CN113372552A - Polytriazole resin, condensate, preparation method and application thereof - Google Patents
Polytriazole resin, condensate, preparation method and application thereof Download PDFInfo
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- CN113372552A CN113372552A CN202010163663.0A CN202010163663A CN113372552A CN 113372552 A CN113372552 A CN 113372552A CN 202010163663 A CN202010163663 A CN 202010163663A CN 113372552 A CN113372552 A CN 113372552A
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- polyethylene glycol
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- 239000011347 resin Substances 0.000 title claims abstract description 125
- 229920005989 resin Polymers 0.000 title claims abstract description 123
- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 86
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 80
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 claims abstract description 5
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 54
- 238000010125 resin casting Methods 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 46
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 22
- XCJNTCCFVMAYRG-UHFFFAOYSA-N CC1=C(C=CC(=C1)N=[N+]=[N-])C2=CC=C(C=C2)N=[N+]=[N-] Chemical group CC1=C(C=CC(=C1)N=[N+]=[N-])C2=CC=C(C=C2)N=[N+]=[N-] XCJNTCCFVMAYRG-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000000465 moulding Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
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- 125000002355 alkine group Chemical group 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 33
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 30
- 238000005266 casting Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- 238000004821 distillation Methods 0.000 description 15
- 238000005498 polishing Methods 0.000 description 15
- 238000007711 solidification Methods 0.000 description 15
- 230000008023 solidification Effects 0.000 description 15
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- 239000000126 substance Substances 0.000 description 11
- 238000002411 thermogravimetry Methods 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000013001 point bending Methods 0.000 description 8
- 229940068918 polyethylene glycol 400 Drugs 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 238000010998 test method Methods 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- OIDACLQVAGIDMT-UHFFFAOYSA-N n-(1-benzylpiperidin-4-yl)-2,4-dichlorobenzamide Chemical compound ClC1=CC(Cl)=CC=C1C(=O)NC1CCN(CC=2C=CC=CC=2)CC1 OIDACLQVAGIDMT-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 239000011157 advanced composite material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 238000012512 characterization method Methods 0.000 description 4
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- 238000000921 elemental analysis Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 4
- 229940085675 polyethylene glycol 800 Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- 150000003852 triazoles Chemical group 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- -1 alkynyl compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000010981 drying operation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- 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
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/06—Polyhydrazides; Polytriazoles; Polyamino-triazoles; Polyoxadiazoles
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses polytriazole resin, a condensate, and a preparation method and application thereof. The polytriazole resin is a copolymer prepared by performing 1, 3-dipolar cycloaddition reaction on terminal azido polyethylene glycol, 4 '-diazido methyl biphenyl and N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane; the preparation method of the polytriazole resin comprises the following steps: under the condition of the existence of an organic solvent, the end azido polyethylene glycol, 4 '-diazido methyl biphenyl and N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane are subjected to polymerization reaction to prepare the polytriazole resin. The polytriazole resin prepared by the method has ideal toughness and bending performance, good solubility, good heat resistance and good thermal stability, and is expected to be widely applied to the fields of aviation, aerospace and the like.
Description
Technical Field
The invention relates to polytriazole resin, a condensate, and a preparation method and application thereof.
Background
Advanced composite materials and their technology are important material bases and leading technologies for aerospace. The advanced resin-based composite material can obviously reduce the mass of an aircraft, the weight of a manufactured part is reduced by 20-30% compared with that of a traditional aerospace structure material, but with the development of aerospace manufacturing technology towards high speed and multi-functionalization, the weight reduction is no longer the only purpose of the application of the composite material in the aircraft, and advanced equipment such as high-speed airplanes, aerospace airplanes, aero-engines and the like also provides performance requirements of heat resistance, molding process, good toughness and the like for advanced composite material resin matrixes. Reasonable structure and material design are utilized, the toughness of the matrix resin is improved, and the application range of the advanced composite material in the aerospace field can be expanded. Therefore, how to obtain a thermosetting resin having excellent toughness while ensuring good heat resistance has been the focus of research. In recent years, a series of polytriazole resins have been prepared and systematically studied by the advanced resin composite research laboratory at the university of east China's science using the 1, 3-dipolar cycloaddition reaction of an alkynyl compound and an azido compound. Research shows that the polytriazole resin can be cured at low temperature, the cured resin has excellent processability, thermal property and mechanical property, and can be used as a resin matrix of an advanced composite material, but the polytriazole resin has poor toughness. At present, the research on toughening polytriazole resin is rarely reported.
Therefore, there is a need in the art to develop a polytriazole resin that has excellent mechanical properties, such as good toughness, good thermal stability and good solubility.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect of poor toughness of polytriazole resin in the prior art, and provides polytriazole resin, a cured product, and preparation methods and applications thereof. The polytriazole resin prepared by the method has ideal toughness and bending performance, good solubility, good heat resistance and good thermal stability, and is expected to be widely applied to the fields of aviation, aerospace and the like.
The invention solves the technical problems through the following technical scheme.
The invention provides polytriazole resin which is a copolymer prepared from azido-terminated polyethylene glycol, 4 '-diazide methyl biphenyl and N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane through a 1, 3-dipolar cycloaddition reaction;
wherein, the structural formula of the azido-terminated polyethylene glycol is shown as follows:
the structural formula of the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane is shown as follows:
the structural formula of the 4, 4' -diazido methyl biphenyl is shown as follows:
the molar ratio of azido to alkynyl is 1: (1.02-1.10); the mol ratio of the azido-terminated polyethylene glycol to the 4, 4' -diazido-methyl biphenyl is 1: (3.5-20.5).
In the present invention, the molar ratio of the azide group to the alkyne group is preferably 1: (1.03-1.07), more preferably 1: 1.05. as is known in the art, the alkynyl group is derived from N, N, N ', N' -tetrapropargyl-4, 4 '-diamino-diphenylmethane, 1 mole of N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane containing 4 moles of alkynyl group; the azide group is derived from azido-terminated polyethylene glycol and 4,4 '-diazido-methyl biphenyl, 1mol of azido-terminated polyethylene glycol contains 2mol of azide group, and 1mol of 4, 4' -diazido-methyl biphenyl contains 2mol of azide group.
