CN107118483B - High-intensity high-density HTPB and preparation method thereof - Google Patents

High-intensity high-density HTPB and preparation method thereof Download PDF

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Publication number
CN107118483B
CN107118483B CN201710486454.8A CN201710486454A CN107118483B CN 107118483 B CN107118483 B CN 107118483B CN 201710486454 A CN201710486454 A CN 201710486454A CN 107118483 B CN107118483 B CN 107118483B
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htpb
density
temperature
performed polymer
micron order
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CN107118483A (en
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蔡贾林
罗观
王德海
刘慧慧
史远通
郑保辉
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Institute of Chemical Material of CAEP
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/02—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/38—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/42—Casting under special conditions, e.g. vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
    • B29C39/22—Component parts, details or accessories; Auxiliary operations
    • B29C39/44—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter

Abstract

The invention discloses the preparation methods of high-intensity high-density HTPB a kind of, comprising the following steps: ingredient；The dehydration of HTPB performed polymer；Surfactant and micron order SiO2Dispersion；By treated, HTPB performed polymer is stirred evenly with mixed liquor, and adding curing agent continues to stir evenly, and constant temperature obtains mixed material to 50~55 DEG C of temperature；Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 53~58 DEG C of temperature of charge, vacuum degree≤- 0.092Mpa；Step F: it is heating and curing: the mold after casting complete being placed in 12~15h of heating at 50~60 DEG C of temperature, is then opened.The present invention is by introducing micron order SiO2And cooperates plasticizer DOA and surfactant Span 80 that can effectively improve the density and intensity of HTPB, while keeping the preferable rheological characteristic of HTPB.

