CN106519226A - Three-functional-group alkyne derived polytriazole resin and preparation method thereof - Google Patents
Three-functional-group alkyne derived polytriazole resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to novel three-functional-group alkyne derived polytriazole resin and a preparation method thereof; aromatic propargyl ether is prepared by a substitution reaction of an aromatic type trihydric phenol compound, and then undergoes a 1,3-dipolar cycloaddition reaction with azide to prepare the novel three-functional-group alkyne derived polytriazole resin. The novel three-functional-group alkyne derived polytriazole resin has more benzene ring structures, has better heat resistance, and is expected to be used as a resin matrix of aerospace structural materials and the like and is widely applied.
Description
【Technical field】
The present invention relates to resin technology field, specifically, is polytriazoles derived from a kind of trifunctional alkynes
Resin and preparation method thereof.
【Background technology】
Polytriazoles resin is that one kind carries out 1,3- dipole-diople interactions by polynary azido compound and alkynyl compoundss
Reaction forms the class high performance resin containing 1,2,3-triazoles ring in backbone structure.Polytriazoles resin has good
Good processing characteristics, curing reaction can occur if 70 DEG C at a lower temperature, the resin tool solidifying to form
There is good heat stability.
1893, and Michael [Michael A..J Parkt Chem, 1893 (48)：94] find azido compound
1,3- Dipolar Cycloaddition can occur at 60～80 DEG C with alkynyl compoundss, formed containing-two replacement of Isosorbide-5-Nitrae and
1,5- bis- replacements -1,2,3-triazoles cycle compound, its reaction equation are as follows：
The later stage sixties 20th century, Johnson et al. have found have simultaneously under study for action in molecular structure
The compound of azido and alkynyl can occur intramolecular 1,3- Dipolar Cycloaddition, generate main chain and contain
The linear polymer of 1,2,3-triazoles ring, the polymer of the type have good heat stability [[1] K.E
Johnson, J.A.Lovinger, C.O.Parker, et al., Polym Lett, 1966,4 (12), 977；[2]M.G.
Baldwin, K.E.Johnson, J.A.Lovinger, et al., Polym Lett, 1967,5 (11), 803].20
When the eighties in century, Mock et al. have found that the reagent with amino is catalyzed with some, the 1,3- of nitrine-alkynyl
Dipolar Cycloaddition only generates the triazole ring structure of Isosorbide-5-Nitrae replacement.2002, East China University of Science's yellow hair
Flourish laboratory begins one's study the reaction of alkynes and nitrine, and using alkynes and nitrine thermal response preparing polytriazoles
Resin.The same year, Sharpless et al. report the 1,3- of the nitrine-alkynyl for having used cuprous salt (CuI) to be catalyzed
Dipolar Cycloaddition, it is found that the additive reaction speed of catalysis improves 106Times, and there is vertical structure to select
Property, Isosorbide-5-Nitrae-dibasic 1,2,3-triazoles compound is only generated, Sharpless proposes Click chemical concepts.
In recent years, more and more researcheres utilize alkynes and the click-reaction of nitrine to design new macromolecule,
Design and functionalization, the surface for preparing macromolecule prepolymer, particularly branched polymer is modified etc..In height
Molecule new material is designed and in synthesis, introduces the good phenyl ring of symmetry or fragrant miscellaneous in polymer macromolecule chain
Ring is a main path for obtaining heat-resistant polymer.Pyridine ring is a rigid heteroaromatic molecule,
With armaticity, symmetry, alkalescence and polarity.Research shows that the polymer that main chain contains pyridine ring has
Excellent heat stability.In addition, 1,2,3-triazoles ring has conjugated structure, therefore the polytriazoles containing pyridine ring
Resin will be a polymer that class heat resistance is good, chemical property is more stable.
Research shows that the resin containing triazole ring is a kind of with higher glass transition temperature (Tg) on main chain
Polymer.2007, polytriazoles resins of the Nicolas Le Bauta et al. to different cross-linked network structures
Solidification process studied, as a result show, regardless of whether addition catalyst, solid at different temperatures
The Tg of the polytriazoles resin of change is above 50～60 DEG C of solidification temperature, has good heat stability.
[N.L.Bauta, D.D.Diaz, H.R.Brown, et al., Polym, 2007,48,239]
East China University of Science Du Lei, yellow hair honor et al. are added using 1, the 3- dipole-rings of azido under low temperature and alkynyl
Polytriazoles resin is prepared for into reaction, a class is successfully developed and be there is excellent processability, hot property and machine
The resin of the new low-temperature curable of tool performance, wherein comprising various cross-linked network structures and line style containing three
The polymer of azoles ring, this series of resin not only Td5It is very high, and possess very high glass transition
Temperature, highest can be up to 325 DEG C；Fibrous composite has higher mechanical property, T700 carbon fibers
Composite bending strength reaches 2000MPa, and bending moduluses reach 150GPa, has at 180 DEG C high
Retention rate.[a. ten thousand is inner strong, and Hu Yanhong, Luo Yonghong, Rong Zhuxia, surrounding, yellow hair are flourish, Qi Huimin, Du
It is of heap of stone, Chen Xiangbao. the 13rd national composite academic conference, Chinese Chengdu, 2004.11. composites-
Cost, environment and industrialization, Chen Xiangbao chief editors, aircraft industry publishing house：Beijing, 2004, pp327～331；
B. retinue's bright red, Luo Yonghong, Wan Liqiang, Qi Huimin, yellow hair are flourish, Du Lei, macromolecule journal,
2005,4,560～565；C.ZL 200610055771.6,2006；D.ZL 201110263712.9,2011；e.
ZL 200710043631.1,2007].Part polytriazoles resin hot property is as shown in table 1.
1 polytriazoles resin system hot property of table
Note：A represents azido compound, and B represents alkynyl compoundss, and subscript represents functional group's number, such as A2B4Represent two functional group's nitrine and four alkynes
Base polymerizable resin system.
【The content of the invention】
It is an object of the invention to overcome the deficiencies in the prior art, there is provided gather derived from a kind of trifunctional alkynes
Triazole resin and preparation method thereof.Existing polytriazoles resin system has certain limitation on molecular structure
Property, the fat chain structure in main chain reduces the rigidity of polymer, so as to limit polymer heat-resistant.
It is contemplated that exploitation is a kind of being polymerized by rigid trifunctional propargyl ether monomer and azido compound
Heat-resisting polytriazoles resin.
The purpose of the present invention is achieved through the following technical solutions：
Polytriazoles resin derived from a kind of trifunctional alkynes, its structural formula are Formulas I or Formula II,
Or be：
In polytriazoles resin derived from trifunctional alkynes, the chemical constitution of trifunctional propargyl ether is as follows：
Wherein
In the chemical constitution of described trifunctional propargyl ether, the degree of functionality of propargyl ether is 3, phenyl ring
Number is 3, improves the rigidity of polytriazoles resin, makes polytriazoles resin have good thermostability.
Polytriazoles resin and preparation method thereof derived from a kind of trifunctional alkynes, first with the ternary of invention
Phase transfer reaction prepares ternary propargyl ether compound to phenolic compound in the basic conditions with halo propine,
Carry out reaction again with azido compound and generate polytriazoles resin；Which concretely comprises the following steps：
(1) synthesis of trihydric phenol pyridine
" one kettle way " prepares trihydric phenol pyridine：By hydroxy benzaldehyde, hydroxy acetophenone, ammonium acetate and acetic acid add
Enter in there-necked flask, hydroxy benzaldehyde, hydroxy acetophenone, ammonium acetate three's gross mass accounts for acetum matter
Amount 60～80%；Reaction temperature is 100～120 DEG C, 4～12h of response time；Benzaldehyde and 1-Phenylethanone.
Mol ratio [benzaldehyde]/[vinegar of mol ratio [benzaldehyde]/[1-Phenylethanone .]=1.0: 2.0～2.2, benzaldehyde and ammonium acetate
Sour ammonium]=1.0: 1.3～13；After reaction terminates, question response solution is cooled to room temperature, is poured into deionized water
In, obtain half sticky mass of yellow；The thick substances are washed till into neutrality, yellow solid matter is obtained.
Solid matter Jing mass fractions are recrystallized to give yellow flat crystal ternary for 70～90% ethanol waters
Phenol pyridine；
Pyridine ring is a rigid heteroaromatic molecule, with armaticity, symmetry, pyridine ring and three
The introducing of individual phenyl ring, improves the rigidity of polytriazoles resin, has polytriazoles resin higher thermally-stabilised
Property, glass transition temperature Tg is more than 250 DEG C；Mass fraction is tied again for 70～90% ethanol waters
The trihydric phenol pyridine stable crystal form that crystalline substance is obtained, purity are high, and purity is up to 98%, and recrystallization loss is little；
(2) preparation of ternary propargyl ether compound
Using ternary phenolic compound, phase transfer reaction preparation ternary is propargyl in the basic conditions with halo propine
Base ether compound, its concrete structure are as follows：
The synthesis of ternary propargyl ether compound is carried out in biphase, is organic faciess and water phase respectively；
Ternary phenolic compound, phase transfer catalyst and NaOH solution is added in a kettle., treats above-mentioned mixing
Thing stir after dropwise Deca halo propine, reaction temperature is 50～55 DEG C, and the response time is 4～6h；
Ternary phenolic compound and halo propine press group molar ratio [phenolic hydroxyl group]/[halides]=1.0: 1.0～1.7, more
Desirable 1.0: 1.0～1.3；Ternary phenolic compound is 7.0: 1.0～3.0 with the mol ratio of phase transfer catalyst；
Obtain ternary propargyl ether compound；
Described organic faciess may be selected acetonitrile, DMSO, THF, halo propine etc.；Halo propine is used as having
Machine phase, can both participate in reaction, reduce the use of other organic faciess again, and make reaction simpler, drop
Low reaction cost.
Described water mutually may be selected NaOH solution, Na2CO3Solution etc.；
Described phase transfer catalyst is tetrabutyl ammonium bromide, benzyltriethylammoinium chloride or benzyl trimethyl
Ammonium chloride；The high catalytic efficiency of such catalyst, shortens response time, advantage of lower cost.
Described halo propine is chloride, bromide or iodide；
Described ternary phenolic compound is specially ternary propargyl ether phenylpyridine and ternary propargyl ether benzene
Base ethane.The ternary phenolic compound symmetry is good, and phenolic hydroxyl group uniform spatial distribution, beneficial to halo propine
React, improve the yield of ternary propargyl ether compound.
(3) prepare polytriazoles resin derived from trifunctional alkynes
Ternary propargyl ether compound and azido compound [4,4 '-biphenyl dimethyl nitrine (BAMBP) with
And 1,3,5- triazido -2,4,6- trimethylbenzenes (TAMTMB)] press group molar ratio (azido group)
/ (alkynyl group)=1.0: 1.0～1.30 are mixed in organic solvent, ternary propargyl ether compound with it is folded
The gross mass of nitrogen compound occupies machine solution quality 40～80%, can more be 50～70%；Reaction temperature is
40～90 DEG C, can be more 50～60 DEG C, and 3～6h of response time can more be 5h；After reaction terminates, instead
Thing is answered to be cooled to room temperature；Obtain polytriazoles resin solution derived from trifunctional alkynes.
Described organic solvent selects acetone, and dichloromethane is a kind of in THF, DMSO or DMF.
Described organic solution, solute be ternary propargyl ether compound, azido compound
Solution：Ternary propargyl ether compound, azido compound, organic solvent (acetone, dichloromethane, THF,
DMSO, DMF)；Organic solution is ternary propargyl ether compound, azido compound and organic solvent；
Solute is 40～80% in the mass fraction of organic solution.
Compared with prior art, the positive effect of the present invention is：
Novel polytriazole resin derived from a kind of trifunctional alkynes of present invention synthesis, has the characteristics that：
Ternary propargyl ether compound contains three phenyl ring, improves the rigidity of polytriazoles resin, makes polytriazoles tree
Fat has higher heat stability, and glass transition temperature Tg is more than 250 DEG C；Ehter bond is incorporated into into three
In the backbone structure of azoles resin, make polytriazoles resin that there is good processing characteristics, be soluble in acetone, THF,
DMSO and DMF polar solvents；Novel polytriazole resin has preferable mechanical property, as advanced
The resin matrix of composite, is expected to be used widely in fields such as space flight and aviation, armament equipments.
【Specific embodiment】
Derived from a kind of trifunctional alkynes of the invention presented below, polytriazoles resin and preparation method thereof is concrete
Embodiment.
