CN108559434B - Three-functionality terminal alkenyl energetic adhesive and synthesis method thereof - Google Patents
Three-functionality terminal alkenyl energetic adhesive and synthesis method thereof Download PDFInfo
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- CN108559434B CN108559434B CN201810442119.2A CN201810442119A CN108559434B CN 108559434 B CN108559434 B CN 108559434B CN 201810442119 A CN201810442119 A CN 201810442119A CN 108559434 B CN108559434 B CN 108559434B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
Abstract
The invention discloses a trifunctional end alkenyl energetic adhesive and a synthesis method thereof, wherein the structural formula of the trifunctional end alkenyl energetic adhesive is shown as a formula (I), and the synthesis process comprises the following steps: the trifunctional poly-3-nitrate methyl-3-methyl oxa-cyclobutadine is used as a raw material, 3-isocyanic acid propylene is added, and the trifunctional alkenyl group-containing energy-containing adhesive is obtained through addition reaction. The synthesis method is convenient for large-scale preparation, and the double bonds endow the adhesive with the capability of curing at room temperature. The invention is mainly used for composite solid propellant.
Description
Technical Field
The invention relates to a trifunctional alkenyl energetic adhesive, belonging to the field of solid propellants.
Background
Currently, isocyanate curing systems have the problem of relatively high curing temperatures. The isocyanate curing system used for curing hydroxyl-terminated polybutadiene (HTPB) is cured to form polyurethane, has high curing temperature and is sensitive to moisture, for example, the isocyanate curing system consisting of Toluene Diisocyanate (TDI) and HTPB has the curing temperature of 60 ℃.
In order to solve the problems of high curing temperature and sensitivity to moisture in the traditional curing mode, a room temperature curing technology of nitrile oxide is developed. The curing agent nitrile oxide has high activity and is easy to produce curing crosslinking reaction with double bond containing adhesive, so that the curing temperature of the curing system is low and can be as low as 25-35 ℃. For example, the hogchuan subject of the science and technology university in southwest is listed in "synthesis of terephthalonitrile oxide and its room temperature curing property" fine chemical industry, 2017 (9): 1063-1069 use nitrile oxide to effect curing of the liquid polybutadiene rubber at room temperature. However, the elastomer formed after curing is free of energy and has a tensile strength of only 0.45 MPa.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide an energy-containing adhesive which not only contains nitrate energy-containing groups but also can improve the tensile strength and a synthetic method thereof.
The conception of the invention is as follows: curing of trifunctional poly (3-nitrate methyl-3-methyloxacyclobutane) with diisocyanate requires heating to 60 ℃ and is susceptible to blistering under the influence of moisture. In order to reduce the curing temperature, while avoiding the generation of bubbles, the present invention envisages: the three-functionality (poly 3-nitrate methyl-3-methyl oxa-heterocyclic ring) energy-containing adhesive is adopted to react with 3-isocyanic propylene to generate the three-functionality end-alkenyl energy-containing adhesive, and tetramethyl terephthalonitrile oxide is used for curing to perfect a three-dimensional network structure formed after curing.
In order to solve the technical problems, the trifunctional alkenyl functional adhesive disclosed by the invention has the following structural formula:
wherein m is an integer of 5 to 10.
The synthetic route of the trifunctional terminal alkenyl energy-containing adhesive is as follows:
wherein m is an integer of 5 to 10.
The invention relates to a method for synthesizing a trifunctional end-alkenyl energetic adhesive, which comprises the following steps:
adding trifunctional poly (3-nitrate methyl-3-methyl oxa-butadine) into a four-neck round-bottom flask provided with a mechanical stirring and reflux condenser tube, a thermometer and a dropping funnel, dropwise adding 3-isocyanic acid propylene at the temperature of 50 ℃, wherein the dropwise adding time is 10min, after the dropwise adding is finished, heating to 77 ℃, continuing to react for 12-24 h, and removing unreacted 3-isocyanic acid propylene under reduced pressure to obtain the trifunctional terminal alkenyl energetic adhesive; wherein the molar ratio of the trifunctional poly (3-nitrate methyl-3-methyl oxa-heterocyclic ring) to the 3-isocyanic propylene is 1: 3-3.4.
