CN105753799A - Energy-containing terminal alkynyl curing agent and preparation method thereof - Google Patents
Energy-containing terminal alkynyl curing agent and preparation method thereof Download PDFInfo
- Publication number
- CN105753799A CN105753799A CN201610182532.0A CN201610182532A CN105753799A CN 105753799 A CN105753799 A CN 105753799A CN 201610182532 A CN201610182532 A CN 201610182532A CN 105753799 A CN105753799 A CN 105753799A
- Authority
- CN
- China
- Prior art keywords
- glycidyl ether
- firming agent
- alkynyl radical
- mol ratio
- energy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- 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 an energy-containing terminal alkynyl curing agent. The energy-containing terminal alkynyl curing agent has a structural formula shown in the specification, wherein x, y and z are all positive integers ranging from 2 to 5. The energy-containing terminal alkynyl curing agent is mainly used for a solid propellant.
Description
Technical field
The present invention relates to a kind of end alkynyl radical firming agent, it is adaptable to solid propellant field.
Background technology
In recent years, it is high that solid propellant is not required nothing more than its energy by people, is both and also requires micro-cigarette, few cigarette and Low vulnerability, and thinks that Development of Novel energetic binder system is one of effective way simultaneously taking into account these contradictions of solution.Azido binder has that positive generation heat, burning be fast, energy height, combustion gas cleaning, Heat stability is good and the advantage such as mechanical sensitivity is low, thus is the important goals competitively studied of countries in the world.Since Vandenberg in 1972 after synthesizing GAP soon, azido binder agent is used widely in gun propellant, propellant, gas generator and high explosive, due to containing energy, therefore it is used to replace tradition inert binder (such as HTPB or HTPE).Azido binder is the high molecular polymer containing terminal hydroxy group, general in use and polyfunctionality isocyanate curing agent forms isocyanate cure systems, reacted by terminal hydroxy group and NCO and solidify, but the isocyanate curing agent in this type of curing system has high activity, Yi Yushui or Bronsted acid fast reaction generates CO2, the solidification process of propellant forms a lot of pore so that the density of propellant declines, and affects its mechanical property, makes the safety and reliability of propellant also decline simultaneously.And along with energetic material energy level improves constantly, some novel green energetic materials such as ADN (ADN), hydrazine nitroform (HNF) run into poor compatibility, poor stability problem when using azido binder/isocyanate cure systems.
In order to solve the problems referred to above that isocyanate curing agent exists, scientific research personnel have developed a kind of non-isocyanate firming agent, i.e. end alkynyl radical firming agent, utilizes the solidification occurring 1,3-Dipolar Cycloaddition formation polytriazoles cross-linked elastomer to complete azido binder between carbon-to-carbon triple bond and azido.Such as TrondH.Hagen et al. " Curingofglycidyl-azide-polymer (GAP) diolusingisocyanate, isocyanate-free, synchronousdual, andsequentialdualcuringsystems " Propellants, Explosives, Pyrotechnics, 2015,40:275-284 discloses a kind of end alkynyl radical firming agent, i.e. two propinyl hydroquinone (BPHQ), and its structural formula is as follows:
BPHQ and two degree of functionality GAP carries out curing reaction, solidifies the film mechanical property obtained when BPHQ/GAP mol ratio is 1.0 and 1.3 as follows respectively: hot strength is 0.34MPa, and elongation percentage is 68%；Hot strength is 0.57MPa, and elongation percentage is 48%, and the mechanical property of film is on the low side.
Summary of the invention
The technical problem to be solved is the deficiency overcoming background technology, it is provided that a kind of mechanical property higher containing can end alkynyl radical firming agent and preparation method thereof.
Insight of the invention is that 1) in end alkynyl radical firming agent molecule, introduce highly polar group azacyclo-construction unit, the mechanical property of elastomer is improved by strengthening intermolecular active force；2) in end alkynyl radical firming agent, introduce the polyether chain of flexibility, improve the elongation percentage of elastomer；3) in end alkynyl radical firming agent, introduce nitrate group and improve the energy of elastomer.
