CN105753799B - One kind end alkynyl radical curing agent containing energy and preparation method thereof - Google Patents
One kind end alkynyl radical curing agent containing energy and preparation method thereof Download PDFInfo
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- CN105753799B CN105753799B CN201610182532.0A CN201610182532A CN105753799B CN 105753799 B CN105753799 B CN 105753799B CN 201610182532 A CN201610182532 A CN 201610182532A CN 105753799 B CN105753799 B CN 105753799B
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- curing agent
- alkynyl radical
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/30—Only oxygen atoms
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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
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses one kind end alkynyl radical curing agent containing energy, its structural formula are as follows：
Description
Technical field
The present invention relates to a kind of end alkynyl radical curing agent, suitable for solid propellant field.
Background technology
In recent years, people did not required nothing more than its energy height to solid propellant, were both also to require micro- cigarette, few cigarette and low rapid wear
Property, and think that Development of Novel energetic binder system is to take into account one of effective way for solving these contradictions simultaneously.Nitrine bonds
Agent has fast positive generation heat, burning, energy height, combustion gas cleaning, heat endurance good and the advantages such as mechanical sensitivity is low, thus is generation
The important goal that various countries of boundary are competitively studied.After Vandenberg in 1972 synthesizes GAP soon, azido binder agent is in rifle
It is used widely in big gun propellant powder, propellant, gas generator and high explosive, due to containing energy, therefore is used to replace
Traditional inert binder (such as HTPB or HTPE).Azido binder is the high molecular polymer containing terminal hydroxy group, when in use typically
Isocyanate cure systems are formed with polyfunctionality isocyanate curing agent, are solidified by terminal hydroxy group and NCO reaction,
But the isocyanate curing agent in such curing system has high activity, Yi Yushui or Bronsted acid fast reaction generation CO2,
Many stomatas are formed in the solidification process of propellant so that the density of propellant declines, and influences its mechanical property, while to push away
The safety and reliability for entering agent also declines.And as energetic material energy level improves constantly, some novel greens contain energy
Material such as ADN (ADN), hydrazine nitroform (HNF) run into compatible when using azido binder/isocyanate cure systems
Poor, the stability difference problem of property.
In order to solve above mentioned problem existing for isocyanate curing agent, scientific research personnel have developed a kind of non-isocyanate and consolidate
Agent, i.e. end alkynyl radical curing agent, polytriazoles is formed using 1,3- Dipolar Cycloadditions occur between carbon-to-carbon triple bond and azido
Cross-linked elastomer completes the solidification of azido binder.Such as Trond H.Hagen et al.《Curing of glycidyl-
azide-polymer(GAP)diol using isocyanate,isocyanate-free,synchronous dual,and
sequential dual curing systems》Propellants,Explosives,Pyrotechnics,2015,40:
275-284 discloses a kind of end alkynyl radical curing agent, i.e. two propinyl hydroquinones (BPHQ), its structural formula is as follows：
BPHQ and two degree of functionality GAP carries out curing reaction, solidifies what is obtained when BPHQ/GAP mol ratios are 1.0 and 1.3
Film mechanical property difference is as follows：Tensile strength is 0.34MPa, elongation percentage 68%；Tensile strength is 0.57MPa, elongation percentage
For 48%, the mechanical property of film is relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of background technology, there is provided a kind of mechanical property is higher to be contained
Energy end alkynyl radical curing agent and preparation method thereof.
Idea of the invention is that：1) highly polar group azacyclo- construction unit is introduced in end alkynyl radical solidifies agent molecule, led to
Crossing strengthens intermolecular active force to improve the mechanical property of elastomer；2) polyethers of flexibility is introduced in end alkynyl radical curing agent
Chain, improve the elongation percentage of elastomer；3) nitrate group is introduced in end alkynyl radical curing agent to improve the energy of elastomer.
In order to solve the above-mentioned technical problem, the end alkynyl radical curing agent provided by the invention containing energy, its structural formula are as follows：
Wherein, x, y, z are 2~5 positive integer.
The synthetic route of the present invention is as follows：
Wherein, x, y, z are 2~5 positive integer.
