CN115028834B - Polyaryltriazole and preparation method and application thereof - Google Patents
Polyaryltriazole and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 64
- 239000000178 monomer Substances 0.000 claims description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 29
- -1 aryl alkyne Chemical class 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 150000001345 alkine derivatives Chemical class 0.000 claims description 7
- 239000002685 polymerization catalyst Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 125000001425 triazolyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 41
- 102100038077 CD226 antigen Human genes 0.000 description 36
- 101000884298 Homo sapiens CD226 antigen Proteins 0.000 description 36
- 101000670986 Homo sapiens Symplekin Proteins 0.000 description 36
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 32
- 239000002904 solvent Substances 0.000 description 30
- OHJIHGVLRDHSDV-BNAVIEMTSA-N OC(=O)CCC\C=C/C[C@@H]1[C@@H](/C=C/[C@@H](O)CCCCC)C[C@@H]2C(C)(C)[C@H]1C2 Chemical compound OC(=O)CCC\C=C/C[C@@H]1[C@@H](/C=C/[C@@H](O)CCCCC)C[C@@H]2C(C)(C)[C@H]1C2 OHJIHGVLRDHSDV-BNAVIEMTSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000001914 filtration Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 18
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 239000000543 intermediate Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 230000001376 precipitating effect Effects 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000007858 starting material Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 150000001540 azides Chemical class 0.000 description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 description 8
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- LXAHHHIGZXPRKQ-UHFFFAOYSA-N 5-fluoro-2-methylpyridine Chemical compound CC1=CC=C(F)C=N1 LXAHHHIGZXPRKQ-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 235000010378 sodium ascorbate Nutrition 0.000 description 7
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 7
- 229960005055 sodium ascorbate Drugs 0.000 description 7
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- AEAPKLGWVGQIOY-UHFFFAOYSA-N C#CCC(C=C(C=C1)S(C(C=C2)=CC=C2O)(=O)=O)=C1O Chemical compound C#CCC(C=C(C=C1)S(C(C=C2)=CC=C2O)(=O)=O)=C1O AEAPKLGWVGQIOY-UHFFFAOYSA-N 0.000 description 4
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 150000003852 triazoles Chemical group 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229920000491 Polyphenylsulfone Polymers 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 125000001399 1,2,3-triazolyl group Chemical class N1N=NC(=C1)* 0.000 description 2
- GFBKCJQKMJUEHL-UHFFFAOYSA-N 1-(azidomethyl)-2-[4-[4-[2-(azidomethyl)phenyl]phenyl]phenyl]benzene Chemical compound C1(=CC=C(C=C1)C1=CC=CC=C1CN=[N+]=[N-])C1=CC=C(C=C1)C1=CC=CC=C1CN=[N+]=[N-] GFBKCJQKMJUEHL-UHFFFAOYSA-N 0.000 description 2
- HMUGRILXVBKBID-UHFFFAOYSA-N 1-(bromomethyl)-4-[4-(bromomethyl)phenyl]benzene Chemical group C1=CC(CBr)=CC=C1C1=CC=C(CBr)C=C1 HMUGRILXVBKBID-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000012650 click reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- HRDCVMSNCBAMAM-UHFFFAOYSA-N 3-prop-2-ynoxyprop-1-yne Chemical compound C#CCOCC#C HRDCVMSNCBAMAM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006352 cycloaddition reaction Methods 0.000 description 1
- 238000000354 decomposition reaction 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
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- CTRLRINCMYICJO-UHFFFAOYSA-N phenyl azide Chemical class [N-]=[N+]=NC1=CC=CC=C1 CTRLRINCMYICJO-UHFFFAOYSA-N 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 238000001955 polymer synthesis method Methods 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a polyaryltriazole and a preparation method and application thereof. The polyaryltriazole has a structure shown as a formula (I):wherein R is n is an integer of 26 to 45. The polyaryltriazole provided by the invention has better high temperature resistance by introducing the framework structure of the benzene ring and the triazole ring; and is also soluble in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained through CuAACP polymerization, the preparation condition is mild, and the cost of the required raw materials is low.
Description
Technical Field
The invention belongs to the field of high polymer preparation, and particularly relates to a polyaryltriazole and a preparation method and application thereof.
Background
Since the discovery by Michel of 1893 that azidobenzenes and alkyne dimethyl dicarboxylic acids react to form 1,2, 3-triazoles, this 1, 3-cycloaddition reaction by azides and alkynes has become one of the most important processes for the preparation of 1,2, 3-triazole compounds and derivatives thereof. Click chemistry is a new chemical concept proposed by Sharpless in 2001, and refers to a nearly perfect organic reaction, which has modularization, high reaction efficiency, mild condition, good atomic economy, wide substrate application range and good selectivity. Has the advantages of no toxic by-products, simple purification and the like, and can be widely applied to the aspects of preparation, surface modification and the like of drug carrier materials, biological functional materials and photoelectric functional materials.
In the development of click chemistry, polymer scientists develop a brand new polymer synthesis method by utilizing the advantages of simple and efficient click chemistry reaction conditions, and directly apply the method to the preparation of novel polymers, namely click polymerization. At present, a plurality of click reactions are developed into click polymerization, wherein one of the most influencing factors is Cu (I) catalyzed azido-alkyne click polymerization (CuAACP), and the method has the advantages of high reaction efficiency, mild condition, good atomic economy, insensitivity to water and oxygen, good product stereoselectivity and the like, and has wide application in the aspects of molecular design and synthesis of high polymer materials. The diazo and dialkynyl monomers can be heated or subjected to 1,3 dipolar cycloaddition reaction under the catalysis of Cu (I) to obtain a plurality of polytriazole high polymer materials with excellent performances, the triazole ring produced by using the azides and the alkynes has the characteristics of rigidity and high temperature resistance, and the polytriazole can be developed into high-performance resin and is expected to be applied to various fields as engineering plastics. Chinese patent 'a trifunctional alkyne-derived polytriazole resin and its preparation method' disclose that aromatic type ternary phenols compound is used to prepare aromatic type propargyl ether through substitution reaction, then 1, 3-dipolar cycloaddition reaction is carried out with azide compound to prepare trifunctional alkyne-derived novel polytriazole resin, the trifunctional alkyne-derived novel polytriazole resin has more benzene ring structures, better heat resistance, and T g 310 ℃; t (T) d5 361 ℃. The Chinese patent 'resin containing the polytriazole and the composite material thereof and the preparation method' disclose that the resin is prepared by 1, 3-dipolar cycloaddition reaction, the reaction is efficient, the temperature is lower, and the condition is mild; the obtained resin has excellent processability, can be crosslinked and cured at 60-80 ℃, has excellent mechanical property and heat resistance, has the bending strength of 1450-1500 MPa, the bending modulus of 140-145 GPa and the interlayer shearing strength of 50-55 MPa of the T700 unidirectional carbon fiber reinforced composite material, and has the advantages of high heat resistance, low cost, high heat resistance, and the like g Is 251 ℃; t (T) d5 360 ℃. The prepared polytriazole resin has the advantages of good performance, complex process, higher reaction conditions and the like, and the higher raw material cost also limits the application prospect.
Therefore, the polytriazole resin which has better high temperature resistance and is easy to synthesize and prepared at low cost is of great research value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings in the prior art and provides a polyaryltriazole. The polyaryltriazole provided by the invention has better high temperature resistance by introducing the framework structure of the benzene ring and the triazole ring; and is also soluble in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained through CuAACP polymerization, the preparation condition is mild, and the cost of the required raw materials is low.
Another object of the present invention is to provide a process for preparing the above polyaryltriazole.
Another object of the present invention is to provide the use of the above-mentioned polyaryltriazoles for the preparation of high temperature resistant resins.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
a polyaryltriazole having a structure according to formula (i):
wherein R is
n is an integer of 27 to 52.
The polyaryltriazole provided by the invention contains a framework structure of benzene ring and triazole ring, and is matched with other specific structures and groups to obtain the T-shaped polyaryltriazole g (glass transition temperature) of 196.4-230.6 ℃, T dmax The maximum thermal cracking temperature in nitrogen reaches 385.1-395.7 ℃, and the heat resistance is excellent; and has better solubility in various organic solvents and excellent processability.
In addition, the polyaryltriazole provided by the invention can be prepared through Cu (I) -catalyzed azido-alkyne cycloaddition reaction, the reaction condition is mild, and the cost of the required raw materials is low.
Preferably, said R is
Preferably, n is an integer of 35 to 45.
Preferably, the average molecular weight of the polyaryltriazole is 11000 to 17000.
The preparation method of the polyaryltriazole comprises the following steps:
the method comprises the steps of carrying out click polymerization reaction on a two-end aryl Die nitrogen monomer shown in a formula (II) and a two-end aryl alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the polyaryltriazole;
the preparation method provided by the invention takes the two-end aryl Die nitrogen monomer and the two-end aryl alkyne monomer as raw materials, and is prepared by utilizing a click reaction with high efficiency, and has the advantages of simple process, no intermediate product, mild reaction condition and high reaction efficiency.
Preferably, the di-terminal aryl Die nitrogen monomer is obtained by the following process: raw materials: 4,4' -dimethylbiphenyl, paraxylene or metaxylene, and NBS (N-bromosuccinimide) react under an initiator (such as dibenzoyl peroxide) to generate benzyl bromide, and nucleophilic substitution reaction of the benzyl bromide and sodium azide is carried out to obtain the di-end aryl Die nitrogen monomer.
4,4' -dimethylbiphenyl, paraxylene and metaxylene are cheap and easy to obtain, and the cost is low.
More preferably, the molar ratio of dibenzoyl peroxide, raw material and NBS is 1 (30-60) (80-120).
More preferably, the temperature of the reaction of the raw material and NBS is 70-80 ℃ and the time is 1-5 h.
More preferably, a solvent, such as CCl, is also present in the reaction system of the starting material and NBS 4 The concentration of the raw materials in the reaction system is 0.4-0.5 g/L.
More preferably, the molar ratio of benzyl bromide to sodium azide is 1 (2-3).
More preferably, the reaction of the raw material and NBS further comprises the step of reduced pressure evaporation and silica gel column chromatography.
Specifically, the reaction process of the raw materials and NBS is as follows: mixing raw materials, N-bromosuccinimide and dibenzoyl peroxide, and adding CCl under nitrogen 4 The solvent is stirred, condensed and refluxed at 70-80 ℃ and reacted overnight. The solvent is removed by reduced pressure evaporation after filtration, and the residue is purified by silica gel column chromatography by using petroleum ether/dichloromethane (10:1/v: v) as eluent, thus obtaining the benzyl bromide.
More preferably, the nucleophilic substitution reaction is carried out at a temperature of 55 to 65 ℃ for a time of 1 to 5 hours.
More preferably, a solvent such as DMF is also present in the reaction system of the nucleophilic substitution reaction, and the concentration of benzyl bromide in the reaction system is 0.4 to 0.5g/L.
More preferably, the nucleophilic substitution reaction further comprises the steps of extraction, washing, drying, reduced pressure evaporation and silica gel column chromatography.
Specifically, the nucleophilic substitution reaction process is as follows: adding benzyl bromide and sodium azide into a reactor, adding DMF solvent under nitrogen atmosphere, stirring at 55-65 ℃ for reaction overnight, pouring deionized water after the reaction liquid is cooled to room temperature, extracting with diethyl ether, collecting an organic layer, washing with saturated saline water, drying with anhydrous magnesium sulfate, filtering, evaporating under reduced pressure to remove diethyl ether solvent, and carrying out silica gel column chromatography on the product by using petroleum ether/dichloromethane (10:1/v: v) as eluent to obtain the di-end group aryl Die nitrogen monomer.
Preferably, the click polymerization catalyst is a monovalent copper salt catalyst.
Preferably, the molar ratio of the click polymerization catalyst to the nitrogen monomer of the two-terminal aryl Die is (1-3): 50.
Preferably, the temperature of the click polymerization reaction is 30-80 ℃.
Preferably, the molar ratio of the di-terminal aryl Die nitrogen monomer to the di-terminal aryl alkyne monomer is 1:1.
Specifically, the click polymerization reaction process is as follows: sequentially adding a two-end aryl alkyne monomer and a two-end aryl Die nitrogen monomer into a reactor, adding a DMSO solvent to dissolve the two-end aryl alkyne monomer and the two-end aryl Die nitrogen monomer, and stirring for a period of time at 30-80 ℃ in a nitrogen atmosphere. Copper sulfate pentahydrate and sodium ascorbate are dissolved in deionized water, and the solution is gradually added into the reaction solution dropwise through a constant pressure dropping leak for overnight reaction. After the reaction is finished, pouring the reaction solution into saturated aqueous solution of EDTA disodium, precipitating, filtering, washing with deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring into mixed solution of methanol and water, precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain the polyaryltriazole.
The application of the polyaryltriazole in preparing the high-temperature resistant resin is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the polyaryltriazole provided by the invention has better high temperature resistance by introducing the framework structure of the benzene ring and the triazole ring; and is also soluble in various organic solvents, and has excellent processability; in addition, the polyaryltriazole can be obtained through CuAACP polymerization, the preparation condition is mild, and the cost of the required raw materials is low.
Drawings
FIG. 1 is a diagram of a di-terminal aromatic Die nitrogen monomer II-1 and its starting material, intermediate in CDCl 3 A kind of electronic device 1 H NMR comparison.
FIG. 2 is a diagram of a di-terminal aromatic Die nitrogen monomer II-2 and its starting material, intermediate in CDCl 3 A kind of electronic device 1 H NMR comparison.
FIG. 3 is a diagram of a di-terminal aromatic Die nitrogen monomer II-3 and its starting material, intermediate in CDCl 3 A kind of electronic device 1 H NMR comparison.
FIG. 4 is a chart showing the preparation of a di-terminal phenylsulfone ether alkyne monomer III and its starting material, intermediate in CDCl 3 A kind of electronic device 1 H NMR comparison.
Fig. 5 is a DSC curve of PTA1, PTA2, PTA3, and PTA1', PTA2', PTA3'.
Fig. 6 is a graph of TG (a) and DTG (b) for PTA1, PTA2, PTA3 and PTA1', PTA2', PTA3'.
Detailed Description
The invention is further illustrated below with reference to examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. The experimental procedures in the examples below, without specific details, are generally performed under conditions conventional in the art or recommended by the manufacturer; the raw materials, reagents and the like used, unless otherwise specified, are those commercially available from conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art in light of the above teachings are intended to be within the scope of the invention as claimed.
The reagents selected for each of the examples of the present invention were all commercially available.
Example 1
This example provides a di-terminal aryl Die nitrogen monomer II-1 to a di-terminal aryl Die nitrogen monomer II-3 and a polyaryltriazole (designated PTA 1) prepared by the following procedure:
(1) 9.1130g (50 mmol) of 4,4' -dimethylbiphenyl, 17.7984g (100 mmol) of N-bromosuccinimide and 0.2422g (1 mmol) of dibenzoyl peroxide are placed in a flask equipped with reflux condensation200ml CCl was added to a three-necked flask of a tube under nitrogen atmosphere 4 The solvent was stirred at 78 ℃ under reflux with stirring and reacted overnight. After filtration, the solvent was removed by evaporation under reduced pressure, and the residue was purified by silica gel column chromatography using petroleum ether/methylene chloride (10:1/v: v) as an eluent to give 12.6100g of a white solid powder, namely 4,4' -dibromomethylbiphenyl, in 74.2% yield.
1.70g (5 mmol) of 4,4 '-dibromomethylbiphenyl, 0.780g (12 mmol) of sodium azide were introduced into a three-necked flask with a rotor, 20ml of DMF solvent was added under nitrogen atmosphere, the reaction was stirred at 60℃overnight, deionized water (30 ml) was poured after the reaction solution cooled to room temperature, the mixture was extracted with diethyl ether (3X 20 ml), the organic layer was collected, washed with saturated brine (3X 20 ml), dried over anhydrous magnesium sulfate, filtered and evaporated under reduced pressure to remove the diethyl ether solvent, and the product was purified by silica gel column chromatography using petroleum ether/methylene chloride (20:1/v: v) as eluent to give white solid 4,4' -biphenyl dibenzylazide (designated as a di-terminal aromatic Die nitrogen monomer II-1) 1.230g in 93.1% yield.
FIG. 1 shows that the di-terminal aryl Die nitrogen monomer II-1, the raw material and the intermediate thereof are in CDCl 3 A kind of electronic device 1 H NMR comparison. From the nuclear magnetic resonance spectrum, the nuclear magnetic resonance of the 4,4' -dimethylbiphenyl material to the bromine intermediate revealed that the peak of methyl hydrogen at 2.48ppm of the original material disappeared, and that the chemical shift of methylene hydrogen at 4.57ppm occurred, indicating that the hydrogen at the α position of the material had undergone NBS reaction, yielding a benzyl bromide intermediate. The nuclear magnetic comparison of the bromine intermediate and the azide product can find that the chemical shift of hydrogen on methylene is obviously shifted to a high field to 4.42ppm mainly because the polarity of azide is smaller relative to bromine, so that the chemical shift is changed, further the nucleophilic substitution reaction of sodium azide and benzyl bromide is shown, the azide product is synthesized, and the successful preparation of the di-end aryl Die nitrogen monomer II-1 is verified.
(2) 17.80-g N-bromosuccinimide (NBS, 100 mmol), 5.3082g of paraxylene (50 mmol), 0.2422g of dibenzoyl peroxide (BPO, 1 mmol) and 60mL of carbon tetrachloride were put into a 250mL three-necked flask equipped with a rotor, the suspension was filtered after condensing and refluxing at 78℃for 12 hours under nitrogen atmosphere, the filtrate was concentrated, and recrystallized from methanol to give 8.2312g of white crystals (1, 4-bis- (bromomethylbenzene) in 62.4% yield.
2.6395g (10 mmol) of 1, 4-bis- (bromomethylbenzene) and 1.430g (22 mmol) of sodium azide were added to a 100mL three-necked flask equipped with a rotor, 20mL of DMF was added under nitrogen atmosphere and reacted at 60℃for 10 hours, the reaction solution was poured into 100mL of deionized water, extracted three times with 30mL of anhydrous diethyl ether, the organic phase was collected, washed with 100mL of saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated after filtration to give 1.7216g of p-diazidobenzyl (designated as a two-terminal aromatic Die nitrogen monomer II-2) in 91.5% yield.
FIG. 2 is a schematic diagram of a di-terminal aromatic Die nitrogen monomer II-2 and its starting materials, intermediates in CDCl 3 A kind of electronic device 1 H NMR comparison. From the figure, it was found that the peak of methyl hydrogen at 2.48ppm of the starting material disappeared, and that a chemical shift of methylene hydrogen occurred at 4.50ppm, indicating that the hydrogen at the α position of the starting material had undergone an NBS reaction, yielding a benzyl bromide intermediate. Similar to synthetic monomer 1, the nuclear magnetism comparison of the bromine intermediate and the azide product can find that the chemical shift of hydrogen on methylene is obviously shifted to 4.36ppm to a high field, mainly because the polarity of azide is smaller than that of bromine, so that the chemical shift is changed, further the nucleophilic substitution reaction of sodium azide and benzyl bromide is illustrated, and the two-end aryl Die nitrogen monomer II-2 is successfully prepared.
(3) Into a 250mL three-necked flask equipped with a rotor was charged 17.80g g N-bromosuccinimide (NBS, 100 mmol), 5.3083g meta-xylene (50 mmol), 0.2422g dibenzoyl peroxide (BPO, 1 mmol) and 60mL carbon tetrachloride, and the mixture was refluxed at 78℃for 12 hours under a nitrogen atmosphere. The suspension was filtered, the filtrate was concentrated, and recrystallized from methanol to give 6.8342g of white crystals (1, 3-bis- (bromomethylbenzene) in 51.8% yield.
2.6395g (10 mmol) of 1, 3-bis- (bromomethylbenzene) and 1.430g (22 mmol) of sodium azide were added to a 100mL three-necked flask equipped with a rotor, 20mL of DMF was added under nitrogen atmosphere and reacted at 60℃for 10 hours, the reaction solution was poured into 100mL of deionized water, extracted three times with 30mL of anhydrous diethyl ether, the organic phase was collected, washed with 100mL of saturated saline solution, dried over anhydrous magnesium sulfate, and the solvent was evaporated after filtration to give 1.7126g of m-diazidobenzyl (designated as a two-terminal aromatic Die nitrogen monomer II-3) as an oily liquid in 91.0% yield.
FIG. 3 is a diagram of a di-terminal aromatic Die nitrogen monomer II-3 and its starting materials, intermediates in CDCl 3 A kind of electronic device 1 H NMR comparison. From the figure, it was found that the peak of methyl hydrogen at 2.43ppm of the starting material disappeared, and that a chemical shift of methylene hydrogen occurred at 4.51ppm, indicating that NBS reaction of hydrogen at the α position of the starting material occurred, yielding a benzyl bromide intermediate. The nuclear magnetism comparison of the bromine intermediate and the azide product can find that the chemical shift of hydrogen on methylene is obviously shifted to 4.38ppm towards the high field, which indicates that nucleophilic substitution reaction of sodium azide and benzyl bromide is carried out, and the two-terminal aryl Die nitrogen monomer II-3 is successfully prepared.
(4) 0.1261g (1 mmol) of paradiyne and 0.2643g (1 mmol) of 4,4' -biphenyldibenzyl azide were charged into a three-necked flask equipped with a rotor, and dissolved in 20ml of DMSO solvent, and stirred at 45℃for 30 minutes under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10ml of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20ml deionized water for three times, filtering, dissolving the filter cake in DMSO solvent, pouring 50ml mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.2891g of pale yellow solid powder which is PTA1, and the yield is 74.1%.
Meanwhile, the embodiment also provides a polyphenylsulfone ether triazole (PTA 1') as a comparison, the structural formula is shown in the specification,wherein R is->The preparation process is as follows:
(1) To a 100mL three-necked flask, 2.5027g (10 mmol) of p-methylbenzene, 3.5688g (30 mmol) of 3-bromopropyne, 5.5284g (40 mmol) of anhydrous potassium carbonate and 50mL of anhydrous acetone solvent were added, nitrogen was introduced, the reaction was stirred overnight at 60℃and followed by thin plate chromatography TLC, the reaction was stopped after completion of the reaction, the potassium carbonate was removed by filtration, the reaction solution was poured into 100mL of deionized water, extracted 3 times with 50mL of ethyl acetate, the organic layer was collected, washed twice with saturated brine, dried over anhydrous magnesium sulfate and the solvent was removed under reduced pressure to give 2.7838g of propargyl-4, 4' -sulfonyldiphenol ether (noted as a di-end-phenylsulfone ether alkyne monomer III) as a white solid product in a yield of 85.3%.
FIG. 4 is a diagram of a di-terminal phenylsulfone ether alkyne monomer III and its starting materials, intermediates in CDCl 3 A kind of electronic device 1 H NMR comparison. From the figure, the hydrogen of the raw material-OH disappears at 10.54ppm, characteristic absorption peaks of the hydrogen in-CH 2 and C≡CH respectively appear at 4.90ppm and 3.64ppm of the product, and the area percentage of peaks at four places of 1,2,3 and 4 in the product is 2:2:2:1, which is consistent with the theoretical value, so that the preparation of the di-end-group phenylsulfone ether alkyne monomer III is successfully carried out.
(2) 0.3264g (1 mmol) of propargyl-4, 4 '-sulfonyldiphenol ether and 0.2643g (1 mmol) of 4,4' -biphenyldibenzyl azide were charged into a three-necked flask equipped with a rotor, and dissolved in 20mL of DMSO solvent, and stirred at 45℃for 30 minutes under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL deionized water for three times, filtering, dissolving the filter cake in DMSO solvent, pouring 50mL mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.4378g of pale yellow solid powder which is PTA1', and the yield is 74.1%.
Example 2
This example provides a polyaryltriazole (designated PTA 2) prepared by the following procedure:
0.1261g (1 mmol) of paradiyne and 0.1882g (1 mmol) of paradiyne were charged into a three-necked flask with a rotor, dissolved in 20ml of DMSO solvent and stirred under nitrogen at 45℃for 30min. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10ml of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20ml deionized water for three times, filtering, dissolving the filter cake in DMSO solvent, pouring 50ml mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.2363g of pale yellow solid powder which is PTA2, and the yield is 75.2%.
Meanwhile, this example also provides a polyphenylsulfone ether triazole (designated as PTA 2') as a comparison. The structural formula of the compound is shown in the specification,wherein R is->The preparation process is as follows:
0.3264g (1 mmol) of propargyl-4, 4' -sulfonyldiphenol ether and 0.1882g (1 mmol) of p-diazepine benzyl are charged into a three-necked flask equipped with a rotor, and 20mL of DMSO solvent is added to dissolve the mixture, and the mixture is stirred under nitrogen at 45℃for 30 minutes. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL of deionized water for three times, filtering, dissolving a filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.3870g of pale yellow solid powder which is PTA2', wherein the yield is 75.2%.
Example 3
This example provides a polyaryltriazole (designated PTA 3) prepared by the following procedure:
0.1261g (1 mmol) of paradiyne and 0.1882g (1 mmol) of m-diazepine are introduced into a three-necked flask with a rotor, dissolved in 20ml of DMSO solvent and stirred under nitrogen at 45℃for 30min. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10ml of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20ml deionized water for three times, filtering, dissolving the filter cake in DMSO solvent, pouring 50ml mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.2401g of pale yellow solid powder which is PTA3, and the yield is 76.4%.
Meanwhile, this example also provides a polyphenylsulfone ether triazole (designated as PTA 3') as a comparison. The structural formula of the compound is shown in the specification,wherein R is->The preparation process is as follows:
0.3264g (1 mmol) of propargyl-4, 4' -sulfonyldiphenol ether and 0.1882g (1 mmol) of m-diazepin were charged into a three-necked flask equipped with a rotor, and 20mL of DMSO solvent was added to dissolve the mixture, followed by stirring at 45℃for 30 minutes under nitrogen atmosphere. 0.0125g (5% mmol) of copper sulphate pentahydrate and 0.0198g (10% mmol) of sodium ascorbate were dissolved in 10mL of deionized water, and added dropwise to the reaction solution with constant pressure drop leak, and reacted overnight. After the reaction, pouring the reaction solution into saturated aqueous solution of saturated EDTA disodium, precipitating, filtering, washing with 20mL of deionized water for three times, filtering, dissolving the filter cake in DMSO solvent, pouring 50mL of mixed solution of methanol/water (3:2/v: v), precipitating precipitate, washing with methanol for 2-3 times, drying and weighing to obtain 0.3967g of pale yellow solid powder which is PTA3', and the yield is 76.4%.
Performance test:
(1) Determination of molecular weight and distribution coefficient
The molecular weights and distribution coefficients of PTA1, PTA2, PTA3 provided in examples 1 to 3 were measured, and the results are shown in table 1 below.
Table 1 molecular weight and distribution coefficients of PTA1, PTA2, PTA3 provided in examples 1 to 3
(2) Thermal performance testing
The thermal performance of PTA1, PTA2, PTA3 and PTA1', PTA2', PTA3' provided in examples 1 to 3 was tested. Tg test process and conditions are that the temperature is raised from 40 ℃ to 300 ℃ at a heating rate of 10 ℃/min, then the temperature is lowered to 40 ℃ at a cooling rate of 30 ℃/min, and finally the temperature is raised to 250 ℃ at a heating rate of 10 ℃/min.
And under the nitrogen atmosphere, the thermal weight loss test shows that the protective gas flow is 30ml/min, the purge gas flow is 30ml/min, and the temperature is increased from 40 ℃ to 600 ℃ at the heating rate of 10 ℃/min, so that the thermal weight loss spectrum of the sample is obtained.
Fig. 5 is a DSC curve of PTA1, PTA2, PTA3, PTA1', PTA2', PTA3'.
Fig. 6 is a graph of TG (a) and DTG (b) for PTA1, PTA2, PTA3 and PTA1', PTA2', PTA3'.
Table 2 shows the thermal performance test results of PTA1, PTA2, PTA3, PTA1', PTA2', PTA3'.
Table 2 results of thermal performance testing of PTA1, PTA2, PTA3, PTA1', PTA2', PTA3
As can be seen from fig. 5, 6 and table 2, PTA1, PTA2 and PTA3 have better high temperature resistance, and the high temperature resistance of PTA1, PTA2 and PTA3 is correspondingly better than that of PTA1', PTA2' and PTA3'.
The glass transition temperature of the polytriazole PTA1-PTA3, which is measured, is the order of PTA1> PTA2> PTA3, can be explained from the molecular structure of three polymers, the main chain of the PTA1 contains a biphenyl structure with higher rigidity, the movement of chain segments is limited to a large extent, the Tg is maximum, the interval between molecules of the PTA3 is larger due to the spiral-like structure, the chain is not orderly stacked, the free volume is larger, and the glass transition temperature is greatly reduced relative to PTA1 and PTA 2. Compared with PTA1-PTA3, PTA1'-PTA3' has a larger degree of reduction in glass transition temperature, and the biggest reason is that the flexibility of a polymer is improved after the-O-group in the alkyne monomer is introduced into the main chain of the polytriazole, the rotation resistance in the molecular chain is smaller, and the glass transition temperature is reduced.
Comparing the results of the thermal stability of the PTA1-PTA3 polymers, the thermal stability of PTA1 is the best, the residual mass at 600 ℃ is the highest, mainly because the rigidity of PTA1 is the highest, the stacking of molecular chains is more compact, the acting force between molecular chains is larger, the polymer is decomposed by heating to a higher temperature, the molecular weight of PTA3 is higher, but the stacking between molecular chains is looser, as can be seen from the DTG curve, when the temperature rises to a certain stage, the decomposition rate is increased, the mass is rapidly reduced, and the residual rate at 600 ℃ is the lowest. The differences between PTA1'-PTA3' are small compared to the thermal stability of PTA1-PTA3, and the trends of TG and DTG curves are also very similar, and analyzing the cause may have two aspects: on the one hand, the flexibility of PTA1'-PTA3' is relatively large, the stacking between molecular chains is relatively loose, and the difference between PTA3 and PTA1 and PTA2 is not as large. On the other hand, PTA3' has a larger molecular weight than PTA1' and PTA2', and the difference of thermal stability is reduced to a certain extent, so that the three polytriazole resins macroscopically show smaller difference of thermal stability.