In the present invention, the molar ratio of the azido-terminated polyethylene glycol to the N, N '-tetrapropargyl-4, 4' -diamino-diphenylmethane may be conventional in the art, and is preferably 1: (2.57-10.5), more preferably 1: (2.57-8), more preferably 1: (2.57-5.35), for example, 1: 2.625, 1: 3.5 or 1: 5.25.
in the present invention, the molar ratio of the azido-terminated polyethylene glycol to the 4, 4' -diazido-methyl biphenyl is preferably 1: (4-19), more preferably 1: (4-14), more preferably 1: (4-9), for example, 1: 5.67. in the invention, the dosage of the azido-terminated polyethylene glycol is not selected at will, and the research and development process finds that when the molar ratio of the azido-terminated polyethylene glycol to the 4, 4' -diazido-methyl biphenyl is more than 1: 3.5, although the toughness is enhanced, the thermal stability, heat resistance and bending property are inferior; when the molar ratio of the azido-terminated polyethylene glycol to the 4, 4' -diazido-methyl biphenyl is less than 1: at 20.5, the effect of improving the toughness is not obvious.
Preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: (4-19), the average molecular weight of the azido-terminated polyethylene glycol is 400-800, preferably 400 or 600.
Preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: (4-9), the average molecular weight of the azido-terminated polyethylene glycol is 400-800, preferably 400 or 600;
preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: 5.67, the average molecular weight of the azido-terminated polyethylene glycol is 400.
In the present invention, n in the azido-terminated polyethylene glycol is preferably 6 to 16, more preferably 11.
In the present invention, the azido-terminated polyethylene glycol may have an average molecular weight of 200 to 1200, preferably 400 to 800, such as 600.
In the invention, the polytriazole resin is easily dissolved in one or more of acetone, tetrahydrofuran, acetonitrile, ethyl acetate, a chlorinated hydrocarbon solvent, dimethyl sulfoxide and N, N-dimethylformamide.
The invention also provides a preparation method of the polytriazole resin, which comprises the following steps: and in the presence of an organic solvent, carrying out polymerization reaction on the azido-terminated polyethylene glycol, the 4,4 '-diazido-methylbiphenyl and the N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane to obtain the polytriazole resin.
In the present invention, the organic solvent may be an organic solvent which is conventionally used in the chemical field, can dissolve the raw material, and is easily removed by distillation under reduced pressure, and for example, acetone may be used.
In the present process, the conditions of the polymerization reaction may be those conventional in the art for such reactions. The polymerization temperature is preferably 50 to 70 ℃, more preferably 60 ℃. The polymerization time is preferably 3 to 6 hours, and more preferably 4 hours.
In the method, the solid content of the reaction system before the polymerization reaction can be conventional in the art, and is preferably 50-70%. The solid content is the percentage of the total mass of the azido-terminated polyethylene glycol, the 4,4 '-diazido-methylbiphenyl and the N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane in the total mass of the reaction system.
In the present invention, the polymerization reaction further comprises a solvent removal step after the polymerization reaction is completed. The conditions and methods of solvent removal can be conventional in the art.
In the present invention, the preparation method of the azido-terminated polyethylene glycol can be conventional in the art, and preferably comprises the following steps:
a. under the condition of inert atmosphere and organic solvent, mixing polyethylene glycol and thionyl chloride, and reacting to prepare chlorinated polyethylene glycol;
b. and reacting the chlorinated polyethylene glycol with sodium azide in the presence of an organic solvent.
In the preparation process of the azido-terminated polyethylene glycol, in step a, the inert atmosphere can be an inert atmosphere conventionally used in the art, and preferably nitrogen.
In the preparation process of the azido-terminated polyethylene glycol, in step a, the organic solvent may be an organic solvent which is conventional in the chemical field, can dissolve raw materials, and is easily removed by reduced pressure distillation, for example, toluene.
In the preparation process of the azido-terminated polyethylene glycol, in step a, the molar ratio of the polyethylene glycol to the thionyl chloride can be a molar ratio which is conventional in the reaction of the type in the field, and is preferably 1: (7-9), more preferably 1: 8.
in the preparation process of the azido-terminated polyethylene glycol, in step a, the thionyl chloride is preferably added in the form of a thionyl chloride solution. The concentration of the thionyl chloride in the thionyl chloride solution can be conventional in the art, and the molar volume ratio of the thionyl chloride to the thionyl chloride solution can be generally 0.05-0.2 mol/mL, for example, 0.1 mol/mL. In the thionyl chloride solution, the solvent may be an organic solvent which is conventionally used in the chemical field to dissolve the raw material and is easily removed by distillation under reduced pressure, and may be, for example, toluene.
In the preparation process of the azido-terminated polyethylene glycol, in step a, the thionyl chloride solution is preferably added dropwise. The dropping time can be 1-3 h, preferably 2 h.
In the preparation process of the azido-terminated polyethylene glycol, in step a, the mixing temperature can be a temperature conventionally used in the reaction in the field, and preferably room temperature.
In the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction temperature can be a temperature conventionally used in the reaction in the field, preferably 70-90 ℃, and more preferably 80 ℃.
In the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction time can be the time conventionally used in the field, preferably 35 to 45 hours, and more preferably 40 hours.
In the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction is finished and then further comprises solvent removal and drying treatment. Wherein the solvent removal operations and conditions may be conventional in the art. The drying operation and conditions may be conventional in the art and may typically be vacuum drying.
In the preparation process of the azido-terminated polyethylene glycol, in the step b, the organic solvent can be an organic solvent which is conventional in the chemical field, can dissolve raw materials and is easy to remove by reduced pressure distillation, and for example, the organic solvent can be N, N-dimethylformamide.
