CN106565392A - Composite plasticizer used for HTPB-based explosives and propellants, and preparation method thereof - Google Patents

Composite plasticizer used for HTPB-based explosives and propellants, and preparation method thereof Download PDF

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Publication number
CN106565392A
CN106565392A CN201610900010.XA CN201610900010A CN106565392A CN 106565392 A CN106565392 A CN 106565392A CN 201610900010 A CN201610900010 A CN 201610900010A CN 106565392 A CN106565392 A CN 106565392A
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China
Prior art keywords
atoleine
preparation
htpb
weight
composite elasticizer
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CN201610900010.XA
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CN106565392B (en
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焦清介
欧亚鹏
朱艳丽
闫石
郭学永
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a c Composite plasticizer used for HTPB-based explosives and propellants, and a preparation method thereof. The composite plasticizer contains, by weight, 1-99% and preferably 20-80% of dioctyl adipate and 1-99% and preferably 20-80% of liquid paraffin. The preparation method is characterized in that the composite plasticizer is obtained through reduced-pressure heating rotary evaporation treatment of the dioctyl adipate and the liquid paraffin. The composite plasticizer has the advantages of good intersolubility with HTPB, low water content, high purity, high combustion heat and good vacuum stability, and the explosives have the advantages of high solid content, adjustable mechanical performances, good usability, short preparation time and low energy consumption when the composite plasticizer is applied to the HTPB-based explosives and the propellants.

