CN115784815B - Butyloxapol flame retardant material and preparation method and application thereof - Google Patents

Butyloxapol flame retardant material and preparation method and application thereof Download PDF

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CN115784815B
CN115784815B CN202211453540.6A CN202211453540A CN115784815B CN 115784815 B CN115784815 B CN 115784815B CN 202211453540 A CN202211453540 A CN 202211453540A CN 115784815 B CN115784815 B CN 115784815B
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flame retardant
butyl hydroxy
retardant material
parts
hydroxyl
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CN115784815A (en
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张文超
杜寒莹
杨荣杰
何快
黄洪勇
徐纪琳
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Shanghai Aerospace Chemical Engineering Institute
Beijing Institute of Technology BIT
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Shanghai Aerospace Chemical Engineering Institute
Beijing Institute of Technology BIT
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Abstract

The invention provides a butanediol flame retardant material, a preparation method and application thereof, and belongs to the technical field of functional materials. The preparation raw materials of the butyl hydroxy flame-retardant material comprise 50-80 parts of a butyl hydroxy bonding system, 15-42 parts of a flame retardant and 3-8 parts of a low heat conduction additive, wherein the heat conduction coefficient of the low heat conduction additive is less than 0.2W/m.K; the hydroxyl-terminated polybutadiene adhesive system comprises hydroxyl-terminated polybutadiene, a plasticizer and a curing agent, wherein the mass ratio of the hydroxyl-terminated polybutadiene to the plasticizer to the curing agent is 100: (0-40): (5-8). The invention adopts the butyl hydroxy adhesive system as the matrix material of the butyl hydroxy flame retardant material, and the butyl hydroxy flame retardant material has better flame retardant property and lower heat conductivity coefficient by adding the flame retardant and the low heat conduction additive, so the butyl hydroxy flame retardant material can be used as a flame retardant layer to be applied to a butyl hydroxy composite solid propellant intermittent charging structure.

Description

Butyloxapol flame retardant material and preparation method and application thereof
Technical Field
The invention relates to the technical field of functional materials, in particular to a hydroxyl flame retardant material and a preparation method and application thereof.
Background
The butyl hydroxy composite solid propellant has the advantages of excellent performance, low price, moderate energy level, low risk level and good mechanical property, and becomes one of the most commonly used modern composite solid propellants. In the prior art, a two-stage engine is usually needed to realize double thrust, but the mode has the problems of short range and large negative mass. To address this problem, two stages of propellants may be provided in a single stage engine to achieve dual thrust. However, if two stages of propellants are placed in sequence directly in the engine housing, combustion of one stage of propellant during use will ignite the other stage of propellant, resulting in a failed launch problem.
Disclosure of Invention
The invention aims to provide a butylhydroxy flame-retardant material, a preparation method and application thereof, and the butylhydroxy flame-retardant material provided by the invention has good flame retardant property and low heat conductivity coefficient, and can be used as a flame-retardant layer in a butylhydroxy composite solid propellant intermittent charging structure.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a butyl hydroxy flame-retardant material, which comprises, by mass, 50-80 parts of a butyl hydroxy bonding system, 15-42 parts of a flame retardant and 3-8 parts of a low heat conduction additive; the heat conductivity coefficient of the low heat conduction additive is less than 0.2W/m.K;
the hydroxyl-terminated polybutadiene adhesive system comprises hydroxyl-terminated polybutadiene, a plasticizer and a curing agent, wherein the mass ratio of the hydroxyl-terminated polybutadiene to the plasticizer to the curing agent is 100: (0-40): (5-8).
Preferably, the hydroxyl group content of the hydroxyl-terminated polybutadiene is 0.65 to 0.80mmol/g.
Preferably, the plasticizer is dioctyl sebacate.
Preferably, the curing agent comprises toluene diisocyanate or isophorone diisocyanate.
Preferably, the flame retardant comprises one or more of melamine polyphosphate, ammonium polyphosphate, hexachlorocyclotriphosphazene, tris (2, 3-dibromopropyl) isocyanurate and triphenyl phosphate.
