阅读说明：本技术 一种热塑性燃气发生剂及其制备方法 (Thermoplastic gas generating agent and preparation method thereof ) 是由 刘轩 孙林 孙晓飞 黄波 张军民 乔应克 陈维余 易飞 李志勇 李旭光 熊培祺 于 2019-10-24 设计创作，主要内容包括：本发明提供一种高强度的热塑性燃气发生剂及其制备方法,包含如下质量配比的组分：氧化剂：60％～80％,降温剂：1％～20％,热塑性粘合剂体系：6％～20％,键合剂：0.1％～2％,功能助剂：1％～5％。本发明制备的热塑性燃气发生剂不含有金属粉末,具有较低的燃温,键合剂的使用,改善了粘合剂体系与固体填料间的界面作用,显著提高了热塑性燃气发生剂的力学性能。(The invention provides a high-strength thermoplastic gas generating agent and a preparation method thereof, wherein the high-strength thermoplastic gas generating agent comprises the following components in parts by mass: oxidizing agent: 60% -80%, cooling agent: 1% -20%, thermoplastic adhesive system: 6% -20%, bonding agent: 0.1-2%, functional assistant: 1 to 5 percent. The thermoplastic gas generating agent prepared by the invention does not contain metal powder, has lower combustion temperature, improves the interface action between an adhesive system and solid filler by using a bonding agent, and obviously improves the mechanical property of the thermoplastic gas generating agent.)

1. A high strength thermoplastic gas generant characterized by: the components of the gas generating agent comprise an oxidant, a temperature reducing agent, a thermoplastic adhesive system, a bonding agent and a functional auxiliary agent;

calculated by taking the total mass of the gas generating agent as 100 percent, the mass percentage of each component in the gas generating agent is as follows:

60 to 80 percent of oxidant

1 to 20 percent of cooling agent

6 to 20 percent of thermoplastic adhesive system

0.1 to 2 percent of bonding agent;

1% -5% of functional auxiliary agent;

the bonding agent is a mixture of tetrabutyl titanate (TBT) and isopropyl triisostearate (TTIP).

2. A high strength thermoplastic gas generant in accordance with claim 1 wherein: the oxidant is at least one of Ammonium Nitrate (AN) and Ammonium Perchlorate (AP).

3. A high strength thermoplastic gas generant in accordance with claim 1 wherein: the cooling agent is at least one of Oxamide (OAM) and Ammonium Oxalate (AOA).

4. A high strength thermoplastic gas generant in accordance with claim 1 wherein: the thermoplastic adhesive system comprises an adhesive and a plasticizer, wherein the adhesive accounts for 5-10% and the plasticizer accounts for 1-10% of the total mass of the gas generating agent.

5. The high strength thermoplastic gas generant of claim 4 wherein: the adhesive is an ethylene-vinyl acetate copolymer, the trade name EVA420, the melting point: 73-78 ℃.

6. The high strength thermoplastic gas generant of claim 4 wherein: the plasticizer is at least one of diisooctyl sebacate (DOS), Acetyl Triethyl Citrate (ATC) and dibutyl phthalate (DBP).

7. A high strength thermoplastic gas generant in accordance with claim 1 wherein: the mass ratio of tetrabutyl titanate to isopropyl triisostearate in the bonding agent is 3: 1-9.

8. A high strength thermoplastic gas generant in accordance with claim 1 wherein: the functional auxiliary agent is N, N-diphenyl-p-phenylenediamine (DPPD), N-phenyl-2-naphthylamine (anti-aging agent D), N-phenyl-N-cyclohexane-p-phenylenediamine (anti-aging agent 4010), carbon black (C) and chromium oxide (Gr)₂O₃) Vanadium pentoxide (V)₂O₅) Iron oxide (Fe)₂O₃) Octyl Ferrocene (OFC) and katoxin (GFP).

9. A method for preparing a high strength thermoplastic gas generant, the method comprising the steps of:

(1) heating the adhesive;

(2) adding an oxidant, a cooling agent, a plasticizer, a bonding agent and a functional auxiliary agent into the heated adhesive in the step (1), and continuously heating and stirring to prepare slurry;

(3) and (3) pouring the slurry obtained in the step (2), and then standing and forming to obtain the high-strength thermoplastic gas generating agent.

10. The method of claim 9, wherein the high-strength thermoplastic gas generant is prepared by:

in the step (1), the heating temperature is 85-90 ℃;

in the step (2), stirring is carried out in a vertical mixer, the heating temperature is 85-90 ℃, and the stirring time is 60-110 min;

and (3) in the step of pouring, the casting is carried out by adopting vacuum spraying and pouring into a mould or an engine, and then the casting is carried out at room temperature for solidification and molding.

Technical Field

The invention relates to a high-strength thermoplastic gas generating agent and a preparation method thereof, belonging to the technical field of composite solid propellants.

Background

Compared with the traditional thermosetting gas generating agent, the thermoplastic gas generating agent taking the thermoplastic elastomer as the adhesive has no limit of casting 'pot life', has excellent mechanical property and repeatable processing property, can realize the continuity of the production of the propellant and the maximum recycling of the waste propellant, improves the production efficiency of the propellant, reduces the production cost, and in recent years, the thermoplastic gas generating agent becomes an important direction for the development of the solid propellant due to the unique property thereof, thereby arousing more and more intense research interest of scientific research workers.

The existing thermoplastic gas generator has poor mechanical property, and the tensile strength is generally lower than 0. Mpa.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the bonding agents with complementary advantages are combined for use, the mechanical property of the thermoplastic gas generating agent is obviously improved, meanwhile, the thermoplastic gas generating agent is mixed at a lower temperature, the intrinsic safety of the production process is improved, the curing process is omitted in the production process of products, the production period is shortened, the production efficiency is improved, the production cost is reduced, and the prepared gas generating agent has a wide application prospect.