In the preparation process of the azido-terminated polyethylene glycol, in the step b, the molar ratio of the chlorinated polyethylene glycol to the sodium azide can be the molar ratio which is conventional in the reaction in the field, and is preferably 1: (4-6), more preferably 1: 5.
In the preparation process of the azido-terminated polyethylene glycol, in the step b, the reaction temperature can be a temperature conventional in the field, preferably 70-90 ℃, and more preferably 80 ℃.
In the preparation process of the azido-terminated polyethylene glycol, in the step b, the reaction time can be the time conventional in the field, preferably 20-30 h, and more preferably 24 h.
In the preparation process of the azido-terminated polyethylene glycol, in the step b, after the reaction is finished, post-treatment is carried out; the post-treatment operation is preferably carried out as follows: cooling, filtering, extracting, drying and removing the solvent to obtain the azido-terminated polyethylene glycol.
Wherein the cooling operation and conditions may be conventional in the art. The filtration operations and conditions may be conventional in the art. The extraction may be carried out in conventional manner, typically using methylene chloride and water, and collecting the methylene chloride phase. Preferably, the extraction is repeated 5-7 times. The drying operation and conditions may be conventional in the art, and may be generally drying with anhydrous magnesium sulfate. The solvent removal operations and conditions may be conventional in the art. The solvent removal further comprises a drying treatment, and the operation and conditions of the drying can be conventional in the field, and can be vacuum drying generally.
The invention also provides a preparation method of the polytriazole resin casting body condensate, which specifically comprises the following steps: the polytriazole resin is cured and molded to obtain the cured product of the polytriazole resin casting body.
The conditions and methods for curing and shaping can be those conventional in the art for such reactions. The temperature of the curing molding is preferably 60 to 220 ℃, and more preferably 80 to 210 ℃. The time for curing and molding is preferably 18-22 h.
In a preferred embodiment, the curing molding is performed in a segmented manner, and the curing is performed at 60-80 ℃ and then at 100-210 ℃.
In a preferred embodiment, the curing molding is performed in a segmented manner, and the curing molding is performed by firstly preserving heat for 10-12 hours at 60-80 ℃, then preserving heat for 1-3 hours by heating to 110-120 ℃, then preserving heat for 1-3 hours by heating to 140-150 ℃, then preserving heat for 1-3 hours by heating to 170-180 ℃, and preserving heat for 1-3 hours by heating to 200-210 ℃.
In a preferred embodiment, the curing and forming are performed in a segmented manner, and the curing and forming are performed by firstly preserving heat at 80 ℃ for 12 hours, then preserving heat at 120 ℃ for 2 hours, then preserving heat at 150 ℃ for 2 hours, then preserving heat at 180 ℃ for 2 hours, and then preserving heat at 210 ℃ for 2 hours.
The invention also provides a polytriazole resin casting body condensate prepared by the preparation method of the polytriazole resin casting body condensate.
In the method, the 5 wt% thermal weight loss temperature T of the solidified material of the polytriazole resin casting bodyd5May be 330 to 351 ℃, preferably 331 to 350 ℃, such as 341 ℃ or 345 ℃.
In this method, the glass transition temperature T of the cured product of the cast polytriazole resingCan be 100 to 209 ℃, preferably 107 to 195 ℃, such as 122 ℃, 158 ℃, 169 ℃ or 190 ℃.
In the present invention, the bending strength of the cured product of the polytriazole resin casting may be 83-125.8 MPa, preferably 83.99-114 MPa, such as 84.27MPa, 104.5MPa, 108.4MPa or 113.1 MPa.
In the present invention, the flexural modulus of the cured product of the polytriazole resin casting may be 2.2-3.0 GPa, preferably 2.24-2.91 GPa, for example 2.24 + -0.04 GPa, 2.31 + -0.02 GPa, 2.57 + -0.01 GPa, 2.57 + -0.02 GPa, 2.60 + -0.05 GPa or 2.91 + -0.01 GPa.
In this method, the impact strength of the cured product of the polytriazole resin casting body can be adjustedIs 41.5 to 80kJ/m2Preferably 46.4 to 79.6kJ/m2For example 62.1kJ/m2Or 70.4kJ/m2。
The invention also provides application of the polytriazole resin as a tough material in the field of military industry or aerospace industry.
In the invention, the room temperature can be 10-30 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: according to the invention, the polytriazole resin with the main chain containing the long-chain polyether structure is synthesized, the flexible chain is introduced into the main chain structure of the polytriazole resin, so that a larger free movement space is obtained between rigid rings (benzene ring and triazole ring) in a polytriazole resin system, and when the polytriazole resin is impacted, more energy can be absorbed, so that the toughness of the polytriazole resin is greatly improved; meanwhile, the introduction of ether bond endows the polytriazole resin with good processing performance, and the resin is easily dissolved in solvents such as acetone, THF, acetonitrile, ethyl acetate, chlorohydrocarbon solvents, strong polar solvents DMSO and DMF except methanol, petroleum ether and diethyl ether at room temperature. And the high thermal stability of the polytriazole resin condensate is kept. As a resin matrix of an advanced composite material, the resin is expected to be widely applied in the fields of aerospace and the like.
Drawings
FIG. 1 is an SEM photograph showing an impact cross-section of a cured product of the polytriazole resin obtained in comparative example 1.
FIG. 2 is an SEM photograph showing a cross-section of a cured product of a cast product of the polytriazole resin EPTA-4-20 obtained in example 4.
FIG. 3 is an SEM photograph showing a cross-section of a cured product of a cast product of the polytriazole resin EPTA-6-20 obtained in example 5.
FIG. 4 is an SEM photograph showing a shock section of a cured product of a cast product of the polytriazole resin EPTA-8-20 obtained in example 6.