Embodiment 1
The preparation of polytriazoles resin P-PTA-32
The synthesis of (1) 2,4,6- tri- (4- hydroxy phenyls) pyridine (HPP)
By hydroxy benzaldehyde (25mmol, 3.053g), parahydroxyacet-ophenone (50mmol, 6.8075
G) it is added to one and agitator, thermometer and backflow are housed with ammonium acetate (325mmol, 25.052g)
In the 100mL there-necked flasks of device, solvent acetic acid (58.19ml) is eventually adding.Then will reaction temperature
Degree is raised to 120 DEG C of back flow reaction 6h.Lower the temperature afterwards, treat that solution is cooled to room temperature, be poured into deionization
In water, half sticky mass of yellow is obtained.The thick substances are washed till into neutrality, yellow solid matter is obtained.
70% ethanol waters of solid matter Jing (ethanol: water=7: yellow flat crystal 3) is recrystallized to give,
Yield is 58%, and purity is 97.6%, and fusing point is 208 DEG C；FTIR (KBr, v, cm-1)：3390(-OH
Stretching vibration peak), 3034 (C-H stretching vibration peaks on phenyl ring), 1599,1546,1513,1444 (benzene
The vibration absorption peak of ring skeleton), 1399 (C-N flexural vibrations peaks), 1236 (Ar-O stretching vibration peaks),
825,753,646 (C-H flexural vibrations peaks on phenyl ring)；1H-NMR (DMSO) δ (ppm, H
Subscript represents locations of structures)：6.89-6.93 (d, 6H, H2,6), 7.83-7.88 (m, 4H, H4,5),
8.13-8.15 (m, 4H, H3), 9.72 (s, 2H, H1), 9.80 (s, 1H, H7).Its structure is：
The synthesis of (2) 2,4,6- tri- (the propargyl epoxide-phenyl of 4-) pyridine (POPP)
By 20%NaOH solution (95ml), HPP (0.04mmol, 14.2g) and tetrabutyl ammonium bromide
(0.004mmol, 1.29g) is mixed in 100mL there-necked flasks.Treat that said mixture stirs
Afterwards, by propargyl bromide, (0.13mmol, 15.46) is slowly dropped in mixed liquor in 20min, heats up
To 50-55 DEG C of reaction 5h.After reaction terminates, the extraction of reaction solution Jing dichloromethane, separatory funnel are separated,
Water phase is removed, solvent is then distilled off, is repeatedly washed with methanol, obtain white powder, yield is 95%,
Purity is 97.2%, fusing point：107℃；1H-NMR(CDCl3, TMS) and δ (ppm, H subscript tables
Show locations of structures)：2.59-2.60 (t, 3H, H1,9), 4.80-4.81 (s, 6H, H2,8), 7.13-7.17
(d, 6H, H3,7), 7.73-7.78 (m, 4H, H5,6), 8.16-8.18 (d, 4H, H4), its knot
Structure is：
(3) preparation of P-PTA-32
By POPP (4.9mmol, 2.30g), 4,4 '-biphenyl dimethyl nitrine (BAMBP, 7.0mmol,
1.85g), acetone (4.15g) adds there-necked flask, is made into the solution that solid content is 50%, mechanical agitation,
Logical condensed water, 55 DEG C of reaction 4h.After reaction terminates, reactant is cooled to room temperature, obtains brown P-PTA-32
Resin solution.P-PTA-32 is dissolvable in water the intensive polar solvents such as acetone, THF, DMF, DMSO.DSC
Analysis (10 DEG C/min, nitrogen) shows that resin can solidify at 80～180 DEG C.Resin solution is removed molten
After agent, 80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h of follow procedure solidifications in an oven, obtain brown hard
Hard solidification product.Tg is measured for 250 DEG C by DMA analyses (double cantilevers)；Analyzed by TGA
(10 DEG C/min, nitrogen) measure 5% thermal weight loss temperature T of solidfied materiald5For 357 DEG C.
Embodiment 2
The preparation of polytriazoles resin P-PTA-33
By POPP (4.2mmol, 1.97g), 1,3,5- triazido -2,4,6- trimethylbenzenes (TAMTMB,
4mmol, 1.14g), acetone (4.67g) add there-necked flask, be made into the solution that solid content is 40%,
Mechanical agitation, leads to condensed water, 55 DEG C of reaction 3h.After reaction terminates, reactant is cooled to room temperature, obtains
Brown P-PTA-33 resin solution.P-PTA-33 is dissolvable in water acetone, THF, DMF, DMSO etc.
Intensive polar solvent.Dsc analysis (10 DEG C/min, nitrogen) show that resin can solidify at 80～180 DEG C.