In order to solve above-mentioned technical problem, provided by the invention containing energy end alkynyl radical firming agent, its structural formula is as follows:
Wherein, x, y, z is the positive integer of 2～5.
The synthetic route of the present invention is as follows:
Wherein, x, y, z is the positive integer of 2～5.
Specifically include following steps:
1) with 1,3,5-trihydroxyethyl isocyanuric ester (THEIC) is initiator, boron trifluoride etherate is catalyst, dichloroethanes is solvent, glycidyl ether nitrate (GN) is monomer, by cation ring-opening polymerization mechanism, synthesizes terminal hydroxy group glycidyl ether nitrate ester polyether；The mol ratio of described 1,3,5-trihydroxyethyl isocyanuric ester and glycidyl ether nitrate is 1:6～15, and the mol ratio of 1,3,5-trihydroxyethyl isocyanuric ester and boron trifluoride etherate is 3:1, and reaction temperature is 17 DEG C～20 DEG C.
2) in oxolane medium, with propine bromine, the hydroxyl of terminal hydroxy group glycidyl ether nitrate ester polyether is terminated, form the end alkynyl radical firming agent containing itrate group polyether chain；The mol ratio of described propine bromine and terminal hydroxy group glycidyl ether nitrate ester polyether is 3.1:1, and reaction temperature is 38 DEG C～40 DEG C.
Advantages of the present invention: during the present invention/GAP (mol ratio is 1.0) crosslinked 25 DEG C, hot strength is 0.51MPa, and elongation percentage is 79%；And hot strength is 0.34MPa during BPHQ/GAP (mol ratio is 1.0) crosslinked 25 DEG C in documents, elongation percentage is 68%.During the present invention/GAP (mol ratio is 1.3) crosslinked 25 DEG C, hot strength is 0.72MPa, and elongation percentage is 60%；And hot strength is 0.57MPa during BPHQ/GAP (mol ratio is 1.3) crosslinked 25 DEG C in documents, elongation percentage is 48%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further.
Number-average molecular weight is tested
Equipment: Britain's PL company GPC-50 type chromatograph of gel permeation；
GPC test condition: chromatographic column is PLgelMIXED-E series connection；Mobile phase is THF；Column temperature is 40 DEG C；
Detector is differential refraction detector.
Film Mechanics Performance Testing
Equipment: American I nstron company Instron4505 type universal testing machine；
Method of testing: according to GB/T528-1998.
Embodiment 1
1 synthesis containing energy end alkynyl radical firming agent
The synthesis of 1.1 terminal hydroxy group glycidyl ether nitrate ester polyethers
The tetra-mouthfuls of round-bottomed flasks of 1L being furnished with mechanical agitation, reflux condensing tube, thermometer, Dropping funnel are sequentially added into 200ml dichloroethanes, 43.89g (0.168mol) 1,3,5-trihydroxyethyl isocyanuric ester (THEIC) and 7.09ml (0.056mol) catalyst boron trifluoride etherate, after 30min is stirred at room temperature, start to drip the glycidyl ether nitrate (GN) of 120.07g (1.009mol), polymerization temperature is controlled at 17～20 DEG C, insulation reaction 5h during dropping.Use Na2CO3Aqueous solution terminates reaction, and organic facies is washed to neutrality, concentration, removes crown ether by-product with petroleum ether extraction, obtains light yellow viscous liquid 153.79g, productivity 93.8% after concentration.
Structural characterization: infrared (KBr, cm-1): 3349 (O-H), 1320,934 (azacyclo-s), 1630,1281,870 (-ONO2), 1127 (C-O-C).
1.2 synthesis containing energy end alkynyl radical firming agent
The tetra-mouthfuls of round-bottomed flasks of 500ml being furnished with mechanical agitation, reflux condensing tube, thermometer, Dropping funnel are sequentially added into 200ml oxolane, 53.63g (0.055mol) terminal hydroxy group glycidyl ether nitrate ester polyether and 18.48g (0.165mol) potassium tert-butoxide, stir, heating is to 40 DEG C, state dropping 20.33g (0.171mol) propine bromine in reaction system then up, dropwise rear 38 DEG C～40 DEG C reaction 6h.It is cooled to room temperature, reactant liquor is poured into water, with dichloromethane extraction, wash oil phase with water to neutral, dichloromethane is evaporated off, after vacuum drying, obtains light yellow transparent liquid 55.16g, productivity 92.1%.