FIG. 5 is a graph of infrared analysis of the polytriazole resin EPTA-4-10 obtained in example 2 at various stages during the curing reaction.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The structure of the synthesized azido-terminated polyethylene glycol uses hydrogen nuclear magnetic resonance spectrum (1H-NMR). The structural change during the curing of the polytriazole resin is characterized by infrared spectroscopy (FTIR). Hydrogen nuclear magnetic resonance spectroscopy (1H-NMR) Using a Bruker AVANCE 500 model high resolution Fourier transform nuclear magnetic resonance spectrometer, operating frequency 400MHz, solvent CDCl3TMS is used as an internal standard; fourier Infrared Spectroscopy (FT-IR) analysis Using a Nicolet 6700 Fourier Infrared Spectroscopy, KBr pellet method, from Nicolet, USA, scanning Range 4000--1Resolution of 0.09cm-1And the number of scanning times is 32.
The thermal properties of the thermally cured polytriazole resins can be tested by TGA and DMA; wherein the thermal stability can be tested by Thermal Gravimetric Analysis (TGA) in nitrogen atmosphere to obtain 5% thermal gravimetric temperature (T)d5) (ii) a Wherein, the heat resistance is tested by DMA, and the glass transition temperature (T) can be obtainedg) This reflects the thermal stability and heat resistance of the resin.
The curing process of the polytriazole resin is a step-shaped heating curing process, and a solidified substance of the polytriazole resin casting body is prepared. The bending property of the cured triazole resin casting body is tested by a three-point bending method.
The bending strength of the resin casting body is tested according to GB/T2567-2008, the experimental loading speed is 2mm/min, and the resin casting body is continuously loaded until the test sample is damaged during the experiment.
The content of hydrocarbon nitrogen in organic matters is measured by adopting a German ELEMENTAR VARIO EL III type element analyzer and burning the corresponding reagent in a pure oxygen environment or cracking the reagent in inert gas at high temperature.
Italian CEAST 9050 cantilever beam impact tester 1# is adopted for impact resistance; the reference standard is GB/T1843-2008, and the test method is a non-gap cantilever impact test method.
The hardness testing instrument is an HR-50 Rockwell hardness tester; and polishing the sample strip subjected to impact fracture by using abrasive paper, and testing by using a hardness tester after the surface of the sample is ensured to be flat.
EXAMPLE 1 preparation of polytriazole resin EPTA-4-5
(1) Synthesis of azido-terminated polyethylene glycol having molecular weight of 400(ATPEG400)
a. 32g of polyethylene glycol 400(80mmol) and 200mL of toluene were put into a 500mL three-necked flask under a nitrogen atmosphere, and a mixture of 76g of thionyl chloride (640mmol) and 65mL of toluene was slowly dropped through a constant pressure dropping funnel at room temperature for 2 hours, followed by reaction at 80 ℃ for 40 hours after completion of dropping. After the reaction is finished, the toluene and the unreacted thionyl chloride are removed by reduced pressure distillation, and the transparent dark brown liquid-end chlorinated polyethylene glycol 400 is obtained by vacuum drying, wherein the yield is 80-83%.
b. 8g of the chloro-terminated polyethylene glycol 400(20mmol) obtained in step a, 7g of sodium azide (100mmol) and 350mL of DMF were put in a 500mL three-necked flask and reacted at 80 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered to remove unreacted sodium azide, and then poured into 500mL of deionized water. Extracted with dichloromethane and washed 6 times with deionized water. And drying the organic phase by using anhydrous magnesium sulfate, distilling to remove redundant dichloromethane, and drying in vacuum to obtain the light yellow terminal azido-based polyethylene glycol 400(ATPEG400), wherein the yield is 64-67%.
Structural analysis characterization of ATPEG 400:1H-NMR(CDCl3,TMS)δ(ppm)：3.39(t,4H,N-C-H),3.67(m,28H,H-C-O)。
elemental analysis results: theoretical value: c, 45.71%; h, 7.62%; n, 20.00%; measurement values: c, 46.33%; h, 7.08%; n,19.83 percent.
The value of n for ATPEG400 is 6.
(2) Preparation of polytriazole resin EPTA-4-5
Adding ATPEG400(1.05g,2.50mmol) prepared in the step (1), 4 '-diazido-methyl biphenyl (BPDBA,12.54g,47.50mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 9.76g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-4-5 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-4-5.
The polytriazole resin EPTA-4-5 prepared in example 1 is used to prepare a polytriazole resin casting body cured product, and the preparation method of the polytriazole resin casting body cured product comprises the following steps: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. The polytriazole resin EPTA-4-5 is poured into a mold, after the resin is molten, the mold is kept under vacuum for about 2 hours to remove air and solvent until no air bubbles appear within 3 seconds, and then the mold is transferred to a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 351 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 209 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The bending property of the solidified material of the polytriazole resin casting body is tested by adopting a three-point bending test method, and the result shows that the bending modulus of the polytriazole resin casting body is 2.91 +/-0.01 GPa, and the bending strength of the polytriazole resin casting body is 125.8 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact experiment method, and the result shows that the impact strength is 41.5kJ/m2。
EXAMPLE 2 preparation of polytriazole resin EPTA-4-10
(1) Synthesis of azido-terminated polyethylene glycol having molecular weight of 400(ATPEG400)
a. 32g of polyethylene glycol 400(80mmol) and 200mL of toluene were put into a 500mL three-necked flask under a nitrogen atmosphere, and a mixture of 76g of thionyl chloride (640mmol) and 65mL of toluene was slowly dropped through a constant pressure dropping funnel at room temperature for 2 hours, followed by reaction at 80 ℃ for 40 hours after completion of dropping. After the reaction is finished, the toluene and the unreacted thionyl chloride are removed by reduced pressure distillation, and the transparent dark brown liquid-end chlorinated polyethylene glycol 400 is obtained by vacuum drying, wherein the yield is 80-83%.
b. 8g of the chloro-terminated polyethylene glycol 400(20mmol) obtained in step a, 7g of sodium azide (100mmol) and 350mL of DMF were put in a 500mL three-necked flask and reacted at 80 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered to remove unreacted sodium azide, and then poured into 500mL of deionized water. Extracted with dichloromethane and washed 6 times with deionized water. And drying the organic phase by using anhydrous magnesium sulfate, distilling to remove redundant dichloromethane, and drying in vacuum to obtain the light yellow terminal azido-based polyethylene glycol 400(ATPEG400), wherein the yield is 64-67%.
