, in particular to coated fine-grained ammonium perchlorate and a preparation method and application thereof.
Background
Ammonium Perchlorate (AP) as an oxidant has the characteristics of high density and high available oxygen content, is widely applied to the formulas of composite energetic materials such as solid propellants, mixed explosives, pyrotechnic agents and the like, has the content of 60-80 percent or more, and has direct influence on the combustion performance, the process performance, the mechanical property, the safety performance and the like of the energetic materials.
In the research of the composite solid propellant, the burning rate of the solid propellant can be effectively improved by reducing the particle size of AP, and the burning efficiency of aluminum powder in the propellant can be improved through reasonable grading of coarse, medium and fine particle size AP, so that the introduction of the fine particle size AP realizes the controllable regulation and design of the burning rate and the burning efficiency of the composite solid propellant to a certain extent, and provides effective technical support for the development of a high-performance solid rocket engine.
However, research shows that (such as the explosive and explosive science, 2006, 29 (6): 27-29; initiating explosive devices, 2007, 5: 16-19; solid rocket technology, 2015, 38 (1): 95-97) as the particle size is reduced, the critical electron excitation energy for decomposition of AP is reduced, and the impact sensitivity and the friction sensitivity of the AP are improved. In the process of developing a propellant formula, the addition of fine-grained AP (granularity is less than 10 mu m) can cause the mechanical sensitivity (mainly impact sensitivity and friction sensitivity) of propellant slurry and cured blocks to be sharply improved, so that the danger of the propellant preparation process (mixing, curing, demolding and shaping) is greatly increased, and the safety of a solid propulsion system of a weapon and the safety of the whole combat platform are reduced.
Therefore, research and development of low-sensitivity (insensitive) fine-particle-size AP are one of the key problems that must be solved for developing high-performance and low-risk solid propellants.
In order to solve the problems, domestic and foreign scholars carry out a series of researches to reduce the sensitivity of the fine-grained AP, wherein the coating sensitivity reduction treatment technology has certain advantages. In the case of Aucklandia, et al (blasting apparatus, 2015,43(3):9-13), octadecylamine was used as a coating agent to coat ultrafine AP prepared by jet milling, and the results showed that the mechanical sensitivity of coated AP particles was greatly reduced, and the higher the amount of the coating agent used, the lower the mechanical sensitivity of AP, but the thermal decomposition of AP was adversely affected by the coating agent. Mehilal et al (Propellant, Explositives, Pyrotechnics,2009,34(6): 526-. Plum bin et al (energetic materials, 2014,22(6):792-797) studied the coating of AP with paraffin and Thermoplastic Polyurethane (TPU), and found that the coating desensitizing effect of paraffin or paraffin/TPU composites was superior to that of TPU. The analysis shows that the paraffin substance is easy to absorb heat and melt, the phase change effect is helpful for reducing the heat accumulation in the AP crystal, thereby reducing the probability of hot spot generation, and meanwhile, the coating layer of the wax can also obstruct the heat transmission, thereby reducing the probability of hot spot transmission; the TPU only has a certain buffering and energy absorbing function and lacks the lubricating and friction reducing functions of paraffin. The AP is coated by DOP and paraffin respectively (initiating explosive devices, 2013,6:39-41) in south China sea and the like, and the results show that DOP increases the sensitivity of the AP, and the paraffin can effectively reduce the impact sensitivity of AP particles, so that the coating material with the characteristics of heat absorption and heat insulation is considered to be selected for AP reduction induction. The research shows that the mechanical sensitivity of the fine-grained AP can be effectively reduced by selecting a proper material to coat the fine-grained AP, so that the safety of the formula of the composite energetic material is improved; among common coating materials, the effect of reducing the AP sensitivity of paraffin or a composite coating material containing the paraffin through phase change is obvious, which is consistent with the results of reducing the AP sensitivity of Guo Yong (CN 108456124A, 2018), Singh (US 8216404,2012) and other people in nitramine explosives (RDX, HMX, CL-20) and other energetic materials.
However, paraffin is a nonpolar molecule and has a small surface tension (explosion and impact, 2003,23(2): 169-172); and the surface of the AP particle is a polar surface, and the surface tension is large (initiating explosive device, 2013,6: 39-41). Although paraffin can physically adsorb and wet the surfaces of AP particles, the interfacial tension is large because the polar components of the surface tension of the paraffin and the AP particles are not matched, the interfacial bonding energy is low, and the bonding performance is poor. The weak interface is easy to cause that when the coated AP is subjected to strong stirring, pressure pressing and mechanical shearing in the later propellant forming processing process, the coating layer falls off and the sense reduction effect fails. In order to improve the interface problem, attempts have been made by yankee et al (CN 105152823a,2015) to first modify the surface of fine AP with a bonding agent, then coat it with a functional carbon material, and finally further treat the particles with paraffin wax to obtain low-sensitivity ultra-fine AP. Although the research indirectly reduces the interfacial tension by introducing the bonding agent as the interface transition layer and obtains a certain sense reduction effect, the essence of weak physical acting force between the coating material and the bonding agent transition layer is not changed, and the stable existence and effective action of the coating layer in the later application process of the coated superfine AP cannot be ensured.