Structural characterization: infrared (KBr, cm-1): 3310 (≡ C-H), 2120 (C ≡ C), 1322,938 (azacyclo-s), 1632,1285,876 (-ONO2), 1129 (C-O-C).
Theoretical value average molecular weight is 1089, and actual measurement number-average molecular weight is～1068.
Above-mentioned data confirm that synthesized compound is exactly the end alkynyl radical firming agent containing itrate group polyether chain.
The application performance of 2 present invention
(1) with the compatibility of azido binder
Selecting GAP is binding agent, has investigated the compatibility containing energy end alkynyl radical firming agent and binding agent and reactivity.
The end alkynyl radical firming agent containing energy of the present invention have good compatibility with GAP binding agent, and mixture is as clear as crystal, and the mixed liquor formed can carry out curing reaction smoothly at 50～60 DEG C.
(2) mechanical property of crosslinked
With the end alkynyl radical firming agent containing energy of BPHQ firming agent and the present invention, GAP binding agent is reacted generation crosslinked respectively, and its corresponding mechanical property is in Table 1:
The impact (25 DEG C) on crosslinked mechanical property of table 1 firming agent
| Curing system (mol ratio) | Hot strength, MPa | Elongation percentage, % |
| Firming agent/GAP (1.0) of the present invention | 0.51 | 79 |
| BPHQ/GAP(1.0) | 0.34 | 68 |
| Firming agent/GAP (1.3) of the present invention | 0.72 | 60 |
| BPHQ/GAP(1.3) | 0.57 | 48 |
Visible, the crosslinked mechanical property that the present invention is formed is substantially better than BPHQ.
Claims (4)
1. one kind containing can end alkynyl radical firming agent, it is characterised in that structural formula is as follows:
Wherein, x, y, z is the positive integer of 2～5.
2. the synthetic method containing energy end alkynyl radical firming agent described in a 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, and dichloroethanes is solvent, and glycidyl ether nitrate is monomer, by cation ring-opening polymerization mechanism, synthesizes terminal hydroxy group glycidyl ether nitrate ester polyether；
2) in oxolane medium, with propine bromine, the hydroxyl of terminal hydroxy group glycidyl ether nitrate ester polyether is terminated, form the end alkynyl radical firming agent containing itrate group polyether chain.
3. synthetic method according to claim 2, it is characterized in that described step 1) in 1,3, the mol ratio of 5-trihydroxyethyl isocyanuric ester and glycidyl ether nitrate is 1:6～15,1, the mol ratio of 3,5-trihydroxyethyl isocyanuric esters and boron trifluoride etherate is 3:1, and reaction temperature is 17 DEG C～20 DEG C.