Preferably, the low thermal conductivity additive is a cenosphere.
Preferably, the hollow microsphere comprises one or more of hollow glass microsphere, hollow polystyrene microsphere and hollow phenolic microsphere.
The invention provides a preparation method of the butyl hydroxy flame retardant material, which comprises the following steps:
and mixing the preparation raw materials of the butyl hydroxy flame retardant material, and then performing curing treatment to obtain the butyl hydroxy flame retardant material.
Preferably, the temperature of the curing treatment is 50-65 ℃ and the time is 5-7 days.
The invention provides the application of the butyl hydroxy flame retardant material prepared by the technical scheme or the preparation method of the technical scheme as a flame retardant layer in a butyl hydroxy composite solid propellant intermittent charging structure.
The invention provides a butyl hydroxy flame-retardant material, which comprises, by mass, 50-80 parts of a butyl hydroxy bonding system, 15-42 parts of a flame retardant and 3-8 parts of a low heat conduction additive; the heat conductivity coefficient of the low heat conduction additive is less than 0.2W/m.K; the hydroxyl-terminated polybutadiene adhesive system comprises hydroxyl-terminated polybutadiene, a plasticizer and a curing agent, wherein the mass ratio of the hydroxyl-terminated polybutadiene to the plasticizer to the curing agent is 100: (0-40): (5-8). The invention adopts the butyl hydroxy adhesive system as the matrix material of the butyl hydroxy flame retardant material, and the butyl hydroxy flame retardant material has better flame retardant property and lower heat conductivity coefficient by adding the flame retardant and the low heat conduction additive, so the butyl hydroxy flame retardant material can be used as a flame retardant layer to be applied to a butyl hydroxy composite solid propellant intermittent charging structure.
Drawings
Fig. 1 is a schematic diagram of a discontinuous charging structure of a butyl hydroxy composite solid propellant-flame retardant layer-butyl hydroxy composite solid propellant in the present invention.
Detailed Description
The invention provides a butyl hydroxy flame-retardant material, which comprises, by mass, 50-80 parts of a butyl hydroxy bonding system, 15-42 parts of a flame retardant and 3-8 parts of a low heat conduction additive; the heat conductivity coefficient of the low heat conduction additive is less than 0.2W/m.K;
the hydroxyl-terminated polybutadiene adhesive system comprises hydroxyl-terminated polybutadiene, a plasticizer and a curing agent, wherein the mass ratio of the hydroxyl-terminated polybutadiene to the plasticizer to the curing agent is 100: (0-40): (5-8).
The preparation raw materials of the butyl hydroxy flame retardant material comprise 50-80 parts by mass of a butyl hydroxy bonding system, and can be 50 parts by mass, 55 parts by mass, 60 parts by mass, 65 parts by mass, 70 parts by mass, 75 parts by mass or 80 parts by mass. In the present invention, the hydroxyl-terminated adhesive system preferably comprises hydroxyl-terminated polybutadiene (HTPB), a plasticizer and a curing agent, and the mass ratio of the hydroxyl-terminated polybutadiene, the plasticizer and the curing agent is preferably 100: (0-40): (5 to 8), more preferably 100: (30-40): (7-8). In the present invention, the hydroxyl group content in the hydroxyl-terminated polybutadiene is preferably 0.65 to 0.80mmol/g, and specifically may be 0.65mmol/g, 0.70mmol/g, 0.75mmol/g or 0.80mmol/g. The hydroxyl-terminated polybutadiene with the hydroxyl content is preferably adopted as the adhesive, so that the prepared hydroxyl-terminated polybutadiene is favorable for ensuring that the prepared hydroxyl-terminated polybutadiene has better tensile property. In the present invention, the plasticizer is preferably dioctyl sebacate (DOS); the plasticizer mainly plays a role in adjusting the technological performance, and can enable the preparation raw material mixture to be easier to level in a die when the butyl hydroxy flame-retardant material is prepared. In the present invention, the curing agent preferably includes Toluene Diisocyanate (TDI) or isophorone diisocyanate (IPDI).