Therefore, how to select a proper coating agent to coat the fine-grained AP improves the action strength of the coating agent and the interface of the fine-grained AP on the premise of keeping the excellent sensitivity reducing effect, and is still one of the important directions for the sensitivity reducing research of the fine-grained AP.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provides coated fine-grained ammonium perchlorate and a preparation method and application thereof, wherein the fine-grained AP is coated by a bonding type phase-change coating agent which simultaneously comprises an aziridine ring bonding unit and a long-chain alkyl unit, and in the coating process: the bonding type phase change coating agent is firstly adsorbed to the surface of AP particles through the hydrogen bond action between polar groups such as carbamate groups and ester groups in molecules and ammonium groups and perchlorate groups on the surface of AP, then aziridine rings in the molecules generate ring-opening self-polymerization under the catalysis of the weakly acidic surface of the AP, self-polymerization products form a high-modulus coating shell layer on the surface of the fine-grained AP particles, and long-chain alkyl phase change units are tightly distributed on the surface of the coating shell layer under the action of chemical bonding, namely, the purposes of bonding coating and melting heat absorption and sense reduction are simultaneously achieved by adopting one compound. The coated fine-grained AP is used in the components of the high-burning-rate composite solid propellant, so that the obtained propellant has high burning rate and low risk.
The conception of the invention is as follows: aziridine compounds such as MAPO, HX-752, HX-868, HX-874 and TAZ are high-efficiency bonding agents for AP particles in the solid propellant; the bonding mechanism is that molecules of a bonding agent are adsorbed on the surface of AP particles under the action force of hydrogen bonds and other molecules, then aziridine rings are subjected to ring opening autopolymerization under the catalytic action of weak acidity of AP, a high-modulus polymer shell layer is formed on the surface of the particles, and the adhesion of the AP particles and an adhesive curing system is improved, so that the purposes of interface reinforcement and prevention of 'moisture removal' are achieved. Therefore, the paraffin phase-change material (mainly long-chain alkyl alcohol) containing functional groups such as hydroxyl groups is bonded to aziridine bonding agent molecules (mainly hydroxylated TAZ and homologs thereof) containing the functional groups such as the hydroxyl groups through chemical reaction to obtain the bonding type phase-change coating agent, the coating agent can form a high-modulus shell layer on the surface of AP through ring-opening self-polymerization, has the function of melting phase-change heat absorption, and achieves the purposes of interface enhancement and high-efficiency sense reduction.
In order to achieve the technical effects, the invention adopts the following technical scheme: the coated fine-grained ammonium perchlorate is a core-shell structure formed by the fine-grained ammonium perchlorate and a bonding type phase change coating agent coated on the surface of the fine-grained ammonium perchlorate, and the structural formula of the bonding type phase change coating agent is shown as (I):
wherein R is 1 ＝-CH 3 or-H, R 2 An aliphatic group, an alicyclic group or an aromatic group, wherein n is an integer between 18 and 34; the average particle size of the fine-particle ammonium perchlorate is 2-10 mu m; the mass percentage of the bonded phase change coating agent in the coated fine-grained ammonium perchlorate is 0.5 to 3.0 percent; impact sensitivity of the coated fine-grained ammonium perchlorate0 to 8 percent and 0 to 12 percent of friction sensitivity.
The invention provides a synthesis method of the bonding type phase change coating agent, which comprises the following steps:
s1, dissolving bifunctional isocyanate in an anhydrous organic solvent at room temperature, after the whole reaction system is purged with nitrogen for 30min, slowly dropwise adding an anhydrous organic solution in which long-chain alkyl alcohol is dissolved into the reaction system, slowly heating the reaction system to 60-80 ℃, reacting for 8-12 h, cooling the system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, then pouring the reaction mixed solution into acetonitrile for reverse precipitation, and collecting the precipitate to obtain an intermediate product isocyanate modified long-chain alkyl alcohol.
S2, dissolving aziridine bonding agent molecules containing hydroxyl in an anhydrous organic solvent at room temperature, after purging the whole reaction system with nitrogen for 10-30 min, slowly dropwise adding an organic solution in which an intermediate product is dissolved into the reaction system, slowly heating the reaction system to 60-80 ℃, reacting for 8-12 h, cooling the reaction system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, pouring the reaction mixed solution into acetonitrile for reverse precipitation, collecting precipitates, and drying to obtain the bonding type phase change coating agent.
Further, in the step S1, the bifunctional isocyanate is one of common aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate; the aliphatic diisocyanate is one of hexamethylene diisocyanate and 2,2, 4-trimethylhexane diisocyanate; the alicyclic diisocyanate is one of methyl cyclohexylidene diisocyanate, dicyclohexyl methylene diisocyanate and isophorone diisocyanate; the aromatic diisocyanate is one of diphenylmethane 4, 4' -diisocyanate and toluene diisocyanate;
further, in the step S1, the anhydrous organic solvent is one of methyl acetate, ethyl acetate, butyl acetate, chloroform, dichloroethane, and dioxane having a water content of less than 500 ppm;
further, in the step S1, the number of carbon atoms in the long-chain alkyl alcohol is 18 to 34; the ratio of the total amount of hydroxyl in the long-chain alkyl alcohol to the total amount of isocyanate in the bifunctional isocyanate is 1: 2;
further, in the step S2, the aziridine-based bonding agent molecule D containing a hydroxyl group is one of pentaerythritol-tris (3-aziridinyl) propionate and pentaerythritol-tris [3- (2-methylaziridinyl) ] propionate; the anhydrous organic solvent was the same as in S1.
The invention also provides a preparation method for coating the fine-grained AP by using the bonding type phase change coating agent, which comprises the following steps:
s3, adding the fine-grained AP into an organic solvent at room temperature, and performing ultrasonic dispersion for at least 30min to obtain an AP dispersion liquid; dissolving a bonding type phase change coating agent by using ethyl acetate to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 40-60 ℃ under the stirring condition, reacting for 2-4 h, cooling the system to room temperature after the reaction is finished, finally removing the organic solvent and the ethyl acetate through reduced pressure distillation, and drying to obtain the coated fine-grained AP.