Structural analysis characterization of ATPEG 400:1H-NMR(CDCl3,TMS)δ(ppm)：3.39(t,4H,N-C-H),3.67(m,28H,H-C-O)。
elemental analysis results: theoretical value: c, 45.71%; h, 7.62%; n, 20.00%; measurement values: c, 46.33%; h, 7.08%; n,19.83 percent.
The value of n for ATPEG400 is 6.
(2) Preparation of polytriazole resin EPTA-4-10
Adding ATPEG400(2.10g,5.00mmol) prepared in the step (1), 4 '-diazido-methyl biphenyl (BPDBA,11.88g,45.00mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 9.93g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-4-10 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-4-10.
The polytriazole resin EPTA-4-10 prepared in example 2 is used to prepare a polytriazole resin casting body condensate, and the preparation method of the polytriazole resin casting body condensate comprises the following steps: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. Pouring the polytriazole resin EPTA-4-10 into a mold, after the resin is molten, keeping the mold under vacuum for about 2 hours to remove air and solvent until no bubbles appear within 3 seconds, and then transferring the mold into a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 341 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 190 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The three-point bending test method is adopted to test the bending property of the solidified material of the polytriazole resin casting body, and the result shows that the bending modulus is 2.57 +/-0.02 GPa, and the bending strength is 113.1 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact experiment method, and the result shows that the impact strength is 46.4kJ/m2。
The hardness of the cured product of the polytriazole resin casting was 31. + -. 1.9 Hba.
EXAMPLE 3 preparation of polytriazole resin EPTA-4-15
(1) Synthesis of azido-terminated polyethylene glycol having a molecular weight of 400(ATPEG400) was performed as in step (1) of example 2.
The value of n for ATPEG400 is 6.
(2) Preparation of polytriazole resin EPTA-4-15
Adding ATPEG400(3.15g,7.50mmol) prepared in the step (1), 4 '-diazido-methyl biphenyl (BPDBA,11.23g,42.50mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 10.10g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-4-15 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-4-15.
The polytriazole resin EPTA-4-15 prepared in example 3 was used to prepare a casting cured product of polytriazole resin, and the preparation method of the casting cured product of polytriazole resin was as follows: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. The polytriazole resin EPTA-4-15 is poured into a mold, after the resin is molten, the mold is kept under vacuum for about 2 hours to remove air and solvent until no air bubbles appear within 3 seconds, and then the mold is transferred to a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 345 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 169 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The three-point bending test method is adopted to test the bending property of the solidified material of the polytriazole resin casting body, and the result shows that the bending modulus is 2.57 +/-0.01 Gpa, and the bending strength is 108.4 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact test method, and the result shows that the impact strength is 64.0kJ/m2。
The hardness of the cured product of the polytriazole resin casting was 26. + -. 1.2 Hba.
EXAMPLE 4 preparation of polytriazole resin EPTA-4-20
(1) Synthesis of azido-terminated polyethylene glycol monomer having a molecular weight of 400(ATPEG400) was performed as in step (1) of example 2.
The value of n for ATPEG400 is 6.
(2) Preparation of polytriazole resin EPTA-4-20
Adding ATPEG400(4.2g,10mmol) prepared in the step (1), 4 '-diazido methyl biphenyl (BPDBA,10.56g,40mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 10.26g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-4-20 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-4-20.
The polytriazole resin casting body condensate is prepared by the polytriazole resin EPTA-4-20 prepared in example 4, and the preparation method of the polytriazole resin casting body condensate is as follows: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. The polytriazole resin EPTA-4-20 is poured into a mold, after the resin is molten, kept under vacuum for about 2 hours to remove air and solvent until no bubbles appear within 3 seconds, and then transferred to a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 331 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 158 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The three-point bending test method is adopted to test the bending property of the solidified material of the polytriazole resin casting body, and the result shows that the bending modulus is 2.60 +/-0.05 GPa, and the bending strength is 104.5 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. Using unnotched cantileversThe impact resistance of the beam impact test method is tested, and the result shows that the impact strength is 70.4kJ/m2。
The hardness of the cured product of the polytriazole resin casting was 23. + -. 2.2 Hba.
EXAMPLE 5 preparation of polytriazole resin EPTA-6-20
(1) Synthesis of azido-terminated polyethylene glycol having molecular weight of 600(ATPEG600)
a. 48g of polyethylene glycol 600(80mmol) and 200mL of toluene were put into a 500mL three-necked flask under a nitrogen atmosphere, and a mixed solution of 76g of thionyl chloride (640mmol) and 65mL of toluene was slowly dropped through a constant pressure dropping funnel at room temperature for 2 hours, followed by reaction at 80 ℃ for 40 hours after completion of dropping. After the reaction is finished, the toluene and the unreacted thionyl chloride are removed by reduced pressure distillation, and the transparent dark brown liquid-end chlorinated polyethylene glycol 600 is obtained by vacuum drying, wherein the yield is 70-75%.
b. 12.52g of the terminal chlorinated polyethylene glycol 600(20mmol) obtained in step a, 7g of sodium azide (100mmol) and 350mL of DMF were put in a 500mL three-necked flask and reacted at 80 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered to remove unreacted sodium azide, and then poured into 500mL of deionized water. Extracted with dichloromethane and washed 6 times with deionized water. And drying the organic phase by using anhydrous magnesium sulfate, then distilling under reduced pressure to remove redundant dichloromethane, and drying under vacuum to obtain the faint yellow end azido polyethylene glycol 600(ATPEG600), wherein the yield is 54-60%.