Based on the mass parts of the butyl hydroxy adhesive system, the butyl hydroxy flame retardant material comprises 15-42 parts of flame retardant, and specifically 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or 42 parts. In the present invention, the flame retardant preferably includes one or more of melamine polyphosphate (MPP), ammonium polyphosphate (APP), hexachlorocyclotriphosphazene (PCT), tris (2, 3-dibromopropyl) isocyanurate (TBC) and triphenyl phosphate (TPP), and may specifically be a mixture of APP and MPP, or may be a mixture of PCT, MPP and TPP, or may also be a mixture of TBC, PCT and TPP, or may also be a mixture of APP and PCT; when the flame retardant is a mixture, the components may be mixed in any mass ratio, preferably equal mass. The invention preferably adopts the flame retardant of the type, which is favorable for ensuring that the butyl hydroxy flame retardant material has better flame retardant property.
Based on the mass parts of the butyl hydroxy adhesive system, the preparation raw materials of the butyl hydroxy flame retardant material comprise 3-8 parts of low heat conduction additive, and specifically can be 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, 5.5 parts, 6 parts, 6.5 parts, 7 parts, 7.5 parts or 8 parts. In the present invention, the low thermal conductivity additive is preferably a cenosphere; the hollow microsphere preferably comprises one or more of hollow glass microsphere, hollow polystyrene microsphere and hollow phenolic microsphere; the diameter of the hollow glass beads is preferably 10-100 mu m, more preferably 20-50 mu m; the hollow polystyrene microspheres preferably have a diameter of 50 to 100 μm, more preferably 50 to 70 μm; the hollow phenolic microspheres preferably have a diameter of 10 to 100. Mu.m, more preferably 20 to 50. Mu.m. The low heat conduction additive with the heat conduction coefficient smaller than 0.2W/m.K is preferably adopted, so that the butyl hydroxy flame retardant material has lower heat conduction coefficient.
The invention provides a preparation method of the butyl hydroxy flame retardant material, which comprises the following steps:
and mixing the preparation raw materials of the butyl hydroxy flame retardant material, and then performing curing treatment to obtain the butyl hydroxy flame retardant material.
In the invention, the preparation raw materials except the curing agent are preferably mixed to obtain a first mixture; mixing the first mixture with a curing agent to obtain a second mixture; and heating the second mixture, and then placing the second mixture in a mold for curing treatment to obtain the butyl hydroxy flame-retardant material.
The method for mixing the materials during the preparation of the first mixture and the second mixture is not particularly limited, and the uniform mixing of the materials can be realized. In the present invention, the temperature of the heating treatment is preferably 50 to 60 ℃; the time is preferably 20 to 30 minutes. The present invention preferably provides better flowability of the second mixture by heat treatment, which facilitates rapid leveling of the second mixture in the mold in a later step. In the present invention, the mold is preferably a polytetrafluoroethylene mold. In the present invention, the temperature of the curing treatment is preferably 50 to 65 ℃, and specifically may be 50 ℃, 55 ℃, 60 ℃ or 65 ℃; the time is preferably 5 to 7 days, and may be specifically 5 days, 6 days or 7 days. In the invention, in the curing treatment process, the hydroxyl groups of the hydroxyl-terminated polybutadiene and the isocyanate groups of the curing agent undergo a crosslinking reaction to form urethane bonds. In the invention, the butyl hydroxy flame retardant material is obtained by demolding after the curing treatment.