Further, in the step S3, the organic solvent is one of n-hexane, n-heptane, cyclohexane, benzene, toluene, and xylene; the mass ratio of AP to the organic solvent in the AP dispersion liquid is 1: 5-1: 10;
further, in the step S3, the mass ratio of the bonding type phase change coating agent to the fine-grained AP is 0.5:100 to 3: 100.
The invention also provides a high-burning-rate and low-risk solid propellant, which comprises the fine-grained AP coated by the bonding type phase change coating agent, and the solid propellant also comprises the following components: metal powder, adhesive, plasticizer, burning rate catalyst, curing agent and technological assistant.
The mass percentage of fine-grained AP coated by the bonding type phase change coating agent in the high-burning-rate and low-risk solid propellant is as follows: 35.00 percent.
The invention specifically provides a high-burning-rate low-risk solid propellant which comprises the following components in percentage by mass: medium-particle size AP: 35.00 percent; fine particle size AP coated with a bonded phase change coating agent: 35.00 percent; aluminum powder: 15.00 percent; hydroxyl-terminated polybutadiene: 6.30-8.30%; dioctyl sebacate: 3.25-4.10%; toluene diisocyanate: 0.35 to 0.50 percent; a burning rate catalyst: 2.00-5.00%; and (3) process auxiliary agents: 0.10 percent.
According to the technical scheme, firstly, bifunctional isocyanate and polyurethane of long-chain alkyl alcohol react to modify a functional group of the long-chain alkyl alcohol into an isocyanate group, and then the long-chain alkyl group is bonded to an aziridine bonding agent molecule through the polyurethane reaction to obtain a bonding type phase change coating agent, wherein three aziridine rings are bonding units and the long-chain alkyl group is a phase change unit in the bonding type phase change coating agent. In the process of coating the fine-grained AP, a bonded phase-change coating agent is firstly adsorbed to the surface of AP particles through the hydrogen bond action between polar groups such as carbamate groups and ester groups in molecules and ammonium groups and perchlorate groups on the surface of the AP, then, an aziridine ring in the molecules generates ring-opening self-polymerization under the catalysis of the weakly acidic surface of the AP, a high-modulus coating shell is formed on the surface of the fine-grained AP particles by self-polymerization products, and long-chain alkyl phase-change units are tightly distributed on the surface of the coating shell under the action of chemical bonding, so that a compound has the functions of bonding coating and melting heat absorption and sense reduction. Then a certain amount of bonding type phase change coating agent is coated on the surface of the fine-grained AP through a coating process to form the product of the invention, and the surface of the fine-grained AP is effectively coated by controlling the quantity ratio of the coating object to the coated object and the coating process, so that the purposes of reducing the sensitivity of the fine-grained AP and enhancing the coating interface acting force are achieved.
Compared with the prior art, the invention has the advantages that:
1) the coating agent for coating the fine-grained AP is a coating agent with a special structure, and is obtained by bonding long-chain alkyl onto aziridine bonding agent molecules (hydroxylated TAZ and homologues thereof) through polyurethane reaction of two-step isocyanic acid radicals and hydroxyl groups to form a coated fine-grained AP, wherein the molecular structure of the coating agent can form a high-modulus coating shell layer through self-polymerization of an aziridine ring on the surface of the AP on one hand, and can reduce heat accumulation in an AP crystal through melting phase change of the long-chain alkyl on the other hand, so that the probability of hot spot generation is reduced, the propagation of heat is hindered, the probability of hot spot propagation is reduced, and finally the decomposition ignition reaction of the AP is inhibited.
2) Meanwhile, due to the structure and usage amount design of the coating agent, the phase change unit on the surface of the obtained coating shell layer and the coating shell layer are in a chemical bonding effect, so that the interface effect and stability among the phase change unit, the coating shell layer and the fine-grained AP are enhanced, the problem of failure of the sense reduction effect caused by falling of the coating layer due to shearing, friction and extrusion in the preparation process of the solid propellant can be relieved to a certain extent, and the technology is used for solving the problem of a weak interface between the paraffin coating agent and the AP from the molecular layer surface.
3) The bonding type phase change coating agent used in the invention has a melting peak temperature of 41.9-58.6 ℃ and a melting enthalpy of 74.4-168.5J/g; the impact sensitivity test (10kg drop weight, 25cm, 50mg sample) and the friction sensitivity test (3.92MPa, 90-degree swing angle, 20mg sample) are carried out on the coated fine-grained AP by adopting a GJB 772A-97601.1 method, the impact sensitivity is reduced to 0% -8%, the friction sensitivity is reduced to 0% -12%, the characteristic of low sensitivity is shown, and the safety performance is excellent.
4) The coated fine-grained ammonium perchlorate is applied to a high-burning-rate butylated hydroxytoluene propellant, the burning rate of the propellant under 6.86MPa is tested by adopting a GJB 770B-2005706.2 method, the mechanical sensitivity of the propellant is tested by adopting a GJB 772A-97601.1 method and a 602.1 method, the high burning rate of the propellant is basically kept unchanged, the impact sensitivity is reduced from 76-92% to 28-48%, the friction sensitivity is reduced from 84-96% to 32-48%, and the requirements of the high burning rate and low-risk propellant on the mechanical sensitivity are met.