Structural analysis characterization of ATPEG 600:1H-NMR(CDCl3,TMS)δ(ppm)：3.32(t,4H,N-C-H),3.65(m,48H,H-C-O)。
elemental analysis results: theoretical value: c, 48.75%; h, 8.12%; n, 13.13%; measurement values: c, 49.78%; h, 7.95%; n, 11.89%.
The value of n for ATPEG600 is 11.
(2) Preparation of polytriazole resin EPTA-6-20
Adding ATPEG600(6.4g,10mmol) prepared in the step (1), 4 '-diazido methyl biphenyl (BPDBA,10.56g,40mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 11.19g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-6-20 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-6-20.
The polytriazole resin EPTA-6-20 prepared in example 5 is used to prepare a polytriazole resin casting body cured product, and the preparation method of the polytriazole resin casting body cured product comprises the following steps: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. The polytriazole resin EPTA-6-20 is poured into a mold, after the resin is molten, kept under vacuum for about 2 hours to remove air and solvent until no bubbles appear within 3 seconds, and then transferred to a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 341 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) It was 122 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The bending property of the solidified material of the polytriazole resin casting body is tested by adopting a three-point bending test method, and the result shows that the bending modulus of the polytriazole resin casting body is 2.24 +/-0.04 GPa, and the bending strength of the polytriazole resin casting body is 83.99 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact experiment method, and the result shows that the impact strength is 79.6kJ/m2。
The hardness of the cured product of the polytriazole resin casting was 13. + -. 2.3 Hba.
EXAMPLE 6 preparation of polytriazole resin EPTA-8-20
(1) Synthesis of azido-terminated polyethylene glycol monomer (ATPEG800) having molecular weight of 800
a. 64g of polyethylene glycol 800(80mmol) and 200mL of toluene were put into a 500mL three-necked flask under a nitrogen atmosphere, and a mixed solution of 76g of thionyl chloride (640mmol) and 65mL of toluene was slowly dropped through a constant pressure dropping funnel at room temperature for 2 hours, followed by reaction at 80 ℃ for 40 hours after completion of dropping. After the reaction is finished, the toluene and the unreacted thionyl chloride are removed by reduced pressure distillation, and the transparent dark brown liquid-end chlorinated polyethylene glycol 800 is obtained by vacuum drying, with the yield of 60-72%.
b. 16.94g of the terminal chlorinated polyethylene glycol 800(20mmol) obtained in step a, 7g of sodium azide (100mmol) and 350mL of DMF were put in a 500mL three-necked flask and reacted at 80 ℃ for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered to remove unreacted sodium azide, and then poured into 500mL of deionized water. Extracted with dichloromethane and washed 6 times with deionized water. And drying the organic phase by using anhydrous magnesium sulfate, then distilling under reduced pressure to remove redundant dichloromethane, and drying under vacuum to obtain the faint yellow end azido polyethylene glycol 800(ATPEG800) with the yield of 50-60%.
Structural analysis characterization of ATPEG 800:1H-NMR(CDCl3,TMS)δ(ppm)：3.32(t,4H,N-C-H),3.65(m,68H,H-C-O)。
elemental analysis results: theoretical value: theoretical value: c, 49.26%; h, 8.3%; n, 9.87%; measurement values: c, 50.23%; h, 8.37%; and N, 9.77%.
ATPEG800 has an n value of 16.
(2) Preparation of polytriazole resin EPTA-8-20
Adding ATPEG800(8.6g,10mmol) prepared in the step (1), 4 '-diazido methyl biphenyl (BPDBA,10.56g,40mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 12.15g of acetone into a three-neck flask to prepare an acetone solution with the solid content of 70%, and stirring and reacting at the temperature of 60 ℃ for 4 hours to obtain a clear and uniform light yellow polytriazole resin EPTA-8-20 solution. Acetone was removed by distillation to give yellow polytriazole resin EPTA-8-20.
The polytriazole resin EPTA-8-20 prepared in example 6 was used to prepare a casting cured product of polytriazole resin, and the preparation method of the casting cured product of polytriazole resin was as follows: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. Pouring the polytriazole resin EPTA-8-20 into a mold, after the resin is molten, keeping the mold under vacuum for about 2 hours to remove air and solvent until no air bubbles appear within 3 seconds, and then transferring the mold into a high-temperature oven for curing. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h to cure the casting body, and demoulding after curing to obtain the yellow hard polytriazole resin casting body cured substance.
After the solidification, grinding into powder for thermogravimetric analysis. Under nitrogen atmosphere, the 5% weight loss temperature was 345 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 107 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The bending property of the solidified material of the polytriazole resin casting body is tested by adopting a three-point bending test method, and the result shows that the bending modulus of the polytriazole resin casting body is 2.31 +/-0.02 GPa, and the bending strength of the polytriazole resin casting body is 84.27 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact experiment method, and the result shows that the impact strength is 62.1kJ/m2。
The hardness of the cured product of the polytriazole resin casting was 10. + -. 2.7 Hba.
Comparative example 1
4,4 '-diazido methyl biphenyl (BPDBA,13.20g,50mmol), N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane (TPDDM,9.19g,26.25mmol) and 9.60g of acetone are added into a three-neck flask to prepare an acetone solution with the solid content of 70%, the reaction temperature is 60 ℃, and the mixture is stirred and reacted for 4 hours at the temperature to obtain a clear and uniform light yellow PTA resin solution. Acetone was removed by distillation to give yellow PTA resin.
Preparing the PTA resin prepared in the comparative example 1 into a cured product of a PTA resin casting body, wherein the preparation method of the cured product of the PTA resin casting body comprises the following steps: firstly, polishing a casting body mould, and uniformly spraying a release agent on the surface of the mould; the mold was then placed in a vacuum oven at 60 ℃ to preheat for 1 h. Pouring the PTA resin into a mold, after the resin is molten, keeping the resin under vacuum for about 2h to remove air and solvent until no bubbles appear within 3s, and then transferring the resin into a high-temperature oven to be cured. The curing process comprises the following steps: keeping the temperature at 80 ℃ for 12h to form the casting body, then keeping the temperature at 120 ℃ for 2h, keeping the temperature at 150 ℃ for 2h, keeping the temperature at 180 ℃ for 2h and keeping the temperature at 210 ℃ for 2h in sequence to solidify, and demoulding after the solidification is finished to obtain yellow hard PTA resin casting body condensate.
