CN112920085A - Curing agent containing energy terminal alkenyl, preparation method and application - Google Patents
Curing agent containing energy terminal alkenyl, preparation method and application Download PDFInfo
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- CN112920085A CN112920085A CN202110117013.7A CN202110117013A CN112920085A CN 112920085 A CN112920085 A CN 112920085A CN 202110117013 A CN202110117013 A CN 202110117013A CN 112920085 A CN112920085 A CN 112920085A
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- methyl
- curing agent
- oxetane
- terminal alkenyl
- energy
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- 125000003342 alkenyl group Chemical group 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 42
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 34
- CIPFOSRMMVMZPR-UHFFFAOYSA-N 2,3-dimethyloxetane Chemical compound CC1COC1C CIPFOSRMMVMZPR-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 16
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims abstract description 12
- HXBPYFMVGFDZFT-UHFFFAOYSA-N allyl isocyanate Chemical compound C=CCN=C=O HXBPYFMVGFDZFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 6
- 238000012656 cationic ring opening polymerization Methods 0.000 claims abstract description 4
- 239000004449 solid propellant Substances 0.000 claims abstract description 4
- 230000000903 blocking effect Effects 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 4
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims 1
- 229920001971 elastomer Polymers 0.000 abstract description 21
- 239000000806 elastomer Substances 0.000 abstract description 21
- 238000004132 cross linking Methods 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003380 propellant Substances 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 125000000304 alkynyl group Chemical group 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 4
- 150000001540 azides Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910004679 ONO2 Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DXTCRSXRMZSEQP-UHFFFAOYSA-N 2-benzofuran-1,3-dione;pyridine Chemical compound C1=CC=NC=C1.C1=CC=C2C(=O)OC(=O)C2=C1 DXTCRSXRMZSEQP-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- SZHZCPHKDJWHNG-UHFFFAOYSA-N dipropyl butanedioate Chemical compound CCCOC(=O)CCC(=O)OCCC SZHZCPHKDJWHNG-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- 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
- C06D5/08—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more liquids
-
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses an energy-containing terminal alkenyl curing agent, a preparation method and application thereof, which comprises the steps of firstly, taking trimethylolethane as an initiator, taking 3-nitrate methyl-3-methyl-oxetane as a monomer, adding a solvent and a catalyst, and carrying out a cationic ring-opening polymerization reaction to synthesize hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane; and then, taking dibutyltin dilaurate as a catalyst, and blocking the hydroxyl of the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane by using allyl isocyanate to form the energy-containing terminal alkenyl curing agent. The terminal alkenyl curing agent can be used for preparing solid propellant, and the elastomer prepared by the crosslinking reaction of the terminal alkenyl curing agent and GAP has the tensile strength of 0.881MPa and the elongation of 85.63 percent at the temperature of 20 ℃.
Description
Technical Field
The invention belongs to the technical field of curing propellants, and particularly relates to an energy-containing terminal alkenyl curing agent, a preparation method and application.
Background
The azide adhesive has the advantages of positive heat generation, quick combustion, high energy, clean fuel gas, good thermal stability, low mechanical sensitivity and the like, thereby being an important target for competitive research of countries in the world. Soon since the synthesis of GAP by Vandenberg in 1972, azide adhesives have found widespread use in gun-propellant, rocket propellant, gas generator and high explosive, and have been used to replace traditional inert adhesives (e.g., HTPB or HTPE) due to their energetic nature. The azide adhesive is a high molecular polymer containing terminal hydroxyl, generally forms an isocyanate curing system with a polyfunctional isocyanate curing agent when in use, and is cured by the reaction of the terminal hydroxyl and the isocyanate group, but the isocyanate curing agent in the curing system has high activity and is easy to react with water or protonic acid quickly to generate CO2Many air holes are formed in the curing process of the propellant, so that the density of the propellant is reduced, the mechanical property of the propellant is influenced, and meanwhile, the safety and the reliability of the propellant are also reduced.
In order to solve the above problems of the isocyanate curing agent, a terminal alkynyl curing agent has been developed, and a triazole crosslinked elastomer is prepared by using a curing crosslinking reaction between a terminal alkynyl group in the terminal alkynyl curing agent and an azido group on a GAP side chain, but the obtained elastomer still has a problem of low mechanical properties such as tensile strength and elongation.
Disclosure of Invention
Aiming at the technical requirements, the invention provides an energy-containing terminal alkenyl curing agent, a preparation method and application, and solves the problems of low tensile strength and elongation of the elastomer prepared by the existing terminal alkynyl curing agent and GAP crosslinking reaction.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly discloses an energy-containing terminal alkenyl curing agent, the structural formula is shown as the formula (1):
in the formula (1), x, y and z are positive integers of 2-6.