The preparation method is simple, the reaction condition is mild, the reproducibility is good, and the universality is strong.
Drawings
For a clearer explanation of the embodiments or technical solutions in the prior art of the present application, the drawings used in the description of the embodiments or prior art will be briefly described below, it is obvious that the drawings in the following description are only references to the embodiments in the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows a DSC plot of a bonded phase change capping agent according to example 1 of the present invention;
fig. 2 shows an SEM image of a fine-grained AP in example 1 according to the present invention;
fig. 3 shows an SEM image of a fine-grained AP coated with a bonded phase change capping agent according to example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments used by those skilled in the art without any creative effort belong to the protection scope of the present invention.
Example 1
The preparation process of the bonding type phase change coating agent comprises the following steps:
the preparation method of the bonding type phase change coating agent comprises the following steps:
at room temperature, dissolving 10.0g of hexamethylene diisocyanate A in anhydrous ethyl acetate in a three-neck flask, installing a reflux condenser tube, after the whole reaction system is purged with nitrogen for 30min, slowly dropwise adding an anhydrous ethyl acetate solution in which 41.7g of n-tetradecanol B is dissolved into the reaction system, slowly heating the reaction system to 80 ℃, reacting for 8h, cooling the system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, pouring the reaction mixed solution into acetonitrile for carrying out reverse precipitation, and collecting precipitates to obtain an intermediate product C of the isocyanate modified long-chain alkyl alcohol.
At room temperature, 10.0g of pentaerythritol-tris (3-aziridinyl) propionate molecule D is dissolved in an anhydrous ethyl acetate solvent in a three-neck flask, a reflux condenser tube is installed, after the whole reaction system is purged with nitrogen for 30min, a solution in which 14.3g of an intermediate product C is dissolved is slowly dripped into the reaction system, the reaction system is slowly heated to 80 ℃, the reaction is carried out for 8h, the system is cooled to room temperature after the reaction is finished, the reaction mixed solution is decompressed, rotary evaporated and concentrated, then poured into acetonitrile for reverse precipitation, the precipitate is collected and dried, and the bonding type phase change coating agent is obtained, wherein the yield is 82.0%.
Identifying the structure of the bonding type phase change coating agent:
FT-IR，v max (cm -1 ): 3302. 1538-NH-of-NH-COO-, 3042-CH of an aziridine ring 2 -)，2918、2850、1463、1370(-CH 3 、-CH 2 -), 1734 (C ═ O in (-COO-), 1725 (C ═ O in free-NH-COO-), 1701 (C ═ O in hydrogen bonded-NH-COO-), 1262, and 1065 (C — O-C-) in (-COO-).
The DSC curve of the bonding type phase-change coating agent of the embodiment is shown in figure 1, the melting peak temperature is 58.6 ℃, and the melting enthalpy is 168.5J/g.
The above data indicate that the synthesized compound is a bonded phase change capping agent.
A coated fine-grained AP is prepared by the following steps:
at room temperature, adding 10.0g of fine-grained AP with the average grain size of 2 mu m into 100.0g of n-hexane, and performing ultrasonic dispersion for 30min to obtain AP dispersion liquid; dissolving 0.3g of the bonding type phase change coating agent by using ethyl acetate to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 60 ℃ under the stirring condition, reacting for 2 hours, cooling the system to room temperature after the reaction is finished, finally removing n-hexane and ethyl acetate through reduced pressure distillation, and drying to obtain the coated fine-grained AP.
In the present example, the SEM of the fine particle size AP is shown in fig. 2, and the particles have irregular shapes and sharp profile edges; the SEM of the coated fine-grained AP shows that the particle profile is rounded as shown in fig. 3. The mechanical sensitivity test result shows that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 0%, and the friction sensitivity is 0%.
Example 2
The preparation process of the bonding type phase change coating agent comprises the following steps:
the preparation method of the bonding type phase change coating agent comprises the following steps:
dissolving 10.0g of isophorone diisocyanate A in anhydrous dichloroethane in a three-neck flask at room temperature, installing a reflux condenser tube, purging the whole reaction system with nitrogen for 30min, slowly dropwise adding the anhydrous dichloroethane solution in which 17.2g of n-hexacosanol B is dissolved into the reaction system, slowly heating the reaction system to 70 ℃, reacting for 10h, cooling the system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, pouring the reaction mixed solution into acetonitrile for reverse precipitation, and collecting precipitates to obtain an intermediate product C of the isocyanate modified long-chain alkyl alcohol.
At room temperature, 10.0g of pentaerythritol-tris (3-aziridinyl) propionate molecule D is dissolved in an anhydrous dichloroethane solvent in a three-neck flask, a reflux condenser tube is installed, after the whole reaction system is purged with nitrogen for 30min, a solution in which 14.1g of intermediate product C is dissolved is slowly dripped into the reaction system, the reaction system is slowly heated to 70 ℃, the reaction system is reacted for 10h, the system is cooled to room temperature after the reaction is finished, the reaction mixed solution is decompressed, rotary evaporated and concentrated, poured into acetonitrile for reverse precipitation, the precipitate is collected and dried to obtain the bonding type phase change coating agent, and the yield is 85.1%.
Identifying the structure of the bonding type phase change coating agent:
FT-IR，v max (cm -1 ): 3301. 1539-NH-of-NH-COO-, 3043, -CH of aziridine ring 2 -)，2917、2849、1463、1371(-CH 3 、-CH 2 -), 1732(-C ═ O in COO-), 1721 (free-C ═ O in-NH-COO-), 1700 (hydrogen bonded-C ═ O in-NH-COO-), 1254, 1066 (-C-O-C in COO-).