After the solidification, grinding into powder for thermogravimetric analysis. Under the nitrogen atmosphere, the temperature of 5 percent weight loss is 333 ℃.
After the curing is finished, preparing a DMA sample strip, and testing the glass transition temperature (T) by adopting a double-cantilever modeg) The temperature was 218 ℃.
After the solidification is finished, polishing the sample strip to a test standard size, and testing the size of the sample by the bending performance: 80X 15X 4mm3. The bending property of the solidified material of the polytriazole resin casting body is tested by adopting a three-point bending test method, and the result shows that the bending strength of the polytriazole resin casting body is 84.27 MPa.
The size of the impact resistance test sample is as follows: 80X 10X 4mm3. The impact resistance is tested by adopting an unnotched cantilever beam impact experiment method, and the result shows that the impact strength is 38.0kJ/m2。
Effect example 1
The scanning electron microscope is adopted to characterize the surface appearance of the impact section of the sample obtained when the resin prepared in the embodiments 4-6 and the comparative example 1 is used for testing the impact strength. The scanning electron microscope is a field emission scanning electron microscope of type S-4800 of Hitachi, Japan; the test conditions were: the sample is fixed on a test bench through a conductive carbon adhesive tape, the sample to be observed is subjected to vacuum gold spraying, and then is observed on a scanning electron microscope, wherein the accelerating voltage is 15 kV. Fig. 1 is an SEM image of an impact section of an unmodified polytriazole resin (PTA) in comparative example 1, and fig. 2 to 4 are SEM images of impact sections of polytriazole resins synthesized in examples 4 to 6 (EPTA-i-20, i: 4,6,8), respectively. The figure shows that the polytriazole resin material before toughening and modifying has smooth and flat section, single crack direction and linear expansion, and the polytriazole resin after toughening and modifying has complex crack direction, small crack spacing, deep crack, obvious unevenness and resin characteristics. It is demonstrated that the introduction of the polyether segment can greatly improve the toughness of the polytriazole resin.
Effect example 2
In order to further quantitatively investigate the curing degree of the polytriazole resin EPTA-4-10 obtained in example 2 at different curing stages, FIG. 5 is used as a basis. At 1100cm-1The stretching vibration peak near-C-O is used as an internal measurement standard, 2095cm-1vicinity-N3The intensity change of the asymmetric stretching vibration peak is obvious, the curing process of the resin can be accurately reflected, and the curing reaction degree alpha of the EPTA-4-10 resin at different curing stages is calculated by the following formula:
in the formula, a0And a0 markEach represents-N before the curing reaction of the resin3And-the absorption peak area of C-O; a istAnd aT markRespectively represents a certain stage-N of the resin curing reaction at the time t3And the absorption peak area of-C-O. The results of the quantitative analysis are shown in Table 1.
TABLE 1
As can be seen from Table 1 and FIG. 5, with increasing curing temperature, 2095cm-1vicinity-N3And a characteristic absorption peak of 3034cm for C-1The peak of C-H stretching vibration on the nearby triazole ring is enhanced, indicating that-N3and-C vibrationA 1, 3-dipolar cycloaddition reaction occurs to produce a triazole ring. And 2095cm after curing for 2h at 210 DEG C-1vicinity-N3and-C the characteristic absorption peak almost completely disappeared, indicating that the polytriazole resin EPTA-4-10 system is completely cured. Therefore, the polytriazole resin PTAE-4-10 completes the curing reaction through a curing process of 80 ℃/12h +120 ℃/2h +150 ℃/2h +180 ℃/2h +210 ℃/2 h. Specifically, after the polytriazole resin EPTA-4-10 is reacted at 80 ℃ for 12 hours, the curing reaction process exceeds 74%. After the temperature is raised to 180 ℃ and the reaction is carried out for 2 hours, the curing reaction degree can reach about 96 percent. And then the temperature is continuously increased to 210 ℃ for reaction for 2 hours, and the curing reaction degree tends to 100%.
Claims (10)
1. A polytriazole resin, which is a copolymer prepared by performing 1, 3-dipolar cycloaddition reaction on azido-terminated polyethylene glycol, 4 '-diazido-methylbiphenyl and N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane;
wherein, the structural formula of the azido-terminated polyethylene glycol is shown as follows:
the structural formula of the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane is shown as follows:
the structural formula of the 4, 4' -diazido methyl biphenyl is shown as follows:
the molar ratio of azido to alkynyl is 1: (1.02-1.10); the mol ratio of the azido-terminated polyethylene glycol to the 4, 4' -diazido-methyl biphenyl is 1: (3.5-20.5).
2. The polytriazole resin of claim 1, wherein the molar ratio of the azide groups to the alkyne groups is from 1: (1.03 to 1.07), preferably 1: 1.053;
and/or the mol ratio of the azido-terminated polyethylene glycol to the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane is 1: (2.57-10.5), preferably 1: (2.57-8), more preferably 1: (2.57-5.35), more preferably 1: (2.625-5.25), for example, 1: 3.5;
and/or the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: (4-19), preferably 1: (4-14), more preferably 1: (4-9), for example, 1: 5.67;
preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: (4-19), the average molecular weight of the azido-terminated polyethylene glycol is 400-800, preferably 400 or 600;
preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: (4-9), the average molecular weight of the azido-terminated polyethylene glycol is 400-800, preferably 400 or 600;
preferably, the mol ratio of the terminal azido polyethylene glycol to the 4, 4' -diazido methyl biphenyl is 1: 5.67, the average molecular weight of the azido-terminated polyethylene glycol is 400;
preferably, n in the azido-terminated polyethylene glycol is 6 to 16, more preferably 11;
preferably, the average molecular weight of the azido-terminated polyethylene glycol is 200 to 1200, more preferably 400 to 800, and even more preferably 600.