Description

It is a kind of for HTPB bases explosive and the composite elasticizer and preparation method of propellant
Technical field
The invention belongs to HTPB base cast loadings field, and in particular to a kind of for the compound of HTPB bases explosive and propellant Plasticizer, it is a kind of for HTPB bases explosive and the preparation method of the composite elasticizer of propellant, and be obtained by the preparation method Composite elasticizer.
Background technology
End hydroxy butadiene (HTPB) base cast loading and propellant are low due to its excellent mechanical property and sensitivity Advantage has become the powder charge being most widely used now.For adjust powder charge mechanical property, the purpose such as processing performance and solid content, Needs add plasticizer in HTPB bases cast loading and propellant.The plasticizer being applied at present in HTPB base powder charges mostly is single One esters, such as hexanedioic acid dioctyl ester etc..Because the combustion heat value of esters is relatively low, there is energy using single ester plasticizer Low shortcoming；And, it is relatively low using explosive solid content in the HTPB base powder charges of dioctyl adipate, therefore, hexanedioic acid two is pungent The powder charge energy characteristics of the single ester plasticizer such as ester is not ideal.
Due to there is disadvantages mentioned above, foreign countries have developed the HTPB bases using naphthenic oil and atoleine as plasticizer Powder charge.Functional as the HTPB base charge processes of plasticizer using atoleine, explosive solid content is high；Due to alkane combustion Calorific value is high, therefore good using the HTPB base powder charge energy characteristicses of atoleine.But due to atoleine and the intersolubility of HTPB It is bad, the problems such as plasticizer is migrated in powder charge.There is the disadvantages such as permeability in therefore powder charge.
The forming process of cast class explosive and propellant is consolidated mainly due to terminal hydroxy group macromolecule therein and isocyanates Agent crosslinks reaction and generates network structure.But small molecular weight impurity present in plasticizer and explosive has a strong impact on moisture The carrying out of cross-linking reaction.Especially moisture present in plasticizer can generate carbon dioxide gas with isocyanate curing agent reaction Body, causes the presence of pore in powder charge, has had a strong impact on the quality of powder charge.At present to the plasticizer pretreatment process used in explosive Without clearly regulation, commonly used approach be plasticizer is placed in drying oven be dried it is 1 to 2 all, it is therein to remove Moisture and small molecular weight impurity.But this quadrat method not only needs to consume in the substantial amounts of energy and time, and treated material Small molecular weight impurity and moisture whether remove completely and there is also objection.
Therefore, a kind of new plasticizer of offer is needed badly, the plasticizer water content is low, purity is high, good with the intersolubility of HTPB, The advantages of there is explosive solid content height, mechanical property controllable during powder charge.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the invention provides it is a kind of for HTPB bases explosive and The composite elasticizer of propellant, it is a kind of for HTPB bases explosive and the preparation method of the composite elasticizer of propellant, and by this Composite elasticizer obtained in preparation method.
According to the first aspect of the invention, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant Agent, the composite elasticizer contains dioctyl adipate and atoleine；It is described on the basis of the gross weight of the composite elasticizer The content of dioctyl adipate is 1～99 weight %, and preferably 20～80 weight %, the content of the atoleine is 1～99 Weight %, preferably 20～80 weight %.
According to the second aspect of the invention, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant The preparation method of agent, the method includes：Heating under reduced pressure revolving process is carried out to dioctyl adipate and atoleine, obtains described Composite elasticizer；
Wherein, on the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 1～99 weight Amount %, preferably 20～80 weight %, the content of the atoleine is 1～99 weight %, preferably 20～80 weight %.
According to the third aspect of the invention we, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant Composite elasticizer obtained in the preparation method of agent.
The composite elasticizer of the present invention is good with the intersolubility of HTPB, and combustion heat value is high, and vacuum stability is good.Using the present invention The preparation method for HTPB bases explosive and the composite elasticizer of propellant obtained in composite elasticizer water content is low, purity Height, when being applied to HTPB bases explosive and propellant, explosive solid content is high, mechanical property controllable, good manufacturability；The system Preparation Method takes short, and energy consumption is low.
Specific embodiment
To make the present invention easier to understand, below in conjunction with embodiment the present invention is described in detail, these embodiments are only Play illustrative effect, be not limited to the present invention.
According to the first aspect of the invention, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant Agent, the composite elasticizer contains dioctyl adipate and atoleine；It is described on the basis of the gross weight of the composite elasticizer The content of dioctyl adipate is 1～99 weight %, and the content of the atoleine is 1～99 weight %.
Preferably, on the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 20～80 weights Amount %.
In the present invention, the atoleine contains C16～C24Linear paraffin at least one.It is well known in the art It is that the main component of atoleine is linear paraffin, and its content accounts for 75～100 weight %.
Preferably, the atoleine contains C16～C20Linear paraffin at least one.
Specifically, the atoleine can contain C16～C20Linear paraffin mixture, C18～C20Linear paraffin Mixture, C16～C18Linear paraffin mixture, C20Linear paraffin or C18Linear paraffin.
Preferably, on the basis of the gross weight of the composite elasticizer, the content of the atoleine is 20～80 weight %.
According to the second aspect of the invention, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant The preparation method of agent, the method includes：Heating under reduced pressure revolving process is carried out to dioctyl adipate and atoleine, obtains described Composite elasticizer；
Wherein, on the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 1～99 weight Amount %, the content of the atoleine is 1～99 weight %.
Preferably, on the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 20～80 weights Amount %, the content of the atoleine is 20～80 weight %.
In addition, the atoleine be specifically described and preferable case be described above identical, therefore not to repeat here.
In the present invention, described heating under reduced pressure revolving is processed and can carried out using Rotary Evaporators.