The peak melting temperature was 51.3 ℃ and the enthalpy of fusion was 107.7J/g.
The above data indicate that the synthesized compound is a bonded phase change capping agent.
A coated fine-grained AP is prepared by the following steps:
at room temperature, adding 10.0g of fine grain AP with the average grain diameter of 2 mu m into 70.0g of cyclohexane, and performing ultrasonic dispersion for 30min to obtain AP dispersion liquid; dissolving 0.3g of bonding type phase change coating agent by cyclohexane to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 50 ℃ under the stirring condition, reacting for 3 hours, cooling the system to room temperature after the reaction is finished, finally removing cyclohexane and ethyl acetate by reduced pressure distillation, and drying to obtain the coated fine-grained AP.
The mechanical sensitivity test result shows that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 0%, and the friction sensitivity is 4%.
Example 3
The preparation process of the bonding type phase change coating agent comprises the following steps:
the preparation method of the bonding type phase change coating agent comprises the following steps:
at room temperature, 10.0g of toluene diisocyanate A is dissolved in anhydrous dioxane in a three-neck flask, a reflux condenser tube is installed, after the whole reaction system is purged with nitrogen for 30min, anhydrous dioxane solution in which 15.5g of n-octadecyl alcohol B is dissolved is slowly dripped into the reaction system, the reaction system is slowly heated to 60 ℃ for reaction for 12h, the system is cooled to room temperature after the reaction is finished, the reaction mixed solution is decompressed, spirally steamed and concentrated and poured into acetonitrile for reverse precipitation, and precipitates are collected to obtain an intermediate product C of isocyanate group modified long-chain alkyl alcohol.
At room temperature, 10.0g of pentaerythritol-tris [3- (2-methylaziridinyl) ] propionate molecule D is dissolved in an anhydrous dioxane solvent in a three-neck flask, a reflux condenser tube is arranged, after the whole reaction system is purged with nitrogen for 30min, a solution in which 10.6g of intermediate product C is dissolved is slowly dripped into the reaction system, the reaction system is slowly heated to 60 ℃ and reacts for 12h, the system is cooled to room temperature after the reaction is finished, reaction mixed liquid is decompressed, rotary evaporated and concentrated and then poured into acetonitrile for reverse precipitation, and precipitates are collected and dried to obtain the bonding type phase change coating agent, wherein the yield is 89.4%.
Identifying the structure of the bonding type phase change coating agent:
FT-IR，v max (cm -1 ): 3299. 1537 (-NH-of-NH-COO-), 3045 (-CH in the aziridine ring) 2 -)，2919、2845、1468、1370(-CH 3 、-CH 2 -), 1729(-C ═ O in COO-), 1720 (free-C ═ O in-NH-COO-), 1698 (C ═ O in hydrogen bonded-NH-COO-), 1600 (benzene ring), 1250, 1056 (-C-O-C in COO-).
The peak melting temperature was 41.9 ℃ and the enthalpy of fusion was 74.4J/g.
The above data indicate that the synthesized compound is a bonded phase change capping agent.
A coated fine-grained AP is prepared by the following steps:
at room temperature, adding 10.0g of fine-grained AP with the average grain size of 2 mu m into 50.0g of toluene, and performing ultrasonic dispersion for 30min to obtain AP dispersion liquid; dissolving 0.3g of bonding type phase change coating agent by using toluene to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 40 ℃ under the stirring condition, reacting for 4 hours, cooling the system to room temperature after the reaction is finished, finally removing toluene and ethyl acetate through reduced pressure distillation, and drying to obtain coated fine-grained AP.
The mechanical sensitivity test result shows that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 4%, and the friction sensitivity is 4%.
Example 4
The preparation and application of the bonding type phase change coating agent in this embodiment are the same as those in embodiment 1, and the only difference is that the coating agent solution prepared in this embodiment contains 0.2g of the bonding type phase change coating agent.
The mechanical sensitivity test results show that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 4%, and the friction sensitivity is 8%.
Example 5
The preparation and application of the bonding type phase change coating agent in this example are the same as those in example 1, and the only difference is that the coating agent solution prepared in this example contains 0.05g of the bonding type phase change coating agent.
The mechanical sensitivity test results show that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 8%, and the friction sensitivity is 12%.
Example 6
The preparation and application of the bonding type phase change coating agent in this embodiment are the same as those in embodiment 1, and the only difference is that the average particle size of the fine particle size AP in this embodiment is 7 μm.
The mechanical sensitivity test result shows that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 0%, and the friction sensitivity is 0%.
Example 7
The preparation and application of the bonding type phase change coating agent in this embodiment are the same as those in embodiment 1, and the only difference is that the average particle size of the fine particle size AP in this embodiment is 10 μm.
The mechanical sensitivity test results show that the impact sensitivity of the fine-grained AP in this example is 92%, the friction sensitivity is 96%, the impact sensitivity of the coated fine-grained AP is 0%, and the friction sensitivity is 0%.
Examples 1-7 the test equipment used was as follows:
fourier transform Infrared Spectroscopy (FT-IR) testing Using an Equinox 55 Infrared spectrometer from Bruker, Germany; FT-IR test conditions: room temperature, KBr tableting; the test resolution is 4cm -1 The number of scanning times is 32, and the test range is 400-4000cm -1 。
The thermal analysis test adopts a differential scanning calorimeter 2920 type of American TA company; DSC test conditions: n is a radical of 2 Atmosphere, 10 ℃/min; the test temperature range is 20-100 ℃.