The invention has the advantages that:
the trifunctional end-alkenyl functional adhesive contains nitrate functional groups on one hand and can be cured by bifunctional nitrile oxide on the other hand, and is a room-temperature-curable functional nitrate adhesive. The elastomer formed after curing has energy content and tensile strength of 4MPa, which is greatly improved compared with 0.45MPa in the reference.
Detailed Description
Testing an instrument:
the infrared spectrum test adopts a Nexus 870 Fourier transform infrared spectrometer of Nicolet company in the United states;
the nuclear magnetic resonance test adopts AVANCE AV500 type nuclear magnetic resonance instrument of Bruker company of Germany;
the number average molecular weight was measured by GPC-50 gel permeation chromatography (PL corporation, UK); GPC test conditions: the chromatographic column is series connected by PLGel MIXED-E; the mobile phase is THF; the column temperature was 40 ℃; the detector is a differential refraction detector;
the viscosity test was carried out using a cone and plate VISCOMETER of the GAP 2000+ VISCOMETER type, Brookfiled, USA;
the elastomer mechanical property test adopts an Instron model 4505 universal material tester of the American Instron company.
Example 1
22g (10 mmol) of trifunctional poly (3-nitrate methyl-3-methyloxazetidine) is added into a four-neck round-bottom flask provided with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel, 2.49g (30mmol) of 3-isocyanic propylene is dropwise added at the temperature of 50 ℃ for 10min, the temperature is raised to 77 ℃ after the dropwise addition is finished, the reaction is continued for 12h, and the unreacted 3-isocyanic propylene is removed under reduced pressure, so that 24.4g of light yellow viscous liquid is obtained.
And (3) structural identification:
IR，νmax(cm-1): 3443(-NH), 1727(-C ═ O), 1518 (amide II peak C-N-H), 1112 (fatty ether C-O-C), 1632, 1281, 869 (-ONO)2)。
1H NMR(CDCl3,500MHz)：5.70～5.80(m,1H),5.20～5.30(m,2H),4.31～4.49(m,12H), 4.39～4.41(m,2H),3.25～3.37(m,24H),0.96～1.00(m,18H)；
13C NMR(CDCl3,125MHz)：155.97,134.37,116.31,75.84,74.93,73.77,71.51,66.55, 43.51,40.40,23.32,17.33,16.93,7.51。
Number average molecular weight 1716, viscosity 2906P (20 ℃).
The above data indicate that the synthesized compound is a designed trifunctional terminal alkenyl energy containing adhesive.
Example 2
22g (10 mmol) of trifunctional poly (3-nitrate methyl-3-methyloxazetidine) is added into a four-neck round-bottom flask provided with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel, 2.66g (32mmol) of 3-isocyanic propylene is dropwise added at the temperature of 50 ℃ for 10min, the temperature is raised to 77 ℃ after the dropwise addition is finished, the reaction is continued for 18h, and the unreacted 3-isocyanic propylene is removed under reduced pressure, so that 24.6g of light yellow viscous liquid is obtained.
Example 3
22g (10 mmol) of trifunctional poly (3-nitrate methyl-3-methyloxazetidine) is added into a four-neck round-bottom flask provided with a mechanical stirring device, a reflux condenser tube, a thermometer and a dropping funnel, 2.82g (34mmol) of 3-isocyanic propylene is dropwise added at the temperature of 50 ℃ for 10min, the temperature is raised to 77 ℃ after the dropwise addition is finished, the reaction is continued for 18h, and the unreacted 3-isocyanic propylene is removed under reduced pressure, so that 24.8g of light yellow viscous liquid is obtained.