The invention provides the application of the butyl hydroxy flame retardant material prepared by the technical scheme or the preparation method of the technical scheme as a flame retardant layer in a butyl hydroxy composite solid propellant intermittent charging structure. In the present invention, the thickness of the flame retardant layer is preferably 0.1 to 5cm. The invention preferably bonds the butyl hydroxy flame retardant material as a flame retardant layer on the surface of the butyl hydroxy composite solid propellant to form a discontinuous charging structure of the butyl hydroxy composite solid propellant-flame retardant layer-butyl hydroxy composite solid propellant, so that the combustion of the two-stage butyl hydroxy composite solid propellant is not affected, double thrust is realized in a single-stage engine, and as shown in figure 1 (namely, the flame retardant layers are arranged between the butyl hydroxy composite solid propellant and the engine shell and between the two-stage butyl hydroxy composite solid propellant). The present invention preferably uses glue well known to those skilled in the art to adhere the butyl hydroxy flame retardant material to the surface of the butyl hydroxy composite solid propellant.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The formulation of the butyl hydroxy flame retardant material in this example is: 100g of adhesive, 5g of curing agent, 7.9g of low heat conduction additive and 26.25g of flame retardant; wherein the adhesive is HTPB, and the hydroxyl content is 0.65mmol/g; the curing agent is TDI; the low-heat-conductivity additive is hollow glass beads with the diameter of 20-50 mu m and the heat conductivity coefficient of less than 0.2W/m.K; the flame retardant is obtained by mixing APP and MPP according to a mass ratio of 1:1;
the preparation method of the butyl hydroxy flame retardant material comprises the following steps:
uniformly mixing the adhesive, the low-heat-conductivity additive and the flame retardant to obtain a first mixture;
uniformly mixing the first mixture and a curing agent to obtain a second mixture;
and (3) placing the second mixture in a baking oven at 50 ℃, heating for 30min, pouring into a tetrafluoroethylene mold, and curing for 5 days at 50 ℃ to obtain the butyl hydroxy flame-retardant material.
Example 2
The formulation of the butyl hydroxy flame retardant material in this example is: 100g of adhesive, 40g of plasticizer, 8g of curing agent, 5.92g of low heat conduction additive and 31.08g of flame retardant; wherein the adhesive is HTPB, and the hydroxyl content is 0.75mmol/g; the curing agent is TDI; the low heat conduction additive is hollow polystyrene microsphere with the diameter of 50-70 mu m and the heat conduction coefficient of less than 0.2W/m.K; the flame retardant is obtained by mixing PCT, MPP and TPP according to the mass ratio of 1:1:1;
the preparation method of the butyl hydroxy flame retardant material comprises the following steps:
uniformly mixing an adhesive, a plasticizer, a low heat conduction additive and a flame retardant to obtain a first mixture;
uniformly mixing the first mixture and a curing agent to obtain a second mixture;
and (3) placing the second mixture in a baking oven at 50 ℃, heating for 20min, pouring into a tetrafluoroethylene mold, and curing for 5 days at 65 ℃ to obtain the butyl hydroxy flame-retardant material.
Example 3
The formulation of the butyl hydroxy flame retardant material in this example is: 100g of adhesive, 8g of curing agent, 6.75g of low heat conduction additive and 20.25g of flame retardant; the adhesive is HTPB, and the hydroxyl content is 0.75mmol/g; the curing agent is TDI; the low heat conduction additive is hollow phenolic aldehyde microbeads with the diameter of 20-50 mu m and the heat conduction coefficient of less than 0.2W/m.K; the flame retardant is obtained by mixing TBC, PCT and TPP according to the mass ratio of 1:1:1;
the preparation method of the butyl hydroxy flame retardant material comprises the following steps:
uniformly mixing the adhesive, the low-heat-conductivity additive and the flame retardant to obtain a first mixture;
uniformly mixing the first mixture and a curing agent to obtain a second mixture;
and (3) placing the second mixture in a baking oven at 60 ℃, heating for 20min, pouring into a tetrafluoroethylene mold, and curing for 7 days at 65 ℃ to obtain the butyl hydroxy flame-retardant material.