Comparative example 1
At room temperature, adding 10.0g of fine-grained AP with the average grain size of 2 mu m into 100.0g of n-hexane, and performing ultrasonic dispersion for 30min to obtain AP dispersion liquid; dissolving 0.3g of No. 68 paraffin by using ethyl acetate to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 60 ℃ under the stirring condition, reacting for 2 hours, cooling the system to room temperature after the reaction is finished, finally removing n-hexane and ethyl acetate by reduced pressure distillation, and drying to obtain the coated fine-grained AP.
The mechanical sensitivity test results show that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 8%, and the friction sensitivity is 12%.
Comparative example 2
At room temperature, adding 10.0g of fine-grained AP with the average grain size of 2 mu m into 100.0g of n-hexane, and performing ultrasonic dispersion for 30min to obtain AP dispersion liquid; dissolving 0.15g of pentaerythritol-tris (3-aziridinyl) propionate with ethyl acetate to prepare a coating agent solution, then adding the coating agent solution into the AP dispersion liquid, slowly heating to 60 ℃ under the stirring condition, and reacting for 2 hours; and then dissolving 0.15g of No. 68 paraffin by using ethyl acetate to prepare a coating agent solution, adding the coating agent solution into the AP dispersion liquid, keeping the temperature at 60 ℃ for 2 hours under the stirring condition, cooling the system to room temperature after the reaction is finished, and finally removing n-hexane and ethyl acetate by reduced pressure distillation and drying to obtain the coated fine-grained AP.
The mechanical sensitivity test results show that the impact sensitivity of the fine-grained AP in this example is 96%, the friction sensitivity is 100%, the impact sensitivity of the coated fine-grained AP is 8%, and the friction sensitivity is 12%.
Example 8
The application performance of the coated fine-grained AP in high-burning-rate solid propellant.
The fine-particle size AP coated with the bonded phase-change coating agent prepared in examples 1 to 7 was applied to a high-burning-rate HTPB propellant, and the burning rate and mechanical sensitivity of the propellant were examined. The high-burning-speed HTPB propellant comprises the following components in percentage by weight: medium-particle size AP: 35.00 percent; coated fine-grained AP: 35.00 percent; aluminum powder: 15.00 percent; HTPB: 7.00 percent; dioctyl sebacate: 3.50 percent; toluene diisocyanate: 0.40 percent; a burning rate catalyst: 4.00 percent; and (3) process auxiliary agents: 0.10 percent.
Specifically, 35.00g of medium-particle-size AP, 35.00g of coated fine-particle-size AP prepared in example 1, 15.00g of aluminum powder, 7.00g of HTPB, 3.50g of dioctyl sebacate, 4.00g of burning rate catalyst and 0.10g of process auxiliary agent are weighed, the materials are added into a kneader preheated to 50 ℃, stirred and kneaded for 50min, after uniform mixing, 0.40g of toluene diisocyanate is added, mixing reaction is continued for 40min to obtain slurry with good flowing leveling property, the slurry is poured into a mold preheated to 50 ℃ at constant temperature of 50 ℃, the mold is placed into a 60 ℃ oven, and is solidified for 4d, and the slurry is taken out and cooled to room temperature to obtain the high-burning-rate HTPB propellant.
The resulting propellant was tested for burning rate and mechanical sensitivity.
Examples 9 to 14
Formulation compositions, contents and preparation methods in example 9, example 10, example 11, example 12, example 13 and example 14 are the same as those in example 8, except that the coated fine-particle-size AP in example 9, example 10, example 11, example 12, example 13 and example 14 is the coated fine-particle-size AP prepared in example 2, example 3, example 4, example 5, example 6 and example 7, respectively.
The resulting propellant was tested for burning rate and mechanical sensitivity.
Example 15
Weighing 35.00g of medium-particle-size AP, 35.00g of coated fine-particle-size AP prepared in example 1, 15.00g of aluminum powder, 6.30g of HTPB, 3.25g of dioctyl sebacate, 5.00g of burning rate catalyst and 0.10g of process auxiliary agent, adding the materials into a kneader preheated to 50 ℃, stirring and kneading for 50min, uniformly mixing, adding 0.35g of toluene diisocyanate, continuously mixing and reacting for 40min to obtain slurry with good flowing and leveling properties, pouring the slurry into a mold preheated to 50 ℃ at constant temperature of 50 ℃, putting the mold into a 60 ℃ oven, carrying out curing reaction for 4d, taking out and cooling to room temperature to obtain the high-burning-rate HTPB propellant.
The resulting propellant was tested for burning rate and mechanical sensitivity.
Example 16
Weighing 35.00g of medium-particle-size AP, 35.00g of coated fine-particle-size AP prepared in example 1, 15.00g of aluminum powder, 8.30g of HTPB, 4.10g of dioctyl sebacate, 2.00g of burning rate catalyst and 0.10g of process auxiliary agent, adding the materials into a kneader preheated to 50 ℃, stirring and kneading for 50min, mixing uniformly, adding 0.50g of toluene diisocyanate, continuing mixing and reacting for 40min to obtain slurry with good flowing leveling property, pouring the slurry into a mold preheated to 50 ℃ at constant temperature of 50 ℃, putting the mold into a 60 ℃ oven, curing and reacting for 4d, taking out and cooling to room temperature to obtain the high-burning-rate HTPB propellant.
The resulting propellant was tested for burning rate and mechanical sensitivity.
