CN101775138B - Novel polytriazoles imide resin and preparation method thereof - Google Patents

Novel polytriazoles imide resin and preparation method thereof Download PDF

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CN101775138B
CN101775138B CN2009100452309A CN200910045230A CN101775138B CN 101775138 B CN101775138 B CN 101775138B CN 2009100452309 A CN2009100452309 A CN 2009100452309A CN 200910045230 A CN200910045230 A CN 200910045230A CN 101775138 B CN101775138 B CN 101775138B
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polytriazoles
imide
compound
preparation
reaction
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CN101775138A (en
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杜磊
黄发荣
周小安
万里强
鄂彦鹏
扈艳红
周燕
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Anhui Keda new Mstar Technology Ltd
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East China University of Science and Technology
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Abstract

The invention discloses polyimide with triazole rings in a main chain structure, i.e. polytriazoles imide resin and a preparation method thereof. The method comprises the following steps: firstly, designing and synthesizing binary azides; then, using binary anhydride and m-phenylacetylene as raw materials for designing and synthesizing terminal alkynyl imide compounds; and thirdly, using the terminal alkynyl imide compounds and azides with equimolar amounts to take 1, 3-Dipolar cycloaddition polymerization reaction in a solvent or adopting thermal polymerization reaction, or adopting redox catalysed polymerization for synthesizing novel polytriazoles imide. The polytriazoles imide resin prepared by the method of the invention has good processing performance, has high thermal stability, simultaneously has good mechanical property and electric performance, and embodies the characteristics of high corrosion resistance performance, high binding power and the like of the polytriazoles imide resin. The invention has wide application prospects in the fields of aviation, astronavigation, micro-electronics, automobiles, shipping industries and the like.