Description

High-intensity high-density HTPB and preparation method thereof
Technical field
The invention belongs to polymeric material fields, and in particular to a kind of preparation method of high-intensity high-density HTPB.
Background technique
End hydroxy butadiene (HTPB) has a wide range of applications in many industrial circles.The crosslinked of HTPB has excellent Solvent resistant, oxytolerant ageing properties, and have high fracture toughness, can be used as the matrix of propellant, coating and other materials.Make The mechanical property of HTPB plays conclusive effect to the mechanical property of its final product when for basis material, passes through reasonable selection Molecular weight, curing agent and the plasticizer of HTPB performed polymer can adjust in a certain range the mechanical strength of HTPB, to meet Requirement under different condition, it is more to the research report of this aspect at present.However, HTPB when in face of compared with high shock pressure Intensity it is still inadequate, such as crackle is easy to produce when by elevated pressures using HTPB as the solid propellant of base, about HTPB The enhancing of mechanical property is reported also less at present.
The present invention provides the mechanical property Enhancement Methods of HTPB a kind of, and can not only effectively be mentioned using the method for the present invention The mechanical strength of high HTPB, moreover it is possible to its density be significantly increased, so that providing for acquisition high-density high-strength HTPB basis material can Can, carrying out mechanical property enhancing to HTPB using this method at present, there is not been reported.
Summary of the invention
The object of the present invention is to provide a kind of HTPB of high-intensity high-density, the HTPB of acquisition mechanical strength with higher With higher density.
It is yet another object of the invention to provide the preparation methods of the HTPB of high-intensity high-density a kind of.
In order to reach above-mentioned technical effect, the present invention takes following technical scheme:
A kind of preparation method of high-intensity high-density HTPB, comprising the following steps:
Step A: raw material ingredient: is weighed according to the component of following mass parts: HTPB performed polymer: 93~96 parts, micron order SiO2: 3~5 parts, 2~4 parts of plasticizer, surfactant: 0.2~0.5 part, curing agent: 4.0~4.5 parts；
The dehydration of step B:HTPB performed polymer: by HTPB performed polymer be preheated to 50~55 DEG C and vacuum degree≤- 2~3h of stir process under 0.090Mpa sloughs bubble therein；
Step C: surfactant and micron order SiO2Dispersion: surfactant is dissolved in plasticizer at room temperature and is stirred It mixes uniformly, micron order SiO is then added2And it is uniformly mixing to obtain mixed liquor, mixed liquor is then heated to 50~55 DEG C；
Step D: step B treated HTPB performed polymer is stirred evenly with mixed liquor, curing agent is added and continues to stir Uniformly, and constant temperature is to 50~55 DEG C of temperature, obtains mixed material；
Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 53~58 DEG C of temperature of charge, very Reciprocal of duty cycle≤- 0.092Mpa；
Step F: it is heating and curing: the mold after casting complete being placed in 12~15h of heating at 50~60 DEG C of temperature, is then opened Mould is to obtain the high-intensity high-density HTPB.
Further technical solution is the micron order SiO2Average grain diameter be 6~9 μm.
Further technical solution is that plasticizer is dioctyl adipate (DOA).
Further technical solution is that curing agent is isophorone diisocyanate.
Further technical solution is that surfactant is Span 80.
The present invention also provides the high-intensity high-densities that the preparation method of the high-intensity high-density HTPB is prepared HTPB。
The present invention will be further explained below.
Micron order SiO2As the reinforcing material of HTPB, one side micron order SiO2Addition can destroy HTPB strand Crystallinity, increase solidfied material in rigid joint, to improve the intensity of HTPB.On the other hand, SiO2It is with higher Density introduces SiO in HTPB2It can be improved the density of HTPB bonding system entirety, thus to obtain high-intensitive HTPB base Propellant, composite explosives etc. provide possibility.
Selecting average grain diameter is 6~9 μm of micron order SiO2Particle, can be with HTPB strand with suitable partial size Preferable matching, to reach to the preferable reinforcing effect of HTPB, while micron order SiO2The addition of particle is able to maintain HTPB The viscosity change of system is little, thus do not influence HTPB base propellant, in composite explosives other solid phase components addition.
Nanoscale SiO2Interaction between large specific surface area, nano particle is stronger, and system is viscous after addition HTPB Degree increases sharply, and the bubble under high viscosity in mixed system is difficult to exclude completely, defect to be easy to produce after sample solidification, to influence The intensity and density of HTPB.So this project does not select nanoscale SiO2And that select is micron-sized SiO2Particle.
Surfactant is Span 80, can be to micron order SiO2Particle plays emulsification, to improve SiO2Dispersion it is equal Even property improves the rheological characteristic of HTPB simultaneously.
Span 80 also known as sorbester p17.
Plasticizer is dioctyl adipate DOA, can not only reduce the viscosity of HTPB, and can also be ideal with Span 80 It dissolves each other, gives full play to the surface-active effect of Span 80.
Curing agent is isophorone diisocyanate, because isophorone diisocyanate is that 75% is cis- and 25% is trans- The mixture of isomers is used to solidify HTPB and micro-crystallization is less likely to occur, not will lead to the loss of HTPB intensity.
Moulding by casting is carried out to mixed material using vacuum casting device, can be avoided and generate bubble in forming process, mention High Forming Quality.
Compared with prior art, the present invention have it is below the utility model has the advantages that
The present invention is by introducing micron order SiO2And cooperate plasticizer DOA and surfactant Span 80 can be effectively The density and intensity of HTPB are improved, while keeping the preferable rheological characteristic of HTPB.
Specific embodiment
Below with reference to the embodiment of the present invention, the invention will be further elaborated.
Embodiment 1:
Step A: raw material ingredient: is weighed according to the component of following mass parts: HTPB performed polymer: 94 parts, micron order SiO2: 4 Part, DOA:2 parts, 80:0.2 parts of Span, isophorone diisocyanate: 4.0 parts；
The dehydration of step B:HTPB performed polymer: HTPB performed polymer is preheated to 50 DEG C and at vacuum degree≤- 0.090Mpa Stir process 2h sloughs bubble therein；
Step C: Span 80 being dissolved in DOA at room temperature and is stirred evenly, and micron order SiO is then added2And it stirs evenly Mixed liquor is obtained, mixed liquor is then heated to 50 DEG C；
Step D: step B treated HTPB performed polymer is stirred evenly with mixed liquor, adds and continues isophorone two Isocyanates stirs evenly, and constant temperature obtains mixed material to temperature 50 C；
Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 54 DEG C of temperature of charge, vacuum degree Mixed material is poured into preheated obtain in mold until material is filled up completely full mold with this condition by≤- 0.092Mpa；
Step F: it is heating and curing: the mold after casting complete being placed at 54 DEG C of temperature and heats 15h, then die sinking obtains The high-intensity high-density HTPB.
Every quality index of gained high-density high-strength HTPB is as follows:
(1) material initial viscosity ηα=65 centipoises (20 DEG C)；
(2) 65mm × 15mm × 5mm film actual density ρ=1.045g/cm3；
(3) mechanical property: compression strength: 13.56MPa, tensile strength: 9.63MPa, hardness (shore A): 60.5.
Embodiment 2:
Step A: raw material ingredient: is weighed according to the component of following mass parts: HTPB performed polymer: 95 parts, micron order SiO2: 3 Part, DOA:3 parts, 80:0.3 parts of Span, isophorone diisocyanate: 4.3 parts；
The dehydration of step B:HTPB performed polymer: HTPB performed polymer is preheated to 53 DEG C and at vacuum degree≤- 0.090Mpa Stir process 2h sloughs bubble therein；
Step C: Span 80 being dissolved in DOA at room temperature and is stirred evenly, and micron order SiO is then added2And it stirs evenly Mixed liquor is obtained, mixed liquor is then heated to 53 DEG C；
Step D: step B treated HTPB performed polymer is stirred evenly with mixed liquor, adds and continues isophorone two Isocyanates stirs evenly, and constant temperature obtains mixed material to 53 DEG C of temperature；
Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 57 DEG C of temperature of charge, vacuum degree Mixed material is poured into preheated obtain in mold until material is filled up completely full mold with this condition by≤- 0.092Mpa；
Step F: it is heating and curing: the mold after casting complete being placed at 58 DEG C of temperature and heats 12h, then die sinking obtains The high-intensity high-density HTPB.
Every quality index of gained high-density high-strength HTPB is as follows:
(1) material initial viscosity ηα=60 centipoises (20 DEG C)；
(2) 65mm × 15mm × 5mm film actual density ρ=1.052g/cm3；
(3) mechanical property: compression strength 14.28MPa, tensile strength: 11.06MPa, hardness (shore A) 65.7.
Comparative example (is added without micron order SiO2And surfactant):
Step A: raw material ingredient: is weighed according to the component of following mass parts: HTPB performed polymer: 95 parts, DOA:3 parts, different Buddhist That ketone diisocyanate: 4.3 parts；
The dehydration of step B:HTPB performed polymer: HTPB performed polymer is preheated to 53 DEG C and at vacuum degree≤- 0.090Mpa Stir process 2h sloughs bubble therein；
Step D: step B treated HTPB performed polymer is stirred evenly with DOA mixed liquor, adds continuation isophorone Diisocyanate stirs evenly, and constant temperature obtains mixed material to 53 DEG C of temperature；
Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 57 DEG C of temperature of charge, vacuum degree Mixed material is poured into preheated obtain in mold until material is filled up completely full mold with this condition by≤- 0.092Mpa；
Step F: it is heating and curing: the mold after casting complete being placed at 58 DEG C of temperature and heats 12h, then die sinking obtains The HTPB.
Every quality index of gained high-density high-strength HTPB is as follows:
(1) material initial viscosity ηα=58 centipoises (20 DEG C)；
(2) 65mm × 15mm × 5mm film actual density ρ=0.856g/cm3；
(3) mechanical property: compression strength 3.75MPa, tensile strength: 3.43MPa；, hardness (shore A) 35.6.
Although reference be made herein to invention has been described for explanatory embodiment of the invention, and above-described embodiment is only this hair Bright preferable embodiment, embodiment of the present invention are not limited by the above embodiments, it should be appreciated that those skilled in the art Member can be designed that a lot of other modification and implementations, these modifications and implementations will fall in principle disclosed in the present application Within scope and spirit.