4. synthetic method according to claim 2, it is characterised in that described step 2) in the mol ratio of propine bromine and terminal hydroxy group glycidyl ether nitrate ester polyether be 3.1:1, reaction temperature is 38 DEG C～40 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610182532.0A CN105753799B (en) | 2016-03-28 | 2016-03-28 | One kind end alkynyl radical curing agent containing energy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610182532.0A CN105753799B (en) | 2016-03-28 | 2016-03-28 | One kind end alkynyl radical curing agent containing energy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105753799A true CN105753799A (en) | 2016-07-13 |
| CN105753799B CN105753799B (en) | 2018-01-23 |
Family
ID=56346578
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610182532.0A Active CN105753799B (en) | 2016-03-28 | 2016-03-28 | One kind end alkynyl radical curing agent containing energy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105753799B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942804A (en) * | 2019-04-02 | 2019-06-28 | 西安近代化学研究所 | The poly- 3- nitric acid ester methyl -3- methy oxetane prepolymer of three arm type end alkynyl radicals |
| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06192521A (en) * | 1992-04-21 | 1994-07-12 | Nisshin Fine Chem Kk | Stabilized halogen-containing resin composition |
| 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 |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
| WO2016039277A1 (en) * | 2014-09-08 | 2016-03-17 | 電気化学工業株式会社 | Composition and disassembling method |
-
2016
- 2016-03-28 CN CN201610182532.0A patent/CN105753799B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06192521A (en) * | 1992-04-21 | 1994-07-12 | Nisshin Fine Chem Kk | Stabilized halogen-containing resin composition |
| 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 |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| 张晗昱，等: "端叠氮基聚醚的合成及与多炔固化剂的交联反应", 《火炸药学报》 * |
| 徐若千,等: "三臂型叠氮含能增塑剂GAPA的合成与性能", 《含能材料》 * |
| 曹鹏，等: "固体推进剂用含能胶粘剂的研究进展", 《中国胶黏剂》 * |
| 王连心，等: "聚缩水甘油醚硝酸酯研究进展", 《化学推进剂与高分子材料》 * |
| 陈苏锋，等: "三炔丙基异氰尿酸酯的合成、表征及其非等温固化动力学", 《化工学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942804A (en) * | 2019-04-02 | 2019-06-28 | 西安近代化学研究所 | The poly- 3- nitric acid ester methyl -3- methy oxetane prepolymer of three arm type end alkynyl radicals |
| 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 |
| CN110511372A (en) * | 2019-08-28 | 2019-11-29 | 西安近代化学研究所 | One kind terminal isocyanate group curing agent containing energy and its synthetic method |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105753799B (en) | 2018-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105175707B (en) | A kind of end alkynyl radical curing agent and preparation method thereof | |
| US5681904A (en) | Azido polymers having improved burn rate | |
| CN105753799A (en) | Energy-containing terminal alkynyl curing agent and preparation method thereof | |
| CN107868596A (en) | A kind of three block nitric acid ester adhesive containing energy and its synthetic method | |
| AU621404B2 (en) | Glycidyl azide polymer and method of preparation | |
| Kawamoto et al. | Synthesis and Characterization of Glycidyl Azide‐r‐(3, 3‐bis (azidomethyl) oxetane) Copolymers | |
| CN110590484A (en) | Non-isocyanate-cured azido polyether adhesive system and propellant | |
| CN107674628A (en) | A kind of three block type alkenyl polyether adhesive and its synthetic method | |
| Zhang et al. | Synthesis and characterization of a novel fluorine-containing copolymer P (FPO/NIMMO) as a potential energetic binder | |
| CN108822288A (en) | A kind of alkenyl polyether is containing can nitric acid ester adhesive and its synthetic method | |
| Xu et al. | Structure and mechanical properties of fluorine‐containing glycidyl azide polymer‐based energetic binders | |
| Demirel et al. | A route toward multifunctional polyurethanes using triple click reactions | |
| CN110511372B (en) | Energy-containing terminal isocyanate group curing agent and synthesis method thereof | |
| Dou et al. | Research progress of nitrate ester binders | |
| CN105669493B (en) | A kind of Azide nitrate ester class oligomer and preparation method thereof | |
| Rahm et al. | Design of an ammonium dinitramide compatible polymer matrix | |
| Kawamoto et al. | Synthesis and characterization of GAP/BAMO copolymers applied at high energetic composite propellants | |
| Ou et al. | Development of energetic additives for propellants in China | |
| CN111718480B (en) | Terminal acryloxy polyether curing agent | |
| CN108276939A (en) | A kind of room temperature curing energetic binder and its synthetic method | |
| Cappello et al. | Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants | |
| Bayat et al. | Superior improvement in thermo-mechanical properties of polyurethane based on glycidyl azide polymer/polyethylene adipate | |
| CN115849995B (en) | Adhesive with dual functions on aluminum hydride, preparation method and application | |
| KASZTANKIEWICZ et al. | Synthesis of high-energy polymer–glycidyl azide polymer (GAP) | |
| Barbieri et al. | Synthesis of energetic polyethers from halogenated precursors |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |