CN111019128A - Polytriazole resin toughened by alkynyl polyethylene glycol and preparation method thereof - Google Patents
Polytriazole resin toughened by alkynyl polyethylene glycol and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/08—Polyhydrazides; Polytriazoles; Polyaminotriazoles; Polyoxadiazoles
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Abstract
The invention belongs to the technical field of resin production, and particularly discloses a terminal alkynyl polyethylene glycol toughened polytriazole resin and a preparation method thereof. The resin is a copolymer prepared by carrying out 1, 3-dipolar cycloaddition reaction on a terminal alkynyl polyethylene glycol monomer and a monomer used by polytriazole resin. The resin has good solubility. With the introduction of flexible chains, the toughness of the cured resin is obviously improved, and the impact strength can reach 72.92kJ/m2The glass transition temperature (T) of the resin is increased by 84.8 percent compared with that of the polytriazole resin before modificationg) And 5 wt% thermogravimetric temperature (T)d5) Slightly reduced, can be used as a resin matrix of an aerospace structure composite material and is widely applied.
Description
Technical Field
The invention belongs to the technical field of resin production, and particularly relates to a preparation method of end alkynyl polyethylene glycol toughened polytriazole resin.
Background
Advanced composite materials are important material bases and leading technologies for aerospace (Du-Lai. advanced composite materials and aerospace [ J ] composite materials, 2007,24(1): 1-12). The advanced resin-based composite material can obviously reduce the mass of an airplane, the weight of a manufactured part of the advanced resin-based composite material is usually 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 multiple functions, the weight reduction is no longer the only purpose of applying the composite material in an aircraft, advanced equipment such as high-speed airplanes, aerospace planes, aero-engines and the like puts forward the requirements of heat resistance, a forming process and good toughness performance (Yangtao, Zhanpo, Du billow, and the like) on an advanced composite material resin matrix, and the research progress of toughening and modification of the thermosetting polyimide resin-based composite material [ J ] the aerospace manufacturing technology, 2019,62(10): 66-71). By utilizing reasonable structure and material design, the toughness of the matrix resin is improved, and the application range of the advanced composite material in the field of aerospace (Liulin, Daguangyu, Liwenfeng, and the like.) is expanded. Therefore, it is becoming a focus of research on how to obtain a thermosetting resin having excellent toughness while ensuring good heat resistance. In recent years, the institute of advanced resin matrix composites of the university of eastern science and technology, utilizing the 1, 3-dipolar cycloaddition reaction of alkynyl and azide compounds, prepared a series of polytriazole resins and made systematic studies (Tian J, Wan L, Huang J, et al. preparation and properties of a new poly (triazole) resins and compounds and its, composite [ J ] Polymer Bulletin,2008,60(4): 457. abo 465.) (Wang X, Zo Z, Tian J, et al. Synthesis and catalysis of a new poly (triazole) from N, N-dimethyl-p-propyl oxo-nine [ J ] Polymer Journal,2009,41(6): Li 502. J, J.S. 13, J. (13, J.),502. N, J.) (Polymer J.),498. monomer J.),105, Z.), WanL, HanD, et al, investigation of novel polytriazoles [ J ]. Designed Monomers & Polymers,2016,19(7):1-8.) (Xue L, Wan L, Hu Y, et al, thermal stability of a novel polytriazoles [ J ]. Therochimaacta, 2006,448(2): 147-. Research shows that the polytriazole resin can be cured at low temperature, and the cured resin has excellent processability, thermal property and mechanical property and can be used as a resin matrix of an advanced composite material. Has very important application value for the toughening research of the polytriazole resin. Moreover, the current research on toughening polytriazole resin is rarely reported.
The polymer containing the flexible long-chain structure has excellent toughness, and the toughness of the polytriazole resin can be improved by introducing the long-chain polyether structure into the polytriazole resin.
To date, there have been many reports of chemically modifying methods for introducing soft segments into the backbone structure to toughen thermosetting resins. Zhengben et al bond polyethylene glycol having a flexible long chain structure to furan resin through a chemical reaction to increase its toughness. When the molecular weight of PEG is 400Da, the toughening effect on furan resin is best, when the consumption is 25 wt%, the breaking elongation of the furan resin reaches 5.51%, and the maximum tensile strength can reach 19.9MPa (Zhengben, Biqin, Zhurongyang, and the like.) the research on the polyethylene glycol chemical modification toughening furan resin [ J ] reported by Anhui engineering university, 2015,30(1): 41-43); the preparation method comprises the following steps of (1) carrying out ring-opening addition reaction on ethylene glycol and epoxy resin under the action of a tertiary amine catalyst by virtue of Siberian wormwood herb and the like, and introducing a fatty alcohol flexible chain segment into a main chain structure of the epoxy resin, so that the toughness of the epoxy resin is enhanced (Siberian wormwood herb, Living holly, Zhengyanyu, and the like; ethylene glycol modified epoxy resin and film-forming property [ J ] thereof, wherein 2013,10(46) is 40-43); xiaotianjin greatly improves the toughness by introducing a flexible aryl ether chain segment into the main chain of PMR type polyimide, and has excellent heat-resistant stability and heat-resistant oxidation stability (Xiaotianjin. preparation and research of thermosetting high-temperature-resistant toughened polyimide [ D ]. Beijing: the institute of chemistry of Chinese academy of sciences, 2001);
in conclusion, the polytriazole resin has many excellent properties, but the toughness has room for improvement. The flexible chain segment is introduced into the main chain structure of the polytriazole resin, and the polytriazole resin is chemically modified, so that the toughness of the polytriazole resin can be improved.
Disclosure of Invention
The invention aims to provide the polytriazole resin toughened by the terminal alkynyl polyethylene glycol and the preparation method thereof, the resin can be cured and crosslinked at the temperature of 80-150 ℃, and the formed polytriazole resin containing the flexible long-chain structure has good toughness.
The purpose of the invention is realized by the following technical scheme:
a poly-triazole resin toughened by alkynyl-terminated polyethylene glycol is a copolymer prepared by 1, 3-dipolar cycloaddition reaction of alkynyl-terminated polyethylene glycol monomers, N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane and biphenyl dibenzyl azide;
the structural formula of the end alkynyl polyethylene glycol monomer is as follows:
repeating unit n ═ 22;
the structural formula of the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane is as follows:
the structural formula of the biphenyl dibenzyl azide is as follows:
further, the mol ratio of the terminal alkynyl polyethylene glycol to the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane and the biphenyl dibenzyl azide is 2:49:100, 6:47:100 or 10:45: 100.
According to the invention, the impact strength of the toughened polytriazole resin is 61.09kJ/m2、70.65kJ/m2、72.92kJ/m2；
A cured product T of the toughened polytriazole resind5At 354 deg.C, 344 deg.C, 324 deg.C respectively;
a cured product T of the toughened polytriazole resingAt 223 deg.C, 189 deg.C and 160 deg.C, respectively.
The invention also provides a preparation method of the end alkynyl polyethylene glycol toughened polytriazole resin, which comprises the following steps: under the condition of no solvent, the end alkynyl polyethylene glycol, the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane and the biphenyl dibenzyl azide are mixed and melted to react to prepare the toughened polytriazole resin.
Further, the temperature of the reaction is 70 ℃;
the time for melting the monomers is 12 min;
the reaction time is 5 min;
and after the reaction is finished, obtaining the toughened polytriazole resin.
Further, the resin curing molding operation is to cure at 80 ℃ and then completely cure at 100-150 ℃, and preferably comprises the following steps: the curing and forming can be carried out by firstly preserving heat for 12h at 80 ℃, and then the curing is completed by preserving heat for 2h at 120 ℃ and preserving heat for 2h at 150 ℃.
Further, the terminal alkynyl polyethylene glycol is prepared by the following method:
adding potassium tert-butoxide into a tetrahydrofuran solution of polyethylene glycol under the protection of dry inert gas, wherein the molar ratio of the polyethylene glycol to the potassium tert-butoxide is 1: 2.5; after reacting for 1h at 0 ℃, adding bromopropyne dropwise into the solution, wherein the molar ratio of the bromopropyne to potassium tert-butoxide is 1: 1; after the dropwise addition is finished, reacting for 30min at 0 ℃, and then reacting for 24h at normal temperature; after the reaction was completed, the reaction mixture was washed with saturated brine for 5 times, the organic layer was retained, dried over anhydrous magnesium sulfate, suction-filtered, and then evaporated under reduced pressure at 35 ℃ to remove the solvent, thereby obtaining a terminal alkynyl polyethylene glycol.
The invention also provides a toughened polytriazole resin cured product prepared by the preparation method.
The invention also provides application of the end alkynyl polyethylene glycol toughened polytriazole resin in the fields of aerospace and weapons and equipment.
Detailed description of the invention:
the invention provides a terminal alkynyl polyethylene glycol toughened polytriazole resin and a preparation method thereof, wherein the preparation method comprises the following specific steps:
firstly, preparing an alkynyl-terminated polyethylene glycol monomer:
the preparation of the terminal alkynyl polyethylene glycol monomer comprises the following steps:
structural formula (xvi):
wherein, the repeating unit n is 22.
The specific process flow is as follows: adding potassium tert-butoxide into a tetrahydrofuran solution of polyethylene glycol under the protection of dry inert gas, wherein the molar ratio of the polyethylene glycol to the potassium tert-butoxide is 1: 2.5. After reacting at 0 ℃ for 1h, bromopropyne was added dropwise to the solution, wherein the molar ratio of bromopropyne to potassium tert-butoxide was 1: 1. After the dropwise addition, the reaction is carried out for 30min at the temperature of 0 ℃, and then the reaction is carried out for 24h at the normal temperature. After the reaction, the reaction mixture was washed with saturated brine for 5 times, the organic layer was retained, dried over anhydrous magnesium sulfate, filtered, and then evaporated under reduced pressure at 35 ℃ to remove the solvent, and a pale yellow liquid, which was the target product, terminal alkynyl polyethylene glycol, was obtained.
Step two, preparing polytriazole resin with a main chain containing a long-chain polyether structure:
the specific process flow is as follows: mixing a terminal alkynyl polyethylene glycol monomer and a raw material monomer [ biphenyl dibenzyl azide (BPDBA) and N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane (TPDDM) ] of the polytriazole resin according to a group molar ratio (azido group)/(alkynyl group) ═ 1.0:1.02 at 70 ℃, stirring for 12min until the monomer is melted, and reacting for 5min to obtain the polytriazole resin with the main chain containing a long-chain polyether structure.
Compared with the prior art, the invention has the following positive effects:
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 large moving space is obtained between triazole rings in a polytriazole resin system, and the polytriazole resin can absorb more energy after being impacted, so that the toughness of the polytriazole resin is greatly improved, and the polytriazole resin is expected to be widely applied to the fields of aerospace, weaponry and the like as a resin matrix of an advanced composite material. The ether bond is introduced into the main chain structure of the polytriazole resin, so that the polytriazole resin has good processing performance, is easy to dissolve in polar solvents such as acetone, THF, DMSO and DMF, and keeps high thermal stability of the polytriazole resin.
Drawings
FIG. 1 is a DMA graph of the cured toughened polytriazole resins (TPTA-1, TPTA-2 and TPTA-3) and the non-toughened polytriazole resin (PTA) synthesized in examples 1-3.
FIG. 2 is a TGA curve of the cured products of the toughened polytriazole resins (TPTA-1, TPTA-2 and TPTA-3) synthesized in examples 1-3 and the non-toughened polytriazole resin (PTA) under nitrogen, wherein the dotted line represents the thermal weight loss of the cured products of 5 wt%.
FIG. 3 is SEM pictures of impact cross-sections of comparative example unmodified polytriazole resin (PTA) and the toughened polytriazole resin synthesized in example 3 (TPTA-3).
Detailed Description
The invention provides a specific implementation method of the end alkynyl polyethylene glycol toughened polytriazole resin and a preparation method thereof
Example 1:
synthesizing and curing toughened polytriazole resin TPTA-1, wherein the mol weight of alkynyl of DPPEG in the TPTA-1 accounts for 2% of the total alkynyl.
(1) Synthesis of terminal alkynyl polyethylene glycol monomer (DPPEG) with molecular weight of 1000
Polyethylene glycol (50g, 0.05mol) having a molecular weight of 1000 and 500mL of tetrahydrofuran were added to a 1000mL eggplant-shaped bottle, and the mixture was magnetically stirred until the polyethylene glycol was completely dissolved. A1000 mL four-neck flask equipped with a stirrer, a thermometer, a constant pressure funnel and a vent port is dehydrated by a vacuum flask, and a prepared tetrahydrofuran solution of polyethylene glycol is added under the protection of nitrogen, and then potassium tert-butoxide (14.03g, 0.125mol) is added. After stirring for 1h in an ice-water bath, bromopropyne (14.87g, 0.125mol) was slowly added dropwise thereto through a 50mL constant pressure funnel under a nitrogen blanket. After the dropwise addition, the reaction mixture was stirred in an ice-water bath for 30 min. After completion of the reaction, the reaction mixture was poured into a 2L separatory funnel, and the reaction mixture was washed with saturated saline, and the organic layer was retained and washed five times. Drying over anhydrous magnesium sulfate for 4h, suction filtration, and final removal of tetrahydrofuran and reaction by-products by rotary evaporation under reduced pressure to give a yellow waxy product with a yield of about 40%.
The specific reaction flow is as follows:
nuclear magnetic hydrogen spectrum and infrared spectrum data of DPPE:
FTIR(KBr,v,cm-1) 3240 (peak of. ident.C-H stretching vibration of alkyne), 2105 (peak of C.ident.C stretching vibration of alkyne), 670 (peak of C.ident.C-H bending vibration of alkyne).
1H-NMR(CDCl3,TMS)δ(ppm)：2.45(s,2H,－C≡CH),3.67～3.72(m,88H，－CH2－CH2－O－)，4.23(s,4H,－C－CH2－)。
The results of the elementary analysis of DPPEG are shown in Table 1. The average content of the two measurements is taken as the content of each element, and the C element is taken as the reference, so that the substitution rate of the terminal hydroxyl in the polyethylene glycol can be calculated to be 99%.
TABLE 1 elemental analysis results of DPPEG
(2) Synthesis of toughened polytriazole resin TPTA-1
DPPEG1000(1.87g,1.89mmol), biphenyl dibenzyl azide (BPDBA,25g,94.7mmol), N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane (TPDDM,16.24g,46.4mmol) were added to a 250mL beaker and stirred with a glass rod at 70 ℃ in an oil bath kettle for about 12min, after which the monomers were melted and reacted for 5min to give yellow TPTA-1 resin.
(3) Curing of toughened polytriazole resin TPTA-1
Pouring yellow resin into a mold coated with a release agent and preheated at 70 ℃ for 1h, putting the mold into an oven for vacuum pumping and soaking for 30min, preserving heat at 80 ℃ for 6h to obtain a molded product, preserving heat at 120 ℃ for 2h, preserving heat at 150 ℃ for 2h in sequence, completely curing, and demolding after curing to obtain a yellow hard cured product. T of TPTA-1 resin after curinggAt 223 ℃ Td5At a temperature of 354 ℃ and an impact strength of 61.09kJ/m2。
Example 2:
and (2) synthesizing and curing toughened polytriazole resin TPTA-2, wherein the molar weight of the alkynyl of DPPEG in the TPTA-2 accounts for 6% of the total alkynyl.
(1) Synthesis of toughened polytriazole resin TPTA-2
DPPEG1000(5.61g,5.68mmol), biphenyl dibenzyl azide (BPDBA,25g,94.7mmol), N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane (TPDDM,15.58g,44.5mmol) were added to a 250mL beaker and stirred with a glass rod at 70 ℃ in an oil bath kettle for about 12min, after which the monomers were melted and reacted for 5min to give yellow TPTA-2 resin.
(2) Curing of toughened polytriazole resins TPTA-2
Pouring yellow resin into a mold coated with a release agent and preheated at 70 ℃ for 1h, putting the mold into an oven for vacuum pumping and soaking for 30min, preserving heat at 80 ℃ for 6h to obtain a molded product, preserving heat at 120 ℃ for 2h, preserving heat at 150 ℃ for 2h in sequence, completely curing, and demolding after curing to obtain a yellow hard cured product. T of TPTA-2 resin after curinggAt 189 ℃ and Td5344 ℃ and the impact strength is 70.65kJ/m2。
Example 3:
synthesizing and curing toughened polytriazole resin TPTA-3, wherein the mol weight of alkynyl of DPPEG in the TPTA-3 accounts for 10% of the total alkynyl.
(1) Synthesis of toughened polytriazole resin TPTA-3
DPPEG1000(9.36g,9.47mmol), biphenyl dibenzyl azide (BPDBA,25g,94.7mmol), N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane (TPDDM,14.91g,42.6mmol) were added to a 250mL beaker and stirred with a glass rod at 70 ℃ in an oil bath kettle for about 12min, after which the monomers were melted and reacted for 5min to give yellow TPTA-3 resin.
(2) Curing of toughened polytriazole resins TPTA-3
Pouring yellow resin into a mold coated with a release agent and preheated at 70 ℃ for 1h, putting the mold into an oven for vacuum pumping and soaking for 30min, preserving heat at 80 ℃ for 6h to obtain a molded product, preserving heat at 120 ℃ for 2h, preserving heat at 150 ℃ for 2h in sequence, completely curing, and demolding after curing to obtain a yellow hard cured product. T of TPTA-3 resin after curinggAt 160 ℃ and Td5324 ℃ and the impact strength of 72.92kJ/m2。
The TPTA resin has good solubility, can be dissolved in acetone, THF, acetonitrile, ethyl acetate, chlorohydrocarbon solvent and strong polar solvent except methanol and petroleum ether at room temperature, and is convenient for processing and application of the resin.
FIG. 1 is a DMA graph of a cured product of toughened polytriazole resins (TPTA-1, TPTA-2 and TPTA-3) and a cured product of non-toughened polytriazole resin (PTA) synthesized in examples 1-3. T of PTAgT of TPTA at 245 DEG CgT of TPTA-1 decreases as the proportion of DPPEG increasesgT of TPTA-2 at 223 DEG CgT of TPTA-3 at 189 DEG CgThe temperature was 160 ℃.
FIG. 2 is a TGA curve of the cured toughened polytriazole resin (TPTA-1, TPTA-2 and TPTA-3) and the non-toughened polytriazole resin (PTA) synthesized in examples 1-3, measured under nitrogen, wherein the dotted line represents the thermal weight loss of the cured product of 5 wt%. T of PTAd5At 352 ℃ T of TPTAd5T of TPTA-1 decreases as the proportion of DPPEG increasesd5T of TPTA-2 at 354 ℃d5T of TPTA-3 at 344 DEG Cd5The temperature was 324 ℃.
The impact test and thermal property test results are shown in table 2. With the increase of the proportion of DPPEG, the toughness of TPTA is obviously improved compared with PTA.
TABLE 2 impact test and thermal Performance test results for PTA and TPTA
FIG. 3(a) is an SEM image of impact cross section of unmodified polytriazole resin (PTA). FIG. 3(b) is an SEM image of impact cross-section of the toughened polytriazole resin (TPTA-3) synthesized in example 3. The polytriazole resin material before modification has a smooth and flat section and a single crack direction and linearly expands. The cross section of the polytriazole resin after chemical modification presents obvious shell textures.
The end alkynyl polyethylene glycol toughened polytriazole resin has excellent molding process characteristics, such as low resin viscosity, good solubility, no release of small molecular gas during curing and the like. The condensate of the high-temperature-resistant polytriazole resin has good high-temperature-resistant performance, compared with that before modification, the toughness of the high-temperature-resistant polytriazole resin is greatly improved, and the application range of the polytriazole resin is expanded.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and decorations can be made without departing from the spirit of the present invention, and these modifications and decorations should also be regarded as being within the protection scope of the present invention.
Claims (9)
1. The end alkynyl polyethylene glycol toughened polytriazole resin is characterized in that the end alkynyl polyethylene glycol toughened polytriazole resin is a copolymer prepared by carrying out 1, 3-dipolar cycloaddition reaction on an end alkynyl polyethylene glycol monomer, N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane and biphenyl dibenzyl azide;
the structural formula of the end alkynyl polyethylene glycol monomer is as follows:
repeating unit n ═ 22;
the structural formula of the N, N, N ', N ' -tetrapropargyl-4, 4 ' -diamino-diphenylmethane is as follows:
the structural formula of the biphenyl dibenzyl azide is as follows:
2. the alkynyl-terminated polyethylene glycol-toughened polytriazole resin of claim 1, wherein the molar ratio of the alkynyl-terminated polyethylene glycol to the N, N, N ', N ' -tetraacetylpropyl-4, 4 ' -diamino-diphenylmethane and biphenyldiazenyl azide is 2:49:100, 6:47:100 or 10:45: 100.
3. The terminal alkynyl polyethylene glycol-toughened polytriazole resin of claim 1, wherein the toughened polytriazole resin cured product has impact strengths of 61.09kJ/m2、70.65kJ/m2、72.92kJ/m2；
A cured product T of the toughened polytriazole resind5At 354 deg.C, 344 deg.C, 324 deg.C respectively;
a cured product T of the toughened polytriazole resingAt 223 deg.C, 189 deg.C and 160 deg.C, respectively.
4. The method for preparing the alkynyl-terminated polyethylene glycol-toughened polytriazole resin according to any one of claims 1 to 3, wherein the alkynyl-terminated polyethylene glycol is mixed with the N, N, N ', N ' -tetraacetylpropargyl-4, 4 ' -diamino-diphenylmethane and biphenyldibenzyl azide and melted in the absence of a solvent, and then the mixture is reacted to obtain the toughened polytriazole resin.
5. The method for preparing the terminal alkynyl polyethylene glycol toughened polytriazole resin according to claim 4, wherein the reaction temperature is 70 ℃;
the time for melting the monomers is 12 min;
the reaction time is 5 min;
and after the reaction is finished, obtaining the toughened polytriazole resin.
6. The method for preparing the terminal alkynyl polyethylene glycol toughened polytriazole resin according to claim 4, wherein the resin is cured at 80 ℃ and then fully cured at 100-150 ℃, and further preferably comprises the following steps: the curing and forming can be carried out by firstly preserving heat for 12h at 80 ℃, and then the curing is completed by preserving heat for 2h at 120 ℃ and preserving heat for 2h at 150 ℃.
7. The method for preparing the terminal alkynyl polyethylene glycol toughened polytriazole resin according to claim 4, wherein the terminal alkynyl polyethylene glycol is prepared by a method comprising the following steps:
adding potassium tert-butoxide into a tetrahydrofuran solution of polyethylene glycol under the protection of dry inert gas, wherein the molar ratio of the polyethylene glycol to the potassium tert-butoxide is 1: 2.5; after reacting for 1h at 0 ℃, adding bromopropyne dropwise into the solution, wherein the molar ratio of the bromopropyne to potassium tert-butoxide is 1: 1; after the dropwise addition is finished, reacting for 30min at 0 ℃, and then reacting for 24h at normal temperature; after the reaction was completed, the reaction mixture was washed with saturated brine for 5 times, the organic layer was retained, dried over anhydrous magnesium sulfate, suction-filtered, and then evaporated under reduced pressure at 35 ℃ to remove the solvent, thereby obtaining a terminal alkynyl polyethylene glycol.
8. A toughened cured polytriazole resin prepared by the method of claim 6.
9. The application of the terminal alkynyl polyethylene glycol toughened polytriazole resin in the fields of aerospace and weaponry equipment, as claimed in claim 1.
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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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| 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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