(3) Dissolution test
The dissolution performance of the p-diacetylene benzene (marked as a two-end aryl alkyne monomer III, abbreviated as III) and PTA1, PTA2 and PTA3 prepared in examples 1-3 is tested, wherein the testing process comprises the steps of accurately weighing 0.05g of an object to be tested by an electronic balance, adding the object to be tested into 5mL of solvent, continuously stirring at normal temperature, standing for a certain time, taking an upper solution for analysis at intervals after solid phase is completely precipitated, ending the test after the concentration of the two is basically consistent, and comparing the solubility, and defining the object to be tested as complete dissolution if no object to be tested remains; if the residual quantity of the object to be detected is 1-90%, defining that the object to be detected is partially dissolved; if the residual amount of the object to be measured is more than 90%, it is defined as insoluble.
The test results are shown in Table 3, wherein +: dissolving to: partially dissolving; -: does not dissolve. From Table 2, it can be seen that monomer III is well soluble in the slightly more polar aprotic solvent. PTA1 and PTA2 are relatively poor in solubility and only partially soluble in highly polar solvents such as DMF, DMSO, HFIP, and hardly soluble in aprotic solvents of weak polarity such as chloroform, tetrahydrofuran, etc., while PTA3 is better in solubility than PTA1 and PTA2 and can be better dissolved in aprotic highly polar solvents. The main reason is probably that the meta-position structure of the M3 monomer makes the molecular chain conformation obtained by polymerization take on a spiral structure, and compared with the relatively regular linear structure of PTA1 and PTA2, the space between PTA3 molecules is larger, the solvent is easier to permeate the inside of the high molecular chain, and the solubility is relatively better.
Table 3 results of dissolution test of PTA1, PTA2, PTA3
Those of ordinary skill in the art will recognize that the embodiments herein are intended to assist the reader in understanding the principles of the invention and should be understood that the scope of the invention is not limited to such specific statements and embodiments. Those of ordinary skill in the art can make various other specific modifications and combinations from the teachings of the present disclosure without departing from the spirit thereof, and such modifications and combinations remain within the scope of the present disclosure.
Claims (8)
1. A polyaryltriazole is characterized by having a structure represented by the formula (I):
(I)
Wherein R isThe method comprises the steps of carrying out a first treatment on the surface of the n is an integer of 27 to 52.
2. The polyaryltriazole of claim 1, wherein n is an integer from 35 to 45.
3. The method for preparing the polyaryltriazole according to any one of claims 1 to 2, which is characterized by comprising the following steps: the method comprises the steps of carrying out click polymerization reaction on a two-end aryl Die nitrogen monomer shown in a formula (II) and a two-end aryl alkyne monomer shown in a formula (III) under the action of a click polymerization catalyst to obtain the polyaryltriazole;
(II)
Formula (III).
4. The method for preparing polyaryltriazole according to claim 3, wherein the click polymerization catalyst is a monovalent copper salt catalyst.
5. The method for preparing a polyaryltriazole according to claim 3, wherein the molar ratio of the click polymerization catalyst to the nitrogen monomer of the two-terminal aryl Die is (1-3): 50.
6. The method for preparing polyaryltriazole according to claim 3, wherein the temperature of the click polymerization reaction is 30 to 80 ℃.
7. The process for preparing a polyaryltriazole according to claim 3, wherein the molar ratio of the nitrogen monomer of the two-terminal aryl Die to the alkyne monomer of the two-terminal aryl is 1:1.
8. The use of the polyaryltriazole according to any one of claims 1-2 in the preparation of a high temperature resistant resin.
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| CN106519226A (en) * | 2015-09-11 | 2017-03-22 | 华东理工大学 | Three-functional-group alkyne derived polytriazole resin and preparation method thereof |
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| CN106519226A (en) * | 2015-09-11 | 2017-03-22 | 华东理工大学 | Three-functional-group alkyne derived polytriazole resin and preparation method thereof |
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| Mustafa Arslan等."Dibenzoyldiethylgermane as a visible light photo-reducing agent for CuAAC click reactions".《Polymer Chemistry》.2015,第6卷第8168-8175页. * |
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