According to one preferred embodiment, preparation method of the present invention specifically includes following steps：
1) vacuumize：Dioctyl adipate and atoleine are sealed in revolving bottle, are vacuumized；
2) revolving is processed：At 50～100 DEG C, the dioctyl adipate and atoleine are rotated.
Step 1) in, it is described vacuumize allow the revolving bottle vacuum be -0.1 to 0MPa, it is therefore an objective to by institute The air stated in revolving bottle is extracted completely.
Step 2) in, the temperature that the revolving is processed is preferably 75～95 DEG C.
Step 2) in, the rotating speed that the revolving is processed can be 10～100rpm, preferably 30～70rpm.
Step 2) in, the time that the revolving is processed can be 1～4h, preferably 2～3h.
According to the third aspect of the invention we, the invention provides a kind of compound plasticising for HTPB bases explosive and propellant Composite elasticizer obtained in the preparation method of agent.
The present invention composite elasticizer water content is low, purity is high, vacuum stability is good, be applied to HTPB bases explosive and Good with the intersolubility of HTPB during propellant, explosive solid content is high, mechanical property controllable, good manufacturability.
Hereinafter will be described the present invention by embodiment.
In following examples and comparative example：
Atoleine：Beijing Chemical Plant, main component is C16～C20Linear paraffin.
Hexanedioic acid dioctyl ester；Liaoning Yingkou Tianyun Chemicals Research Institute Co., Ltd..
Solubility parameters：It is measured by swellbility method.
Combustion heat value：According to GJB 772A-97《Explosive test method》The quick-fried hot constant temperature method of method 701.1 and adiabatic method are surveyed Amount.
Vacuum stability：According to GJB772A-97《Explosive test method》The pressure sensor method of method 501.2 is detected.
Explosive viscosity：According to GJB772A-97《Explosive test method》The efflux method of method 412.1 is detected.
Mechanical property：According to GJB772A-97《Explosive test method》The electronic extensometer method of method 417.1 and 418.1 is carried out Detection.
Embodiment 1
The present embodiment be used for illustrate the present invention for HTPB bases explosive and the composite elasticizer and preparation method of propellant.
The composite elasticizer contains dioctyl adipate and atoleine；Gross weight with the composite elasticizer is as base Standard, the content of dioctyl adipate is 33 weight %, and the content of atoleine is 67 weight %.
Above-mentioned composite elasticizer is prepared by operation in detail below：
The first step：Dioctyl adipate and atoleine are sealed in revolving bottle, revolving bottle is reduced pressure using vavuum pump To -0.1MPa；
Second step：To 90 DEG C, it is 50rpm to adjust revolving rotating speed to heating-up temperature, 2h is rotated, so as to obtain composite elasticizer A.
Embodiment 2
The present embodiment be used for illustrate the present invention for HTPB bases explosive and the composite elasticizer and preparation method of propellant.
The composite elasticizer contains dioctyl adipate and atoleine；Gross weight with the composite elasticizer is as base Standard, the content of dioctyl adipate is 66 weight %, and the content of atoleine is 34 weight %.
Above-mentioned composite elasticizer is prepared by operation in detail below：
The first step：Dioctyl adipate and atoleine are sealed in revolving bottle, revolving bottle is reduced pressure using vavuum pump To -0.09MPa；
Second step：To 80 DEG C, it is 60rpm to adjust revolving rotating speed to heating-up temperature, 3h is rotated, so as to obtain composite elasticizer B.
Embodiment 3
The present embodiment be used for illustrate the present invention for HTPB bases explosive and the composite elasticizer and preparation method of propellant.
The composite elasticizer contains dioctyl adipate and atoleine；Gross weight with the composite elasticizer is as base Standard, the content of dioctyl adipate is 50 weight %, and the content of atoleine is 50 weight %.
Above-mentioned composite elasticizer is prepared by operation in detail below：
The first step：Dioctyl adipate and atoleine are sealed in revolving bottle, revolving bottle is reduced pressure using vavuum pump To -0.08MPa；
Second step：To 90 DEG C, it is 40rpm to adjust revolving rotating speed to heating-up temperature, 3h is rotated, so as to obtain composite elasticizer C.
Embodiment 4
The raw material of the composite elasticizer of embodiment 1 is mixed, in being placed in a conventional oven, is dried 1 week at 80 DEG C, so as to To composite elasticizer D.
The composite elasticizer of above-described embodiment 1-4, and the performance parameter of each raw material and HTPB is as shown in table 1.
Table 1
From table 1 it follows that the solubility parameters of the composite elasticizer of embodiment 1-4 most connects with the solubility parameters of HTPB Closely, it is better than dioctyl adipate and atoleine with the intersolubility of HTPB, and combustion heat value is higher than dioctyl adipate, and vacuum is pacified It is qualitative better than dioctyl adipate and atoleine.Solubility parameters of the composite elasticizer A compared with composite elasticizer D is close to HTPB, Combustion heat value is high, and vacuum stability is good, more excellent using composite elasticizer performance obtained in preparation method of the invention.
It is for explosive solid content by the composite elasticizer obtained by embodiment 1-4, dioctyl adipate and atoleine In 85% cast loading, viscosity and the mechanical property of cast loading are shown in Table 2.
Table 2
Plasticising raw material Viscosity/Pas Tensile strength/MPa Elongation at break/% Compressive strength/MPa
Dioctyl adipate 2087.1 0.98 245 1.12
Atoleine 1143.5 1.61 179 2.08
Composite elasticizer A 1394.0 1.52 294 1.97
Composite elasticizer B 1198.7 1.13 276 1.39
Composite elasticizer C 1226.2 1.28 257 1.73
Composite elasticizer D 1438.5 1.42 286 1.89
From Table 2, it can be seen that the solid content prepared using the composite elasticizer obtained by embodiment 1-4 is 85% explosive The viscosity of sample is less than the viscosity of the explosive sample prepared using dioctyl adipate, under identical viscosities, the present invention Composite elasticizer explosive solid content it is higher.The solid content prepared using the composite elasticizer of embodiment 1-4 be 85% it is fried The tensile strength of medicine sample, elongation at break and compressive strength are superior to the explosive sample of dioctyl adipate preparation, its fracture Elongation is better than explosive sample prepared by atoleine.The viscosity and mechanical property of explosive can be according to composite elasticizer of the present invention Composition and compositely proportional regulated and controled, processing performance is preferable.
It is described above embodiments of the invention, described above is exemplary, and non-exclusive, and also not It is limited to disclosed embodiment.In the case of the scope and spirit without departing from illustrated embodiment, for the art Many modifications and changes will be apparent from for those of ordinary skill.