Comparative example 3
The formulation composition and content, preparation method in comparative example 3 were the same as in example 8, except that the fine particle size AP in comparative example 3 was uncoated (average particle size was 2 μm). The resulting propellant was tested for burning rate and mechanical sensitivity.
Comparative example 4
The formulation composition and content, preparation method in comparative example 4 were the same as in example 8, except that the fine particle size AP in comparative example 4 was uncoated (average particle size was 7 μm). The resulting propellant was tested for burning rate and mechanical sensitivity.
Comparative example 5
The formulation composition and amount and preparation method in comparative example 5 are the same as in example 8, with the only difference that the fine particle size AP in comparative example 5 is uncoated fine particle size AP (average particle size of 10 μm). The resulting propellant was tested for burning rate and mechanical sensitivity.
Comparative example 6
The formulation composition and content and preparation method in comparative example 6 are the same as those in example 8, except that the fine particle size AP in comparative example 6 is the coated fine particle size AP obtained in comparative example 1.
The resulting propellant was tested for burning rate and mechanical sensitivity.
Comparative example 7
The formulation composition and amount, and preparation method in comparative example 7 are the same as in example 8, except that the fine particle size AP in comparative example 7 is the coated fine particle size AP obtained in comparative example 2.
The resulting propellant was tested for burning rate and mechanical sensitivity.
From examples 1 to 7, the bonding type phase change coating agent prepared by the invention simultaneously comprises an aziridine ring bonding group aiming at AP and a long-chain alkyl phase change unit with a desensitizing function; compared with the sensitivity of the coated fine-grained AP obtained in the comparative example 1-2, the bonding type phase change coating agent and the paraffin phase change material have excellent sensitivity reduction effect; after being coated by the bonding type phase change coating agent, the impact sensitivity of the fine grain AP is reduced to 0-8% from 92-96%, and the friction sensitivity is reduced to 0-12% from 96-100%. When the average particle size and the content of the coating agent are constant, the type of the coating agent is changed, the friction sensitivity of the coated fine particle size AP is increased along with the reduction of the melting enthalpy of the coating agent, and the impact sensitivity is not obviously changed; when the average particle diameter and the type of the coating agent are fixed, the content of the coating agent is changed, and the impact sensitivity and the friction sensitivity of the coated fine particle size AP are increased along with the decrease of the content of the coating agent. Therefore, the regulation and control of the mechanical sensitivity of the coated fine-grained AP can be realized by regulating the melting enthalpy and the content of the bonding type phase-change coating agent, and the higher the melting enthalpy and the content of the coating agent are, the lower the mechanical sensitivity of the coated fine-grained AP is, and the more excellent the safety performance is.
The burning rates and mechanical sensitivities of the propellants obtained in examples 8 to 16 and comparative examples 3 to 7 are shown in Table 1.
TABLE 1 burning Rate and mechanical sensitivity of propellants
As can be seen from Table 1, after the fine-grained AP coated by the bonding type phase change coating agent is used for replacing the fine-grained AP in the HTPB propellant with high combustion speed, the mechanical sensitivity of the propellant is greatly reduced, the impact sensitivity is reduced from 76-92% to 28-48%, the friction sensitivity is reduced from 84-96% to 32-48%, and the requirements of GJB 6195-2008 on the impact sensitivity of the low-risk propellant is not more than 50% and the friction sensitivity is not more than 48% are met. The burning rates of the propellants obtained in the embodiment group and the comparative embodiment group are higher than 25mm/s, the propellants belong to high-burning-rate propellants, and under the condition that the burning rate catalyst content and the average particle size of AP are the same, after the coated fine-grained AP is used for replacing the fine-grained AP in the propellants, the burning rate of the propellants is not obviously changed, which shows that the burning rate of the high-burning-rate propellants cannot be reduced by the coating agent. When the average particle size of the coated fine-grained AP is constant, the more the content of the coating agent is, or the higher the melting enthalpy is, the larger the sensitivity reduction amplitude of the propellant is, which is consistent with the change rule of the sensitivity of the coated fine-grained AP. As can be seen from comparative examples 1 to 2 and comparative examples 6 to 7, although the sensitivity of the fine-grained AP itself can be greatly reduced by the paraffin phase-change material coating layer without enhanced interfacial effect, the sensitivity of the propellant prepared from the paraffin phase-change material coating layer is not greatly reduced, which indicates that the coating layer is peeled off during the propellant preparation process, and the sensitivity reduction effect is reduced (or failed). Therefore, the bonding type phase change coating agent has a remarkable sense reducing effect in a high-burning-rate propellant, and the condition that a sense reducing coating shell layer of a fine-grained AP surface coated by the bonding type phase change coating agent is not obviously stripped and fallen in the mixing and pouring process (mainly with shearing and friction effects) of the propellant is indirectly demonstrated, so that the paraffin type long-chain alkane phase change unit and the fine-grained AP particle surface have a strong interface effect.
In conclusion, the invention provides coated fine-grained ammonium perchlorate and a preparation method and application thereof, wherein the coated fine-grained AP is obtained by coating the surface of the fine-grained AP by adopting a bonding type phase-change coating agent; the bonding type phase change coating agent is obtained by chemically bonding long-chain alkyl alcohol to aziridine bonding agent molecules containing hydroxyl. After the bonding type phase change coating agent reacts and bonds with the AP surface, a coating shell layer with a strong interface effect and a phase change function is formed, the effect of reducing the sense of the fine-grained AP and the high-burning-rate HTPB propellant containing the fine-grained AP is remarkable, the burning rate of the propellant is not influenced, and the bonding type phase change coating agent has a good application prospect in the high-burning-rate HTPB propellant.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (9)
1. The coated fine-grained ammonium perchlorate is characterized in that the coated fine-grained ammonium perchlorate is a core-shell structure formed by the fine-grained ammonium perchlorate and a bonding type phase change coating agent coated on the surface of the fine-grained ammonium perchlorate, and the structural formula of the bonding type phase change coating agent is shown as (I):
wherein R is 1 ＝-CH 3 or-H, R 2 An aliphatic group, an alicyclic group or an aromatic group, wherein n is an integer between 18 and 34;
the fine-grained ammonium perchlorate is 2-10 mu m in average granularity.