The application performance of the trifunctional end-alkenyl energetic adhesive is as follows:
1) viscosity of trifunctional alkenyl terminated energy-containing adhesives at different temperatures
The trifunctional alkenyl-terminated energy-containing adhesive prepared by the invention is respectively tested for viscosity at different temperatures, and the obtained data are as follows:
TABLE 1 viscosity of trifunctional alkenyl terminated energy adhesives at different temperatures
As can be seen from Table 1, the viscosity of the trifunctional alkenyl group-containing adhesive at 20 ℃ is very high, probably due to the formation of-NH-CO-and-ONO2Hydrogen bonds are formed. Hydrogen bonds are formed between molecules, and the viscosity is generally higher. While the hydrogen bond forming polymer is unstable, heating can disrupt its aggregation. The viscosity gradually decreases as the temperature increases. The viscosity at 60 ℃ was only 49P.
2) Mechanical property of elastomer formed by curing with tetramethyl terephthalonitrile oxide
In a 200mL beaker equipped with magnetic stirring, 15g of trifunctional terminal alkenyl energetic binder of the invention was added at 80gCH2Cl2Dissolving, adding 1.91g of tetramethyl terephthalonitrile oxygen curing agent (wherein n (CNO): n (C) ═ C): 1), stirring uniformly to obtain a light yellow transparent solution, pouring the solution into a watch glass after 5h, curing for one week at room temperature, stamping the obtained elastomer into a dumbbell-shaped sample, and testing the mechanical properties at room temperature, wherein the tensile strength is 4MPa and the elongation is 500%.
Claims (2)
1. A trifunctional alkenyl-terminated energetic binder having a structural formula as shown in formula (I):
wherein m is an integer of 5 to 10.
2. A method of synthesizing the trifunctional alkenyl energetic adhesive of claim 1, comprising the steps of:
adding trifunctional poly (3-nitrate methyl-3-methyl oxa-butadine) into a four-neck round-bottom flask provided with a mechanical stirring and reflux condenser tube, a thermometer and a dropping funnel, dropwise adding 3-isocyanic acid propylene at the temperature of 50 ℃, wherein the dropwise adding time is 10min, after the dropwise adding is finished, heating to 77 ℃, continuing to react for 12-24 h, and removing unreacted 3-isocyanic acid propylene under reduced pressure to obtain the trifunctional terminal alkenyl energetic adhesive; wherein the molar ratio of the trifunctional poly (3-nitrate methyl-3-methyl oxa-heterocyclic ring) to the 3-isocyanic propylene is 1: 3-3.4.
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| US5468841A (en) * | 1994-04-13 | 1995-11-21 | Aerojet General Corporation | Polymerization of energetic, cyclic ether monomers using boron trifluoride tetrahydrofuranate |
| US5952458A (en) * | 1997-06-09 | 1999-09-14 | The Government Of The United States As Represented By The Secretary Of The Navy | Process for preparing a vinyl terminated polymer |
| CN107674628A (en) * | 2017-11-06 | 2018-02-09 | 西安近代化学研究所 | A kind of three block type alkenyl polyether adhesive and its synthetic method |
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| CN107868596A (en) * | 2017-12-08 | 2018-04-03 | 西安近代化学研究所 | A kind of three block nitric acid ester adhesive containing energy and its synthetic method |
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| US5468841A (en) * | 1994-04-13 | 1995-11-21 | Aerojet General Corporation | Polymerization of energetic, cyclic ether monomers using boron trifluoride tetrahydrofuranate |
| US5952458A (en) * | 1997-06-09 | 1999-09-14 | The Government Of The United States As Represented By The Secretary Of The Navy | Process for preparing a vinyl terminated polymer |
| CN107674628A (en) * | 2017-11-06 | 2018-02-09 | 西安近代化学研究所 | A kind of three block type alkenyl polyether adhesive and its synthetic method |
| CN107739588A (en) * | 2017-11-06 | 2018-02-27 | 西安近代化学研究所 | A kind of end polyene-based copolyether adhesive and its synthetic method |
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