Example 4
The formulation of the butyl hydroxy flame retardant material in this example is: 100g of adhesive, 8g of curing agent, 6.75g of low heat conduction additive and 20.25g of flame retardant; the adhesive is HTPB, and the hydroxyl content is 0.70mmol/g; the curing agent is TDI; the low-heat-conductivity additive is hollow glass beads with the diameter of 20-50 mu m and the heat conductivity coefficient of less than 0.2W/m.K; the flame retardant is obtained by mixing APP and PCT according to the mass ratio of 1:1;
the preparation method of the butyl hydroxy flame retardant material comprises the following steps:
uniformly mixing the adhesive, the low-heat-conductivity additive and the flame retardant to obtain a first mixture;
uniformly mixing the first mixture and a curing agent to obtain a second mixture;
and (3) placing the second mixture in a baking oven at 60 ℃, heating for 30min, pouring into a tetrafluoroethylene mold, and curing for 7 days at 50 ℃ to obtain the butyl hydroxy flame-retardant material.
Test case
The performance test is carried out on the butyl hydroxy flame retardant materials prepared in the examples 1 to 4, wherein the limiting oxygen index is tested according to the GB/T2406-93 method, the heat conductivity coefficient is tested according to the GB/T10297-2015 method, and the tensile strength is tested according to the GB/T528-1998 method; the test results are specifically shown in Table 1. As shown in Table 1, the butyl hydroxy flame retardant material provided by the invention has good flame retardant effect, the limiting oxygen index is 25.0-28.0%, the heat conductivity coefficient is low, the heat conductivity coefficient at 25 ℃ is 0.14-0.15W/m.K, and the tensile strength of the butyl hydroxy flame retardant material is 0.49-0.55 MPa.
Table 1 results of Performance test of the Butylene flame retardant materials in examples 1 to 4
Test item Example 1 Example 2 Example 3 Example 4
Limiting oxygen index (%) 26.5 28.0 25.0 25.2
Coefficient of thermal conductivity at 25 ℃ (W/m.K) 0.15 0.14 0.14 0.15
Tensile Strength (MPa) 0.51 0.49 0.50 0.55
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (8)

1. The material is prepared from (by weight parts) a butyl hydroxy adhesive system 50-80 parts, a flame retardant 15-42 parts, and a low heat conduction additive 3-8 parts; the heat conductivity coefficient of the low heat conduction additive is smaller than 0.2W/m.K, and the low heat conduction additive is hollow micro beads;
the hydroxyl-terminated polybutadiene adhesive system comprises hydroxyl-terminated polybutadiene, a plasticizer and a curing agent, wherein the mass ratio of the hydroxyl-terminated polybutadiene to the plasticizer to the curing agent is 100: (0-40): (5-8);
the flame retardant is selected from melamine polyphosphate, ammonium polyphosphate, hexachlorocyclotriphosphazene, tri (2, 3-dibromopropyl) isocyanurate and triphenyl phosphate.
2. The butyl hydroxy flame retardant material according to claim 1, wherein the hydroxyl group content of the hydroxyl terminated polybutadiene is 0.65 to 0.80mmol/g.
3. The butyl hydroxy flame retardant material of claim 1, wherein the plasticizer is dioctyl sebacate.
4. The butyl hydroxy flame retardant material of claim 1, wherein the curative comprises toluene diisocyanate or isophorone diisocyanate.
5. The butyl hydroxy flame retardant material of claim 1, wherein the cenospheres comprise one or more of hollow glass beads, hollow polystyrene beads and hollow phenolic beads.
6. The method for preparing the butyl hydroxy flame retardant material according to any one of claims 1 to 5, comprising the steps of:
and mixing the preparation raw materials of the butyl hydroxy flame retardant material, and then performing curing treatment to obtain the butyl hydroxy flame retardant material.
7. The method according to claim 6, wherein the curing treatment is carried out at a temperature of 50 to 65℃for a period of 5 to 7 days.
8. Use of the butoxide flame-retardant material according to any one of claims 1 to 5 or the butoxide flame-retardant material prepared by the preparation method according to any one of claims 6 to 7 as a flame-retardant layer in a butoxide composite solid propellant intermittent charge structure.
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