2. The coated fine particle size ammonium perchlorate of claim 1, wherein the method of synthesizing the bonded phase change coating agent comprises the steps of:
dissolving bifunctional isocyanate in an anhydrous organic solvent at room temperature by adopting a closed reaction container with a reflux condensation part and a gas source, after nitrogen purging is carried out on the whole reaction system for 30min, slowly dropwise adding an anhydrous organic solution in which long-chain alkyl alcohol is dissolved into the reaction system, slowly heating the reaction system to 60-80 ℃, reacting for 8-12 h, cooling the system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, then pouring the reaction mixed solution into acetonitrile for reverse precipitation, and collecting precipitates to obtain an intermediate product isocyanate modified long-chain alkyl alcohol;
at room temperature, dissolving aziridine bonding agent molecules containing hydroxyl in an anhydrous organic solvent by using a closed reaction container with a reflux condensation part and a connecting gas source, purging the whole reaction system with nitrogen for 10-30 min, slowly dropwise adding an organic solution in which an intermediate product is dissolved into the reaction system, slowly heating the reaction system to 60-80 ℃, reacting for 8-12 h, cooling the system to room temperature after the reaction is finished, carrying out reduced pressure rotary evaporation and concentration on the reaction mixed solution, pouring the reaction mixed solution into acetonitrile for reverse precipitation, collecting precipitates, and drying the precipitates to obtain the bonding type phase change coating agent;
wherein:
the difunctional isocyanate is one of common aliphatic diisocyanate, alicyclic diisocyanate and aromatic diisocyanate; the aliphatic diisocyanate is one of hexamethylene diisocyanate and 2,2, 4-trimethylhexane diisocyanate; the alicyclic diisocyanate is one of methyl cyclohexylidene diisocyanate, dicyclohexyl methylene diisocyanate and isophorone diisocyanate; the aromatic diisocyanate is one of diphenylmethane 4, 4' -diisocyanate and toluene diisocyanate;
the anhydrous organic solvent is one of methyl acetate, ethyl acetate, butyl acetate, trichloromethane, dichloroethane and dioxane with the water content of less than 500 ppm;
the number of carbon atoms in the long-chain alkyl alcohol is 18-34; the ratio of the total amount of hydroxyl in the long-chain alkyl alcohol to the total amount of isocyanate in the bifunctional isocyanate is 1: 2;
the aziridine bonding agent molecule containing hydroxyl is one of pentaerythritol-tri (3-aziridinyl) propionate and pentaerythritol-tri [3- (2-methyl aziridinyl) ] propionate.
3. The coated fine-grained ammonium perchlorate of claim 1, wherein the mass ratio of the bonding type phase change coating agent to the fine-grained ammonium perchlorate is 0.5:100 to 3: 100.
4. The process for the preparation of coated fine-grained ammonium perchlorate according to any one of claims 1 to 3, comprising the following steps:
adding fine-grained ammonium perchlorate into an organic solvent at room temperature, and ultrasonically dispersing for at least 30min to obtain ammonium perchlorate dispersion liquid; dissolving a bonding type phase change coating agent by using ethyl acetate to prepare a coating agent solution, then adding the coating agent solution into the ammonium perchlorate dispersion liquid, slowly heating to 40-60 ℃ under the stirring condition, reacting for 2-4 h, cooling the system to room temperature after the reaction is finished, finally removing the organic solvent and the ethyl acetate through reduced pressure distillation, and drying to obtain the coated fine-grained ammonium perchlorate.
5. The method of preparing coated fine particle size ammonium perchlorate according to claim 4, wherein the organic solvent is one of n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene; the mass ratio of the ammonium perchlorate to the organic solvent in the ammonium perchlorate dispersion liquid is 1: 5-1: 10.
6. The method for preparing the coated fine-grained ammonium perchlorate according to claim 4, wherein the mass ratio of the bonding type phase-change coating agent to the fine-grained ammonium perchlorate is 0.5:100 to 3: 100.
7. A solid propellant, characterized in that it comprises a coated fine-grained ammonium perchlorate according to any one of claims 1 to 3, and in that it further comprises: medium-granularity ammonium perchlorate, metal powder, adhesive, plasticizer, burning rate catalyst, curing agent and technological assistant.
8. The solid propellant of claim 7 wherein the coated fine particle size ammonium perchlorate is present in the following mass percentages: 35.00 percent.
9. The solid propellant according to claim 7, wherein the contents of the components in mass percent are as follows: medium-size ammonium perchlorate: 35.00 percent; low-sensitivity fine-particle ammonium perchlorate: 35.00 percent; aluminum powder: 15.00 percent; hydroxyl-terminated polybutadiene: 6.30-8.30%; dioctyl sebacate: 3.25-4.10%; toluene diisocyanate: 0.35 to 0.50 percent; a burning rate catalyst: 2.00-5.00%; and (3) process auxiliary agents: 0.10 percent.
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