The invention also discloses a preparation method of the energy-containing terminal alkenyl curing agent, which comprises the following steps:
step 1, taking trimethylolethane as an initiator and 3-nitrate methyl-3-methyl-oxetane as a monomer, adding a solvent and a catalyst, and carrying out a cationic ring-opening polymerization reaction to synthesize hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane;
the solvent is dichloromethane or dichloroethane; the catalyst is boron trifluoride diethyl etherate, trifluoromethyl sulfonic anhydride or trifluoromethyl sulfonic acid methyl ester;
and 2, using dibutyltin dilaurate or triphenylbismuth as a catalyst, and blocking the hydroxyl of the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane by using allyl isocyanate to obtain the energy-containing terminal alkenyl curing agent.
Preferably, the reaction temperature of the system in the step 1 is 10-15 ℃, and the reaction time is 5-6 h.
Preferably, the molar ratio of trimethylolethane to 3-nitrate methyl-3-methyl-oxetane is 1:6 to 1: 18; the molar ratio of the trimethylolethane to the catalyst is 6: 1.
Preferably, the solvent is added according to the mass ratio of the monomer to the solvent of 1: 1.2-1: 1.5.
Preferably, in the step 1, firstly, an initiator, a solvent and a catalyst are mixed, stirred for 20-30 min, and then 3-nitrate methyl-3-methyl-oxetane is dropwise added into the mixed solution, the temperature of the whole reaction system is controlled to be 10-15 ℃ during the dropwise adding, and the temperature is kept for 5-6 h after the dropwise adding is finished; after the reaction is finished, separating out an organic phase, cleaning and concentrating to obtain the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane.
Preferably, the reaction temperature of the system in the step 2 is 70-75 ℃, and the reaction time is 6-7 h.
Preferably, in the step 2, the molar ratio of the allyl isocyanate to the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 3.1:1 to 3.3:1, and the mass ratio of the catalyst to the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 0.001:1 to 0.002: 1.
The invention also discloses application of the energy-containing terminal alkenyl curing agent in preparation of a solid propellant.
Compared with the prior art, the invention has the beneficial effects that:
the energy-containing terminal alkenyl curing agent contains a flexible polyether molecular chain, a nitrate group, a carbamate group and a reactive double-bond group, on one hand, the strong hydrogen bond effect among the carbamate groups can promote the microphase separation of the elastomer, and the elastomer is endowed with high mechanical property; on one hand, the chain segment length between crosslinking points and the crosslinking density of the elastomer can be increased, and the mechanical property of the elastomer is improved; nitrate groups, on the other hand, can increase the energy of the elastomer.
When the energy-containing terminal alkenyl curing agent is used specifically, the tensile strength of the elastomer prepared by the crosslinking reaction with GAP at 20 ℃ is 0.881MPa, and the elongation is 85.63%; in contrast, the BPS/GAP crosslinked elastomer of the prior art (reference 1) has a tensile strength of 0.215MPa at 20 ℃ and an elongation of 44.68%.
Detailed Description
According to the invention, carbamate groups are introduced into terminal alkenyl curing agent molecules, and stronger hydrogen bond effect is achieved among the carbamate groups, so that the aggregation of elastomer hard chain segments is facilitated, the microphase separation of the elastomer is promoted, and the tensile strength of the elastomer is improved; the flexible polyether chain is introduced into the terminal alkenyl curing agent, so that the elongation of the elastomer is improved; the energy of the elastomer is increased by incorporating nitrate groups in the terminal alkenyl curing agent.
The synthetic route of the energy-containing terminal alkenyl curing agent is as follows:
in the formula (1), x, y and z are positive integers of 2-6.
The specific synthesis process comprises the following steps:
step 1, taking trimethylolethane as an initiator and 3-nitrate methyl-3-methyl-oxetane as a monomer, adding a solvent and a catalyst, and carrying out a cationic ring-opening polymerization reaction to synthesize hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane;
the solvent is dichloromethane or dichloroethane, preferably, the addition amount of the solvent is 1: 1.2-1: 1.5 of the mass ratio of the monomer to the solvent. The catalyst is boron trifluoride diethyl etherate, trifluoromethyl sulfonic anhydride or trifluoromethyl sulfonic acid methyl ester.
In the invention, the molar ratio of the trimethylolethane to the 3-nitrate methyl-3-methyl-oxetane is preferably 1:6 to 1: 18; the molar ratio of trimethylolethane to the catalyst was 6: 1. The reaction temperature of the system is 10-15 ℃, and the reaction time is 5-6 h.