Claims (10)

1. it is a kind of for HTPB bases explosive and the composite elasticizer of propellant, it is characterised in that the composite elasticizer contains oneself Adipate and atoleine；On the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 1～ 99 weight %, preferably 20～80 weight %, the content of the atoleine is 1～99 weight %, preferably 20～80 weights Amount %.
2. composite elasticizer according to claim 1, wherein, the atoleine contains C16～C24Linear paraffin in It is at least one；Preferably, the atoleine contains C16～C20Linear paraffin at least one.
3. it is a kind of for HTPB bases explosive and the preparation method of the composite elasticizer of propellant, it is characterised in that the method includes： Heating under reduced pressure revolving process is carried out to dioctyl adipate and atoleine, the composite elasticizer is obtained；
Wherein, on the basis of the gross weight of the composite elasticizer, the content of the dioctyl adipate is 1～99 weight %, excellent Elect 20～80 weight % as, the content of the atoleine is 1～99 weight %, preferably 20～80 weight %.
4. preparation method according to claim 3, wherein, the preparation method is comprised the following steps：
1) vacuumize：Dioctyl adipate and atoleine are sealed in revolving bottle, are vacuumized；
2) revolving is processed：At 50～100 DEG C, the dioctyl adipate and atoleine are rotated.
5. the preparation method according to claim 3 or 4, wherein, the atoleine contains C16～C24Linear paraffin in At least one；Preferably, the atoleine contains C16～C20Linear paraffin at least one.
6. preparation method according to claim 4, wherein, step 1) in, described vacuumizing causes the true of the revolving bottle Reciprocal of duty cycle is -0.1 to 0MPa.
7. preparation method according to claim 4, wherein, step 2) in, the temperature that the revolving is processed is 75～95 DEG C.
8. preparation method according to claim 4, wherein, step 2) in, the rotating speed that the revolving is processed is 10～ 100rpm。
9. preparation method according to claim 4, wherein, step 2) in, the time that the revolving is processed is 1～4h.
10. preparation method in claim 3～9 described in any one is obtained for the compound of HTPB bases explosive and propellant Plasticizer.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108147934A (en) * 2018-01-15 2018-06-12 湖北航天化学技术研究所 A kind of low melting point solid thermoplastics propellant and preparation method thereof

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CN101020769A (en) * 2007-03-15 2007-08-22 上海交通大学 Prepn process of thermoplastic wood-plastic composite material based on polyethylene vinyl acetate
CN102021080A (en) * 2010-12-02 2011-04-20 西南林业大学 Epoxy plant oil and preparation method thereof
CN103351837A (en) * 2013-05-10 2013-10-16 北京理工大学 Non-ester plasticizer-containing energetic material casting curing system and curing method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060052500A1 (en) * 2004-09-03 2006-03-09 Fu-Yuan Cheng Rubber eraser and method of fabrication
CN101020769A (en) * 2007-03-15 2007-08-22 上海交通大学 Prepn process of thermoplastic wood-plastic composite material based on polyethylene vinyl acetate
CN102021080A (en) * 2010-12-02 2011-04-20 西南林业大学 Epoxy plant oil and preparation method thereof
CN103351837A (en) * 2013-05-10 2013-10-16 北京理工大学 Non-ester plasticizer-containing energetic material casting curing system and curing method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108147934A (en) * 2018-01-15 2018-06-12 湖北航天化学技术研究所 A kind of low melting point solid thermoplastics propellant and preparation method thereof
CN108147934B (en) * 2018-01-15 2020-09-18 湖北航天化学技术研究所 Low-melting-point thermoplastic solid propellant and preparation method thereof

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