By follow procedure in an oven after resin solution desolvation
80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h solidifies, and obtains the hard cured product of brown.Pass through
DMA analyses (double cantilevers) measures Tg for 310 DEG C；TGA analyses (10 DEG C/min, nitrogen) measures solid
5% thermal weight loss temperature T of compoundd5For 361 DEG C.
Embodiment 3
The preparation of polytriazoles resin E-PTA-32
The synthesis of (1) 1,1,1- tri- [4- (the propargyl epoxides of 2-) phenyl] ethane (POPE)
1,1,1- tri- (4- hydroxy phenyls) ethane (HPE, 5mmol, 1.53g) is dissolved in dimethyl
In the mixed solution of sulfoxide (6ml) and 20% sodium hydroxide (3ml), then by propargyl bromide (18mmol,
2.14g) it is added drop-wise in said mixture in 30min by constant pressure funnel.React after completion of dropwise addition
Mixture is stirred at room temperature 48h.After the completion of reaction, mixture is washed into into neutrality, sucking filtration, drying,
With recrystallizing methanol, light yellow crystal, yield 89%, purity 96.5% is obtained；80.0 DEG C of fusing point.1H-NMR
(CDCl3, TMS) δ (ppm, H subscript represents locations of structures)：2.1 (s, 3H, H5)；2.5 (s,
3H, H1)；4.7 (t, 6H, H2)；6.8 (m, 6H, H3)；7.1 (m, 6H, H4), its knot
Structure formula is：
(2) preparation of E-PTA-32
By POPE (5.25mmol, 2.21g) and BAMBP (7.5mmol, 1.98g) at 70 DEG C
Stir to molten condition.After reaction terminates, reactant is cooled to room temperature, obtains brown E-PTA-32 resin
Solution.E-PTA-32 is dissolvable in water the intensive polar solvents such as acetone, THF, DMF, DMSO.DSC point
Analysis (10 DEG C/min, nitrogen) shows that resin can solidify at 80～180 DEG C.By resin solution desolvation
80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h of follow procedure solidifications in an oven, obtain brown hard afterwards
Cured product.Tg is measured for 258 DEG C by DMA analyses (double cantilevers)；TGA analyses (10 DEG C/min,
Nitrogen) measure 5% thermal weight loss temperature T of solidfied materiald5For 330 DEG C.
Embodiment 4
The preparation of polytriazoles resin E-PTA-33
By POPE (5.25mmol, 2.21g), TAMTMB (5mmol, 1.43g) and acetone (3.64g)
There-necked flask is added, the solution that solid content is 50% is made into, is stirred, lead to condensed water, 55 DEG C of reaction 4h.
After reaction terminates, reactant is cooled to room temperature, obtains brown E-PTA-33 resin solution.E-PTA-33
It is dissolvable in water the intensive polar solvents such as acetone, THF, DMF, DMSO.Dsc analysis (10 DEG C/min, nitrogen
Gas) show, resin can solidify at 80～180 DEG C.Journey is pressed after resin solution desolvation in an oven will
80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h of sequence solidifies, and obtains the hard cured product of brown.Pass through
DMA analyses (double cantilevers) measures Tg for 305 DEG C；TGA analyses (10 DEG C/min, nitrogen) measures solid
5% thermal weight loss temperature T of compoundd5For 354 DEG C.
Embodiment 5
The preparation of unidirectional carbon/P-PTA-32 resin composite materials
Embodiment 1 is prepared P-PTA-32 to be dissolved in acetone, the tree of solid content 33wt% is configured to
Fat glue.After T700 carbon fibers impregnation row's yarn is dried, 15 × 25cm is cut into2The carbon cloth of size, and spread
It is stacked to certain thickness and is placed in press the sheet material for being pressed into about 2mm thickness.Pressing process：After deaerating at 80 DEG C
Cure under pressure.Molding technological condition：80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h, briquetting pressure
6MPa.Bending strength is 1667MPa, and interlaminar shear strength is 65MPa.
Embodiment 6
The preparation of unidirectional carbon/P-PTA-33 resin composite materials
Embodiment 2 is prepared P-PTA-33 to be dissolved in acetone, the tree of solid content 33wt% is configured to
Fat glue.After T700 carbon fibers impregnation row's yarn is dried, 15 × 25cm is cut into2The carbon cloth of size, and spread
It is stacked to certain thickness and is placed in press the sheet material for being pressed into about 2mm thickness.Pressing process：After deaerating at 80 DEG C
Cure under pressure.Molding technological condition：80 DEG C/6h+120 DEG C/2h+150 DEG C/2h+180 DEG C/2h, briquetting pressure
6MPa.Bending strength is 1583MPa, and interlaminar shear strength is 82MPa.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
Logical technical staff, without departing from the inventive concept of the premise, can also make some improvements and modifications,
These improvements and modifications are also should be regarded as in protection scope of the present invention.
Claims (10)
1. polytriazoles resin derived from a kind of trifunctional alkynes, it is characterised in that its structural formula be Formulas I or
Formula II,
Or be：
2. polytriazoles resin derived from a kind of trifunctional alkynes as claimed in claim 1, it is characterised in that
In polytriazoles resin derived from trifunctional alkynes, the chemical constitution of trifunctional propargyl ether is as follows：
Wherein
In the chemical constitution of described trifunctional propargyl ether, the degree of functionality of propargyl ether is 3, phenyl ring
Number is 3.
3. polytriazoles resin and preparation method thereof derived from a kind of trifunctional alkynes, it is characterised in that first
Using the ternary phenolic compound invented, phase transfer reaction prepares ternary alkynes in the basic conditions with halo propine
Ether compound, then reaction generation polytriazoles resin is carried out with azido compound.
4. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 3
Method, it is characterised in which concretely comprises the following steps：
(1) synthesis of trihydric phenol pyridine
" one kettle way " prepares trihydric phenol pyridine：By hydroxy benzaldehyde, hydroxy acetophenone, ammonium acetate and acetic acid add
Enter in there-necked flask, hydroxy benzaldehyde, hydroxy acetophenone, ammonium acetate three's gross mass accounts for acetum matter
Amount 60～80%；Reaction temperature is 100～120 DEG C, 4～12h of response time；Benzaldehyde and 1-Phenylethanone.
The mol ratio 1.0: 1.3～13 of mol ratio 1.0: 2.0～2.2, benzaldehyde and ammonium acetate；After reaction terminates, treat
Reaction solution is cooled to room temperature, is poured in deionized water, obtains half sticky mass of yellow；Should
Thick substances are washed till neutrality, obtain yellow solid matter.Solid matter Jing mass fractions are 70～90%
Ethanol water is recrystallized to give yellow flat crystal trihydric phenol pyridine；
(2) preparation of ternary propargyl ether compound
Using ternary phenolic compound, phase transfer reaction preparation ternary is propargyl in the basic conditions with halo propine
Base ether compound, its concrete structure are as follows：
The synthesis of ternary propargyl ether compound is carried out in biphase, is organic faciess and water phase respectively；
Ternary phenolic compound, phase transfer catalyst and NaOH solution is added in a kettle., treats above-mentioned mixing
Thing stir after dropwise Deca halo propine, reaction temperature is 50～55 DEG C, and the response time is 4～6h；
Ternary phenolic compound and halo propine press group molar ratio 1.0: 1.0～1.7；Ternary phenolic compound and phase
The mol ratio of transfer catalyst is 7.0: 1.0～3.0；Obtain ternary propargyl ether compound；
(3) prepare polytriazoles resin derived from trifunctional alkynes
Ternary propargyl ether compound and azido compound [4,4 '-biphenyl dimethyl nitrine BAMBP and
1,3,5- triazido -2,4,6- trimethylbenzenes (TAMTMB)] press group molar ratio 1.0: 1.0～1.30 and exist
Mixed in organic solvent, it is molten that ternary propargyl ether compound occupies machine with the gross mass of azido compound
Liquid quality 40～80%；Reaction temperature is 40～90 DEG C, 3～6h of response time；After reaction terminates, instead
Thing is answered to be cooled to room temperature；Obtain polytriazoles resin solution derived from trifunctional alkynes.
5. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (2), ternary phenolic compound and halo propine press group molar ratio 1.0: 1.0～
1.7。
6. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (2), ternary phenolic compound and halo propine press group molar ratio 1.0: 1.0～
1.3。
7. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (2), described phase transfer catalyst is tetrabutyl ammonium bromide, three second of benzyl
Ammonium chloride or benzyltrimethylammonium chloride.
8. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (2), described ternary phenolic compound is specially ternary propargyl ether phenyl
Pyridine and ternary propargyl ether diphenylphosphino ethane.
9. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (2), described organic faciess may be selected acetonitrile, DMSO, THF, halo
Propine.
10. polytriazoles resin and its preparation side derived from a kind of trifunctional alkynes as claimed in claim 4
Method, in described step (3), ternary propargyl ether compound is occupied with the gross mass of azido compound
Machine solution quality is 50～70%；Reaction temperature is 50～60 DEG C, and the response time is 5h.
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| CN108440391A (en) * | 2018-04-03 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of 2,4,6- triaryls substituted pyridine derivative |
| CN109369550A (en) * | 2018-12-13 | 2019-02-22 | 利安隆（中卫）新材料有限公司 | A kind of preparation method of triazine-based ultraviolet absorbent |
| CN109400894A (en) * | 2018-06-18 | 2019-03-01 | 上海大学 | Hyperbranched poly triazole functional polymer material and preparation method thereof |
| CN110790927A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN111944145A (en) * | 2019-05-16 | 2020-11-17 | 华东理工大学 | Thermosetting polytriazole ester resin, composite material thereof and preparation method thereof |
| CN111944146A (en) * | 2019-05-16 | 2020-11-17 | 华东理工大学 | Poly-triazole resin containing polyphenyl, composite material thereof and preparation method |
| CN112390948A (en) * | 2020-10-27 | 2021-02-23 | 华南理工大学 | Hyperbranched poly (1, 4, 5-substituted triazole), and preparation method and application thereof |
| CN115028834A (en) * | 2022-06-27 | 2022-09-09 | 东华大学 | Polyaryl triazole and preparation method and application thereof |
| CN117304123A (en) * | 2023-09-27 | 2023-12-29 | 安庆科思化学有限公司 | Preparation method of sun-screening agent Tianlai S |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440391A (en) * | 2018-04-03 | 2018-08-24 | 浙江工业大学 | A kind of preparation method of 2,4,6- triaryls substituted pyridine derivative |
| CN108440391B (en) * | 2018-04-03 | 2019-10-25 | 浙江工业大学 | A kind of preparation method of 2,4,6- triaryl substituted pyridine derivative |
| CN109400894A (en) * | 2018-06-18 | 2019-03-01 | 上海大学 | Hyperbranched poly triazole functional polymer material and preparation method thereof |
| CN109369550A (en) * | 2018-12-13 | 2019-02-22 | 利安隆（中卫）新材料有限公司 | A kind of preparation method of triazine-based ultraviolet absorbent |
| CN109369550B (en) * | 2018-12-13 | 2022-09-20 | 利安隆（中卫）新材料有限公司 | Preparation method of triazine ultraviolet absorbent |
| CN111944146A (en) * | 2019-05-16 | 2020-11-17 | 华东理工大学 | Poly-triazole resin containing polyphenyl, composite material thereof and preparation method |
| CN111944145A (en) * | 2019-05-16 | 2020-11-17 | 华东理工大学 | Thermosetting polytriazole ester resin, composite material thereof and preparation method thereof |
| CN111944146B (en) * | 2019-05-16 | 2022-10-14 | 华东理工大学 | Poly-triazole resin containing polyphenyl, composite material thereof and preparation method |
| CN111944145B (en) * | 2019-05-16 | 2023-11-10 | 华东理工大学 | Thermosetting polytriazole resin, composite material thereof and preparation method thereof |
| CN110790927B (en) * | 2019-11-07 | 2021-09-21 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN110790927A (en) * | 2019-11-07 | 2020-02-14 | 华南理工大学 | Poly-1, 4, 5-substituted triazole and preparation method and application thereof |
| CN112390948A (en) * | 2020-10-27 | 2021-02-23 | 华南理工大学 | Hyperbranched poly (1, 4, 5-substituted triazole), and preparation method and application thereof |
| CN115028834A (en) * | 2022-06-27 | 2022-09-09 | 东华大学 | Polyaryl triazole and preparation method and application thereof |
| CN115028834B (en) * | 2022-06-27 | 2024-03-12 | 东华大学 | Polyaryltriazole and preparation method and application thereof |
| CN117304123A (en) * | 2023-09-27 | 2023-12-29 | 安庆科思化学有限公司 | Preparation method of sun-screening agent Tianlai S |
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