Claims (5)

1. a kind of preparation method of high-intensity high-density HTPB, it is characterised in that the following steps are included:
Step A: raw material ingredient: is weighed according to the component of following mass parts: HTPB performed polymer: 93~96 parts, micron order SiO2: 3~ 5 parts, 2~4 parts of plasticizer, surfactant: 0.2~0.5, curing agent: 4.0~4.5；
The dehydration of step B:HTPB performed polymer: HTPB performed polymer is preheated to 50~55 DEG C and at vacuum degree≤- 0.090Mpa 2~3h of stir process sloughs bubble therein；
Step C: surfactant and micron order SiO2Dispersion: surfactant is dissolved at room temperature in plasticizer stir it is equal It is even, micron order SiO is then added2And it is uniformly mixing to obtain mixed liquor, mixed liquor is then heated to 50~55 DEG C；
Step D: step B treated HTPB performed polymer being stirred evenly with mixed liquor, curing agent is added and continues to stir evenly, And constant temperature obtains mixed material to 50~55 DEG C of temperature；
Step E: moulding by casting is carried out to mixed material using vacuum casting device, controls 53~58 DEG C of temperature of charge, vacuum degree ≤ -0.092Mpa；
Step F: it is heating and curing: the mold after casting complete is placed in 12~15h of heating at 50~60 DEG C of temperature, then die sinking is Obtain the high-intensity high-density HTPB.
2. the preparation method of high-intensity high-density HTPB according to claim 1, it is characterised in that the micron order SiO2 Average grain diameter be 6~9 μm.
3. the preparation method of high-intensity high-density HTPB according to claim 1, it is characterised in that the plasticizer is Dioctyl adipate, the curing agent are isophorone diisocyanate.
4. the preparation method of high-intensity high-density HTPB according to claim 1, it is characterised in that the surface-active Agent is Span 80.
5. a kind of height that the preparation method of high-intensity high-density HTPB according to any one of claims 1 to 4 is prepared Strength high density HTPB.
CN201710486454.8A 2017-06-23 2017-06-23 High-intensity high-density HTPB and preparation method thereof Active CN107118483B (en)

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US20130303649A1 (en) * 2010-12-02 2013-11-14 Kaneka Corporation Active energy ray-curable composition for optical material, cured product, and production method
CN104277754B (en) * 2013-07-29 2016-06-15 湖北航天化学技术研究所 A kind of limit combustion layer material and its preparation method being applicable to NEPE propelling agent
CN106278772B (en) * 2016-07-27 2017-11-10 中国工程物理研究院化工材料研究所 Explosive simulant and preparation method thereof

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