Preferably, the addition sequence of the reactants in step 1 is as follows: firstly, mixing an initiator, a solvent and a catalyst, stirring for 20-30 min, dropwise adding 3-nitrate methyl-3-methyl-oxetane into the mixed solution, controlling the temperature of the whole reaction system to be 10-15 ℃ during dropwise adding, and preserving heat for 5-6 h after dropwise adding; after the reaction is finished, separating out an organic phase, cleaning and concentrating to obtain the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane.
And 2, using dibutyltin dilaurate or triphenylbismuth as a catalyst, and using allyl isocyanate to terminate the hydroxyl of the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane to form a terminal alkenyl curing agent containing a nitrate polyether chain, namely an energy-containing terminal alkenyl curing agent.
Wherein the molar ratio of allyl isocyanate to hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 3.1:1 to 3.3:1, and the mass ratio of the catalyst to hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 0.001:1 to 0.002: 1; the reaction temperature of the system in the step is 70-75 ℃, and the reaction time is 6-7 h.
The terminal alkenyl curing agent prepared by the invention is used for reacting with azide adhesives (such as GAP, PAMMO, PBMO-THF and the like) to prepare solid propellants.
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
The test equipment used in the following examples was:
(1) the infrared spectrum is tested by a Nexus 870 Fourier transform infrared spectrometer of Nicolet company in the United states; (2) the hydroxyl value is tested by adopting a phthalic anhydride-pyridine acylation method; (3) number average molecular weight test equipment: GPC-50 gel permeation chromatography of 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 refractive detector. (4) Mechanical property test equipment: universal materials testing machine model Instron 4505, Instron corporation, usa; the test method comprises the following steps: the stretching rate is 100mm/min, according to GJB770B-2005 method 413.1.
Methylene chloride, dichloroethane, trimethylolethane, boron trifluoride diethyl etherate, dibutyltin dilaurate, and allyl isocyanate, which are used in the following examples of the present invention, are commercially available.
Example 1
Step 1, synthesizing hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane:
150mL of dichloromethane, 9.01g (0.075mol) of trimethylolethane and 1.59mL (0.0125mol) of boron trifluoride-diethyl ether complex catalyst are sequentially added into a 500mL four-neck round-bottom flask equipped with a mechanical stirring device, a reflux condenser, a thermometer and a dropping funnel, 112.73g (0.675mol) of 3-nitrate methyl-3-methyl-oxetane is started to be dropwise added after stirring for 20min at room temperature, the polymerization temperature is controlled to be 10-15 ℃ during the dropwise adding, and the reaction is kept for 6 h. With 5% NaHCO3The reaction was terminated with aqueous solution, the organic phase was separated using a separatory funnel, washed with water to neutrality and concentrated to give 114.31g of a pale yellow viscous liquid, which was designated product 1, in 93.9% yield.
Step 2, synthesizing a terminal alkenyl curing agent containing a nitrate-based polyether chain:
72.09g (0.045mol) of 3-hydroxy terminated poly (3-nitrate methyl-3-methyl-oxetane) were placed in a 500ml three-necked round-bottomed flask equipped with mechanical stirring, reflux condenser and thermometer, heated to 75 ℃ and then 0.14g dibutyltin dilaurate and 11.98g (0.144mol) of allyl isocyanate were added and the reaction was continued for 7h, and excess allyl isocyanate was distilled off under reduced pressure to give 82.91g of a pale red viscous liquid, designated product 2.
Structural characterization of product 1:
infrared (KBr, cm)-1)：3341(O-H),1632、1280、871(－ONO2) 1125 (C-O-C). Number average molecular weight: mn1602. Hydroxyl value: 68.29 mgKOH/g.
The above analytical data confirm that the synthesized product 1 is hydroxy-terminated poly-3-nitrate methyl-3-methyl-oxetane.
Structural characterization of product 2:
IR，νmax(cm-1)：3339(－NH－)，2930、2856(－CH2－)，1737(C＝O)，1658(C＝C)，1628、1281、870(－ONO2)，1129(C-O-C)。
the number average molecular weight was 1840. The alkenyl content was 1.63 mmol/g.
The above data confirm that the synthesized product 2 is an alkenyl-terminated curing agent containing nitrate-based and carbamate-based polyether chains.
Example 2
This example differs from example 1 in that: in the step 1, the catalyst is trifluoromethyl sulfonic anhydride.
The analysis of the structural characteristics of the product 1 and the product 2 of this example shows that the product 1 and the product 2 of this example are the same as those of the example 1.