The technical solution of the invention is as follows:

a high-strength thermoplastic gas generating agent comprises an oxidant, a temperature reducing agent, a thermoplastic adhesive system, a bonding agent and a functional auxiliary agent;

calculated by taking the total mass of the gas generating agent as 100 percent, the mass percentage of each component in the gas generating agent is as follows:

60 to 80 percent of oxidant

1 to 20 percent of cooling agent

6 to 20 percent of thermoplastic adhesive system

0.1 to 2 percent of bonding agent;

1% -5% of functional auxiliary agent;

the oxidant is at least one of Ammonium Nitrate (AN) and Ammonium Perchlorate (AP);

the cooling agent is at least one of Oxamide (OAM) and Ammonium Oxalate (AOA);

the thermoplastic adhesive system comprises an adhesive and a plasticizer, wherein the mass percent of the adhesive is 5-10%, and the mass percent of the plasticizer is 1-10%;

the adhesive is an ethylene-vinyl acetate copolymer, the trade name EVA420, the melting point: 73-78 ℃;

the plasticizer is at least one of diisooctyl sebacate (DOS), Acetyl Triethyl Citrate (ATC) and dibutyl phthalate (DBP);

the bonding agent is a mixture of tetrabutyl titanate (TBT) and isopropyl triisostearate (TTIP), wherein the mass ratio of tetrabutyl titanate to isopropyl triisostearate is 3: 1 to 9;

the functional auxiliary agent is N, N-diphenyl-p-phenylenediamine (DPPD), N-phenyl-2-naphthylamine (anti-aging agent D), N-phenyl-N-cyclohexane-p-phenylenediamine (anti-aging agent 4010), carbon black (C) and chromium oxide (Gr)₂O₃) Vanadium pentoxide (V)₂O₅) Iron oxide (Fe)₂O₃) Octyl Ferrocene (OFC) and katoxin (GFP).

A method of making a high strength thermoplastic gas generant, the method comprising the steps of:

(1) heating the adhesive;

(2) adding an oxidant, a cooling agent, a plasticizer, a bonding agent and a functional auxiliary agent into the heated adhesive in the step (1), and continuously heating and stirring to prepare slurry;

(3) and (3) pouring the slurry obtained in the step (2), and then standing and forming to obtain the high-strength thermoplastic gas generating agent.

In the step (1), the heating temperature is 85-90 ℃;

in the step (2), the heating temperature is 85-90 ℃, and the stirring time is 60-110 min;

and (3) in the step of pouring, the casting is carried out by adopting vacuum spraying and pouring into a mould or an engine, and then the casting is carried out at room temperature for solidification and molding.

Compared with the prior art, the invention has the advantages that:

(1) the invention adopts the bonding agent composed of tetrabutyl titanate and triisostearic acid titanium isopropyl ester, improves the interface action between the inorganic filler and the organic adhesive system, tetrabutyl titanate can chemically react with trace water on the surface of the inorganic filler, improves the lipophilicity of the inorganic filler, improves the compatibility between the inorganic filler and the organic adhesive system, the isopropoxy group in the triisostearic acid titanium isopropyl ester is easy to hydrolyze on the surface of the inorganic filler, generates synergistic action with tetrabutyl titanate to further improve the lipophilicity of the inorganic filler, and simultaneously, the stearic acid long chain in the isopropyl triisostearate can be physically wound with the adhesive, the compatibility between the inorganic filler and an adhesive system is improved, and the bonding agent is used to realize the advantage complementation of tetrabutyl titanate and isopropyl triisostearate, thereby ensuring the bonding effect.

(2) The invention selects the specific type and the specific components of the bonding agent by combining a large number of experiments through theoretical research, and simultaneously gives the specific content of the bonding agent in the thermoplastic gas generating agent, so that the mechanical property of the thermoplastic gas generating agent reaches the optimum.

(3) The thermoplastic gas generating agent provided by the invention realizes mixing and molding at a lower temperature, and improves the intrinsic safety of the production process of the thermoplastic gas generating agent.

(4) The invention provides a high-strength thermoplastic gas generating agent, which comprises the following components in parts by mass: oxidizing agent: 60% -80%, cooling agent: 1-20%, thermoplastic adhesive system: 10-20%, bonding agent: 0.1-2%, functional assistant: 1 to 5 percent. The thermoplastic gas generating agent prepared by the invention does not contain metal powder, has lower combustion temperature, improves the interface action between an adhesive system and solid filler by using a bonding agent, and obviously improves the mechanical property of the thermoplastic gas generating agent.

Detailed Description

Except for the description, the proportion adopted in the invention is the mass ratio.

The obtained gas generating agent is tested for mechanical property, melting point, gas forming amount, residue content and combustion temperature, and the test result shows that the prepared low-melting-point thermoplastic gas generating agent has higher mechanical strength, lower melting point, higher gas forming amount and lower residue content.

Mechanical properties: testing according to GJB770B-2005 gunpowder test method;

melting point: testing according to a Q/G4A-2002 composite solid propellant thermal decomposition temperature test method;

gas forming amount and fuel temperature: testing according to a method and a program for calculating the minimum free energy of the thermal performance of the Q/Gt60-95 composite solid propellant;

content of residue: the test was carried out according to the bomb combustion method for measuring the content of combustion residues of the slow burning agent of Q/Gt 93A-2001.

The following will explain details with reference to specific examples.