Specifically include following steps：
1) with 1,3,5- trihydroxyethyl isocyanuric ester (THEIC) for initiator, boron trifluoride etherate is catalysis
Agent, dichloroethanes are solvent, and glycidol ether nitrate (GN) is monomer, by cation ring-opening polymerization mechanism, synthesize terminal hydroxy group
Glycidol ether nitrate ester polyether；The mol ratio of the 1,3,5- trihydroxyethyl isocyanuric esters and glycidol ether nitrate is
1:The mol ratio of 6~15,1,3,5- trihydroxyethyl isocyanuric ester and boron trifluoride etherate is 3:1, reaction temperature is
17 DEG C~20 DEG C.
2) in tetrahydrofuran medium, the hydroxyl of terminal hydroxy group glycidol ether nitrate ester polyether is sealed with propine bromine
End, forms the end alkynyl radical curing agent containing itrate group polyether chain；Propine bromine and terminal hydroxy group the glycidol ether nitrate gathers
The mol ratio of ether is 3.1:1, reaction temperature is 38 DEG C~40 DEG C.
Advantages of the present invention：Tensile strength is 0.51MPa during 25 DEG C of the present invention/GAP (mol ratio 1.0) crosslinked, is prolonged
Rate is stretched for 79%；And tensile strength is 0.34MPa during 25 DEG C of BPHQ/GAP (mol ratio 1.0) crosslinked in documents,
Elongation percentage is 68%.Tensile strength is 0.72MPa during 25 DEG C of the present invention/GAP (mol ratio 1.3) crosslinked, and elongation percentage is
60%；And tensile strength is 0.57MPa during 25 DEG C of BPHQ/GAP (mol ratio 1.3) crosslinked in documents, elongation percentage
For 48%.
Embodiment
With reference to embodiment, the present invention is described further.
Number-average molecular weight is tested
Equipment：Britain's PL companies GPC-50 type gel permeation chromatographs；
GPC test conditions：Chromatographic column is connected for PLgel MIXED-E；Mobile phase is THF；Column temperature is 40 DEG C；
Detector is differential refraction detector.
Film Mechanics Performance Testing
Equipment：The type universal testing machines of Instron companies of U.S. Instron 4505；
Method of testing：According to GB/T528-1998.
Embodiment 1
The synthesis of the 1 end alkynyl radical curing agent containing energy
The synthesis of 1.1 terminal hydroxy group glycidol ether nitrate ester polyethers
One equipped with mechanical agitation, reflux condensing tube, thermometer, dropping funel 1L four round flask in successively plus
Enter 200ml dichloroethanes, 43.89g (0.168mol) 1,3,5- trihydroxyethyl isocyanuric esters (THEIC) and 7.09ml
(0.056mol) catalyst boron trifluoride etherate, after 30min is stirred at room temperature, start that 120.07g is added dropwise
The glycidol ether nitrate (GN) of (1.009mol), polymerization temperature is controlled during dropwise addition at 17~20 DEG C, insulation reaction 5h.With
Na2CO3Aqueous solution terminating reaction, organic phase are washed to neutrality, concentration, and crown ether accessory substance is removed with petroleum ether extraction, after concentration
To light yellow viscous liquid 153.79g, yield 93.8%.
Structural characterization：Infrared (KBr, cm-1)：3349 (O-H), 1320,934 (azacyclo-s), 1630,1281,870 (-
ONO2), 1127 (C-O-C).
The synthesis of the 1.2 end alkynyl radical curing agent containing energy
One equipped with mechanical agitation, reflux condensing tube, thermometer, dropping funel 500ml four round flask according to
Secondary addition 200ml tetrahydrofurans, 53.63g (0.055mol) terminal hydroxy group glycidol ether nitrate ester polyether and 18.48g
(0.165mol) potassium tert-butoxide, stirs, and is heated to 40 DEG C, states 20.33g is added dropwise in reaction system then up
(0.171mol) propine bromine, 38 DEG C~40 DEG C reaction 6h after being added dropwise.Room temperature is cooled to, reaction solution is poured into water, with two
Chloromethanes extracts, and oil phase is washed with water to neutrality, dichloromethane is evaporated off, after vacuum drying, obtains light yellow transparent liquid
55.16g yield 92.1%.
Structural characterization：Infrared (KBr, cm-1)：3310 (≡ C-H), 2120 (C ≡ C), 1322,938 (azacyclo-s), 1632,
1285th, 876 (- ONO2), 1129 (C-O-C).
Theoretical number-average molecular weight is 1089, and actual measurement number-average molecular weight is~1068.