3. A method for preparing the polytriazole resin according to claim 1 or 2, comprising the steps of: and in the presence of an organic solvent, carrying out polymerization reaction on the azido-terminated polyethylene glycol, the 4,4 '-diazido-methylbiphenyl and the N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane to obtain the polytriazole resin.
4. The process for producing a polytriazole resin according to claim 3, wherein the organic solvent is acetone;
and/or the temperature of the polymerization reaction is 50-70 ℃, preferably 60 ℃;
and/or the time of the polymerization reaction is 3-6 h, preferably 4 h;
and/or the solid content of the reaction system before the polymerization reaction is 50-70%; the solid content is the percentage of the total mass of the azido-terminated polyethylene glycol, the 4,4 '-diazido-methylbiphenyl and the N, N, N', N '-tetrapropargyl-4, 4' -diamino-diphenylmethane in the total mass of the reaction system.
5. The method for preparing the polytriazole resin according to claim 3, wherein the method for preparing the azido-terminated polyethylene glycol comprises the steps of:
a. under the condition of inert atmosphere and organic solvent, mixing polyethylene glycol and thionyl chloride, and reacting to prepare chlorinated polyethylene glycol;
b. and reacting the chlorinated polyethylene glycol with sodium azide in the presence of an organic solvent.
6. The method for preparing polytriazole resin according to claim 5, wherein in the step a of preparing the azido-terminated polyethylene glycol, the inert atmosphere is nitrogen;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the organic solvent is toluene;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the molar ratio of the polyethylene glycol to the thionyl chloride is 1: (7-9), preferably 1: 8;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the thionyl chloride is added in the form of a thionyl chloride solution; preferably, in the thionyl chloride solution, the molar volume ratio of the thionyl chloride to the thionyl chloride solution is 0.05-0.2 mol/mL, more preferably 0.1 mol/mL; preferably, in the thionyl chloride solution, the solvent is toluene;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the thionyl chloride solution is added in a dropwise manner; the dripping time is preferably 1 to 3 hours, and more preferably 2 hours;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the mixing temperature is room temperature;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction temperature is 70-90 ℃, preferably 80 ℃;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction time is 35-45 h, preferably 40 h;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step a, the reaction is finished and then further comprises solvent removal and drying treatment; preferably, the drying is vacuum drying;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step b, the organic solvent is N, N-dimethylformamide;
and/or in the preparation process of the terminal azido-polyethylene glycol, in the step b, the molar ratio of the chlorinated polyethylene glycol to the sodium azide is 1: (4-6), preferably 1: 5;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step b, the reaction temperature is 70-90 ℃, preferably 80 ℃;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step b, the reaction time is 20-30 hours, preferably 24 hours;
and/or in the preparation process of the azido-terminated polyethylene glycol, in the step b, after the reaction is finished, carrying out post-treatment, wherein the post-treatment is carried out according to the following steps: cooling, filtering, extracting, drying and removing the solvent to obtain the azido-terminated polyethylene glycol.
7. A method for preparing a solidified material of a polytriazole resin casting body is characterized by comprising the following steps: the polytriazole resin according to claim 1 or 2, which is cured to form a cured product of the cast polytriazole resin.
8. The method for producing a cured product of a polytriazole resin casting product according to claim 7, wherein the temperature for the curing molding is 60 to 220 ℃, preferably 80 to 210 ℃;
and/or the curing and forming time is 18-22 h;
preferably, the curing molding is performed in a segmented manner, curing is performed at 60-80 ℃, and then curing is performed at 100-210 ℃ after heating;
preferably, the curing molding is carried out in a segmented mode, the temperature is kept for 10-12 hours at the temperature of 60-80 ℃, then the temperature is raised to 110-120 ℃, the temperature is kept for 1-3 hours, then the temperature is raised to 140-150 ℃, the temperature is kept for 1-3 hours, then the temperature is raised to 170-180 ℃, the temperature is kept for 1-3 hours, and then the temperature is raised to 200-210 ℃, and the temperature is kept for 1-3 hours;
more preferably, the curing molding is performed in a segmented manner, the temperature is maintained at 80 ℃ for 12h, the temperature is raised to 120 ℃ for 2h, the temperature is raised to 150 ℃ for 2h, the temperature is raised to 180 ℃ for 2h, and the temperature is raised to 210 ℃ for 2 h.
9. A cured product of a polytriazole resin casting obtained by the method for producing a cured product of a polytriazole resin casting according to claim 7 or 8.
10. Use of a polytriazole resin according to claim 1 or 2 as a tough material in the military or aerospace industry.
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| CN114989427A (en) * | 2022-06-15 | 2022-09-02 | 华东理工大学 | Polytriazole resin toughened by propargyl polypropylene glycol, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102241820A (en) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | Novel polytriazole elastomer and preparation method thereof |
| CN103087671A (en) * | 2011-11-08 | 2013-05-08 | 华东理工大学 | High temperature-resistant damp heat-resistant polytriazole resin adhesive and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102241820A (en) * | 2011-03-03 | 2011-11-16 | 华东理工大学 | Novel polytriazole elastomer and preparation method thereof |
| CN103087671A (en) * | 2011-11-08 | 2013-05-08 | 华东理工大学 | High temperature-resistant damp heat-resistant polytriazole resin adhesive and preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114989427A (en) * | 2022-06-15 | 2022-09-02 | 华东理工大学 | Polytriazole resin toughened by propargyl polypropylene glycol, and preparation method and application thereof |
| CN114989427B (en) * | 2022-06-15 | 2023-11-14 | 华东理工大学 | Polytriazole resin toughened by propargyl polypropylene glycol, preparation method and application thereof |
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