Example 3
This example differs from example 1 in that: in the step 1, the catalyst is methyl trifluoromethanesulfonate.
The analysis of the structural characteristics of the product 1 and the product 2 of this example shows that the product 1 and the product 2 of this example are the same as those of the example 1.
Example 4
This example differs from example 1 in that: the catalyst in step 2 is triphenyl bismuth.
The analysis of the structural characteristics of the product 1 and the product 2 of this example shows that the product 1 and the product 2 of this example are the same as those of the example 1.
Example 5
GAP is selected as an adhesive, the product 2 prepared in the example 1 and the GAP are added into a three-necked bottle with mechanical stirring, and the mixture is stirred for 10-20 min and then is kept stand for 1-2 h. According to the mixing result of the epoxy resin and the epoxy resin, the epoxy resin containing terminal alkenyl curing agent and the GAP adhesive have good miscibility, the mixture is clear and transparent, and the formed mixed solution can be stably subjected to curing reaction at the temperature of 40-50 ℃. Table 1 shows the mechanical properties of the elastomer produced by the reaction of the energy-containing terminal alkenyl curing agent of the invention and GAP.
In addition, the present invention also adopts the research of Thomas Keicher et al, i.e., the alkynyl curing agent disclosed in Isocy anate-free curing of glycidyl-azo-polymer (GAP) with bis-propyl-succinate, 39th Int Annu Conf of ICT,2008, to cure with GAP to prepare the crosslinked elastomer of triazole, the mechanical properties of which are shown in Table 1.
TABLE 1 Effect of curing agent on mechanical Properties of elastomer (20 ℃ C.)
It can be seen that the mechanical property of the poly-triazoline elastomer formed by the reaction of the energy-containing terminal alkenyl curing agent and GAP is obviously superior to that of the BPS-based poly-triazoline elastomer.
Claims (9)
1. An energy-containing terminal alkenyl curing agent is characterized in that the structural formula is shown as the formula (1):
in the formula (1), x, y and z are positive integers of 2-6.
2. The preparation method of the terminal alkenyl curing agent containing energy as claimed in claim 1, characterized by comprising the following steps:
step 1, taking trimethylolethane as an initiator and 3-nitrate methyl-3-methyl-oxetane as a monomer, adding a solvent and a catalyst, and carrying out a cationic ring-opening polymerization reaction to synthesize hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane;
the solvent is dichloromethane or dichloroethane; the catalyst is boron trifluoride diethyl etherate, trifluoromethyl sulfonic anhydride or trifluoromethyl sulfonic acid methyl ester;
and 2, using dibutyltin dilaurate or triphenylbismuth as a catalyst, and blocking the hydroxyl of the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane by using allyl isocyanate to obtain the energy-containing terminal alkenyl curing agent.
3. The preparation method of the energy-containing terminal alkenyl curing agent as claimed in claim 2, wherein the reaction temperature of the system in the step 1 is 10-15 ℃ and the reaction time is 5-6 h.
4. The method for preparing the energy-containing terminal alkenyl curing agent according to claim 2, wherein the molar ratio of trimethylolethane to 3-nitrate methyl-3-methyl-oxetane is 1:6 to 1: 18; the molar ratio of the trimethylolethane to the catalyst is 6: 1.
5. The method for preparing the energy-containing terminal alkenyl curing agent according to claim 2, wherein the solvent is added in a mass ratio of the monomer to the solvent of 1:1.2 to 1: 1.5.
6. The preparation method of the energy-containing terminal alkenyl curing agent as claimed in claim 2, 4 or 5, wherein in the step 1, firstly, the initiator, the solvent and the catalyst are mixed, stirred for 20-30 min, then 3-nitrate methyl-3-methyl-oxetane is dripped into the mixed solution, the temperature of the whole reaction system is controlled to be 10-15 ℃ during dripping, and heat preservation is carried out for 5-6 h after dripping is finished; after the reaction is finished, separating out an organic phase, cleaning and concentrating to obtain the hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane.
7. The preparation method of the energy-containing terminal alkenyl curing agent according to claim 2, wherein the reaction temperature of the system in the step 2 is 70-75 ℃, and the reaction time is 6-7 h.
8. The method of claim 2, wherein in step 2, the molar ratio of allyl isocyanate to hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 3.1:1 to 3.3:1, and the mass ratio of catalyst to hydroxyl-terminated poly-3-nitrate methyl-3-methyl-oxetane is 0.001:1 to 0.002: 1.
9. Use of the terminal alkenyl-containing curing agent of claim 1 for the preparation of solid propellants.
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