Compound synthesized by above-mentioned data confirm that is exactly the end alkynyl radical curing agent containing itrate group polyether chain.
The application performance of 2 present invention
(1) with the compatibility of azido binder
It is adhesive to select GAP, has investigated the compatibility and reactivity of the end alkynyl radical curing agent containing energy and adhesive.
The end alkynyl radical curing agent containing energy of the present invention has good compatibility with GAP adhesives, and mixture is as clear as crystal, institute
The mixed liquor of formation can smoothly carry out curing reaction at 50~60 DEG C.
(2) mechanical property of crosslinked
Containing energy end alkynyl radical curing agent reaction of the GAP adhesives respectively with BPHQ curing agent and the present invention is generated into crosslinked,
Its corresponding mechanical property is shown in Table 1：
Influence (25 DEG C) of the curing agent of table 1 to crosslinked mechanical property
| Curing system (mol ratio) | Tensile strength, MPa | Elongation percentage, % |
| Curing agent/GAP (1.0) of the present invention | 0.51 | 79 |
| BPHQ/GAP(1.0) | 0.34 | 68 |
| Curing agent/GAP (1.3) of the present invention | 0.72 | 60 |
| BPHQ/GAP(1.3) | 0.57 | 48 |
It can be seen that the crosslinked mechanical property that the present invention is formed is substantially better than BPHQ.
Claims (4)
1. one kind end alkynyl radical curing agent containing energy, it is characterised in that structural formula is as follows：
Wherein, x, y, z are 2~5 positive integer.
2. the synthetic method of the end alkynyl radical curing agent containing energy described in a kind of claim 1, it is characterised in that step is as follows：
1) with 1,3,5- trihydroxyethyl isocyanuric ester for initiator, boron trifluoride etherate is catalyst, dichloroethanes
For solvent, glycidol ether nitrate is monomer, by cation ring-opening polymerization mechanism, synthesizes terminal hydroxy group glycidol ether nitrate
Polyethers；
2) in tetrahydrofuran medium, the hydroxyl of terminal hydroxy group glycidol ether nitrate ester polyether is blocked with propine bromine, shape
Into the end alkynyl radical curing agent containing itrate group polyether chain.
3. synthetic method according to claim 2, it is characterised in that 1,3,5- trihydroxyethyl isocyanides are urinated in the step 1)
The mol ratio of acid esters and glycidol ether nitrate is 1:6~15,1,3,5- trihydroxyethyl isocyanuric ester and boron trifluoride second
The mol ratio of ether complexes is 3:1, reaction temperature is 17 DEG C~20 DEG C.
4. synthetic method according to claim 2, it is characterised in that propine bromine and terminal hydroxy group shrink sweet in the step 2)
The mol ratio of oily ether nitrate ester polyether is 3.1:1, reaction temperature is 38 DEG C~40 DEG C.
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| CN109942804B (en) * | 2019-04-02 | 2021-05-18 | 西安近代化学研究所 | Three-arm terminal alkynyl poly-3-nitrate methyl-3-methyloxetane prepolymer |
| CN110511372B (en) * | 2019-08-28 | 2022-04-19 | 西安近代化学研究所 | Energy-containing terminal isocyanate group curing agent and synthesis method thereof |
| CN112920002A (en) * | 2021-01-28 | 2021-06-08 | 西安近代化学研究所 | Energy-containing terminal alkenyl polyether curing agent, preparation method and application |
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| WO2011047738A1 (en) * | 2009-10-23 | 2011-04-28 | Henkel Ireland Ltd. | Aqueous-based composition suitable for use in threadlocking applications |
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| WO2016039277A1 (en) * | 2014-09-08 | 2016-03-17 | 電気化学工業株式会社 | Composition and disassembling method |
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| JPH06192521A (en) * | 1992-04-21 | 1994-07-12 | Nisshin Fine Chem Kk | Stabilized halogen-containing resin composition |
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| WO2011047738A1 (en) * | 2009-10-23 | 2011-04-28 | Henkel Ireland Ltd. | Aqueous-based composition suitable for use in threadlocking applications |
| CN104628494A (en) * | 2013-11-14 | 2015-05-20 | 南开大学 | Nitrate energetic plasticizer and synthesis method thereof |
| WO2016039277A1 (en) * | 2014-09-08 | 2016-03-17 | 電気化学工業株式会社 | Composition and disassembling method |
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