Description

A kind of new polytriazoles imide resin and preparation method thereof
[technical field]
The present invention relates to chemical and material technology field; Relate to a kind of new polytriazoles imide resin and preparation method thereof; Specifically, be a kind of two Terminal Acetylenes base imide compounds and two triazo-compounds warp 1 of utilizing, 3-dipole cycloaddition polyreaction prepares novel polytriazoles imide resin.
[background technology]
In the later stage sixties 20th century, people such as Baldwin find that under study for action the compound that has azido-and alkynyl in the molecular structure simultaneously can take place 1; 3-dipole cycloaddition polyreaction generates 1,4 replacement and 1; 5 substituted line style triazole resins, the polymkeric substance of formation has high thermostability.The eighties in 20th century, when people such as Mock find with the reagent catalysis of some band amino, 1 of nitrine-alkynyl, the 3-Dipolar Cycloaddition only generates 1,4 substituted triazole ring structure.The FSU and domestic Beijing Institute of Technology etc. utilize nitrine and alkyne reaction to prepare novel containing can tackiness agent.2002, East China University of Science is yellow sent out the laboratory flourish and begins one's study the reaction of alkynes and nitrine, and utilizes the thermal response of alkynes and nitrine to prepare the polytriazoles resin.In the same year, people such as Sharpless have reported that with 1 of the catalytic nitrine-alkynyl of cuprous salt (Cu (I)) reaction of 3-dipolar addition finds that catalytic addition reaction speed has improved 10 6Doubly, and have stereoselective, only generate 1, the dibasic 1,2,3-triazoles compound of 4-, Sharpless has proposed the Click chemical concept.
Click reaction is a simple and efficiently building-up reactions in the chemistry, is to be close to perfect chemical reaction, is characterized in that reaction conditions is simple, and insensitive to water and oxygen generally speaking, starting raw material and reagent obtain easily, the productive rate height, and product is easily separated.The 1.3-Dipolar Cycloaddition of nitrine-alkynyl is typical C lick reaction, becomes the focus in the Materials science research.Hawker, people such as Sharpless take the lead in Huisgen1, and the 3-Dipolar Cycloaddition is applied to the synthetic of dendrimer.Afterwards, people utilize Click reaction to synthesize the polymkeric substance of line style, cross-linking type, novel molecular structure such as star-like and hyperbranched in succession.Click reaction as a kind of important compound method in material is synthetic also with other polymerization method, combine like living polymerization, atom transfer radical polymerization method, be widely used in the design and the preparation of novel high polymer material.
East China University of Science is yellow send out the laboratory flourish with azido-and alkynyl take place at a lower temperature 1; The 3-Dipolar Cycloaddition be applied to contain the polymkeric substance of triazole ring synthetic in; Successfully developed and contained 1,4-two replacements and 1,5-two replacements-1; 2, the polytriazoles resin of the line style of 3-triazole ring, crosslinking curing type low-temperature curable.Result of study shows that heat cross-linking solidified polytriazoles resin has excellent processing characteristics, thermal property and mechanical property.Recently, people such as Tang Benzhong also utilize the cycloaddition reaction of on-catalytic nitrine and alkynes, prepared weight-average molecular weight and be 2～30,000 contain phenyl ring line style polytriazoles functional materials.
Triazole ring has good thermotolerance, heatproof oxidation performance and chemical resistant properties as an inflexible aromatic nucleus, and triazole ring has good cohesiveness to metal, can be widely used as the erosion shield of metallic substance.
Polyimide material is the macromolecular material that contains five yuan of imide rings on the molecule main chain; Not only has good heat-resistant; But also have good dimensional stability, oxidative stability, resistance to corrosive chemicals, radioresistance, and favorable mechanical performance and dielectric properties; Therefore have outstanding using value, be widely used in fields such as aerospace, electric and electronic, communications and transportation.
At present, the application form of polyimide has:
1. thin film fabrication.The Kapton film that E.I.Du Pont Company grew up in the sixties is one of polyimide commodity the earliest; Subsequently, Japanese Unitika company has successively developed Upilex-R and Upilex-S film, and these films have low-shrinkage, low heat expansion coefficient, low water absorption, and anti-hydrolytic performance and excellent mechanical property.
2. coating manufacturing.Use as insullac or resistant to elevated temperatures coating.
3. advanced composite material manufacturing.Be widely used in as resistant to elevated temperatures polymer matrix composites on the structural part and engine component of space flight and aviation industry.
4. fiber manufacturing.The fiber isotropic modulus of making is only second to thomel, is the toughener of advanced composite material.
5. foam and engineering plastics manufacturing.The former is as not only high temperature resistant but also low temperature resistant thermal and sound insulating materials, and the latter is mainly used in self-lubricating, sealing, insulation and structured material.
6. in addition, polyimide also is widely used in fields such as microelectronic device, liquid-crystal display, nonlinear optical electric material as functional materials.
But a large amount of researchs show that the molecular chain rigidity of polyimide is bigger, and molecule interchain reactive force is very strong, and molecular chain is closely piled up, and often makes polyimide infusibility indissoluble.To this shortcoming, people have carried out a large amount of research, adopt several different methods to improve the performance of polyimide.In recent years; Through monomeric molecular designing; In molecular structure, introduce special structural units (like, kindliness structural unit, big side group or solvophilic group, distortion and non-coplanar structure), introduce elements such as fragrant heterocycle, fluorine silicon, or polyimide is carried out modification through modes such as copolymerization.The polyimide of having researched and developed at present, has:
1. in dianhydride or diamine monomer, introduce the flowability of flexible structure unit, or improve the solvability and the meltbility of polyimide with raising polyimide molecule chain;
2. in polyimide, introduce distortion and non-coplanar structure, the polyimide molecule segment of formation is distorted, reduce or destroy the conjugated system of polyimide molecule main chain, reduce intermolecular reactive force, thereby improve the solvability of polyimide;
3. on molecular backbone chain, introduce big side group or solvophilic base, reduce the tap density of polymer molecular chain, solvent molecule is infiltrated easily, thereby have good solubility.
In recent years, in the molecular backbone chain of polymkeric substance, introduce the focus that fragrant heterocycle structure has become research.In the molecular backbone chain of polyimide, introduce fragrant heterocycle structure unit and not only can when keeping its very good mechanical properties and resistance toheat, significantly improve its processing characteristics, but also can improve its performance at aspects such as electricity, magnetic.What the fragrant heterocycle structure of introducing was many at present is pyridine ring.Pyridine ring is an inflexible virtue heterocycle molecule, has aromaticity, symmetry, alkalescence and polarity.Result of study shows that the polyimide that main chain contains pyridine ring not only has excellent thermostability, chemicalstability, but also has good solubility and film-forming properties.The polyimide that the preparation main chain contains pyridine ring mainly is to realize through design, synthetic dianhydride or the diamine monomer that contains pyridine ring.People such as John react the dinitro compound that has obtained containing pyridine ring through Claisen-Schmidt, just obtain containing the pyridine diamines through the Pd/C catalytic hydrogenating reduction again.People such as the Li Yanfeng of Lanzhou University have synthesized the serial polyimide that contains pyridine ring.But, containing that the monomeric synthetic difficulty of pyridine ring is big, productive rate is low, cost is high, this has hindered the development that main chain contains the polyimide of pyridine ring to a great extent.
Polyimide has number of ways on synthetic, the polycondensation of aromatic dianhydride and diamines is the universal method of preparation polyimide, and it often needs high-temperature heat treatment just can make its imidization complete, is limited to the application aspect film and coating mostly.In addition, because polyamic acid solution is responsive to temperature when storing, the method for polycondensation has received very big restriction, and therefore, the polyimide of synthetic melt-processable or solubility has just become the emphasis of research.
[summary of the invention]
The objective of the invention is to provides a kind of mechanical property and Good Heat-resistance, solvable fusile processing characteristics to improve greatly through molecular designing with synthetic, the new polytriazoles imide resin that the property of electricity, magnetic aspect is arranged and be prone to process; A purpose more of the present invention is the preparation method of said polytriazoles imide resin is provided, thereby the assurance polyimide to be used more widely.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of polytriazoles imide resin, its chemical structural formula is:
Figure G2009100452309D00041
n＝20～100，
In the formula,
Figure G2009100452309D00042
A kind of in
Figure G2009100452309D00043
;
A kind of in
Figure G2009100452309D00044
;
A kind of in
Figure G2009100452309D00045
;
In described polytriazoles imide resin, the structure of Terminal Acetylenes base imide compound is following:
Figure G2009100452309D00046
A kind of in
Figure G2009100452309D00047
;
A kind of in
Figure G2009100452309D00048
;
In described polytriazoles imide resin, the structure of triazo-compound is following:
Figure G2009100452309D00049
A kind of in
Figure G2009100452309D00052
.
For realizing above-mentioned purpose, the technical scheme that the present invention takes is:
A kind of preparation method of polytriazoles imide resin; It is characterized in that; Prepare polytriazoles imide with Terminal Acetylenes base imide compound and triazo-compound through the chemical cycloaddition polyreaction of the Click of alkynes-nitrine, adopt catalytic polymerization or heat polymerization, its preparation process is:
(1) preparation triazo-compound
With sodiumazide and halohydrocarbon is raw material; Prepare triazo-compound through nucleophilic substitution reaction; Its preparation process is: in solution, carry out the synthetic of triazo-compound, solvent is selected N for use, N '-N (DMF), benzene, toluene, DMSO 99.8MIN. (DMSO) or THF (THF); In reaction kettle, add the mixed solvent of toluene and DMF, both volume ratios are toluene: DMF=1: 1～2, and add-on is that every moles of halogenated hydrocarbon adds 800～1500mL mixed solvent; Add halohydrocarbon, halohydrocarbon is muriate, bromide or iodide; The equivalence ratio that feeds intake of reaction raw materials sodiumazide and halohydrocarbon is 1.0～3.0: 1.0, and temperature of reaction is 20～80 ℃, and the reaction times is 2～10h, and its structural formula is:
Wherein,
Figure G2009100452309D00054
A kind of in
Figure G2009100452309D00055
;
(2) preparation Terminal Acetylenes base imide compound
Through the amine compound reaction of acid anhydrides with the band alkynyl, again with the diacetyl oxide cyclodehydration, synthetic Terminal Acetylenes base imide compound, its preparation process is reacted in two steps and is carried out:
The first step is reacted aromatic anhydride and the aromatic amine of being with alkynyl to the generation amido acid in organic solvent (acetone etc.);
Second step was that catalyzer carries out cyclodehydration with diacetyl oxide as dewatering agent, triethylamine, generated Terminal Acetylenes base imide compound;
These operations should as carrying out under the protective conditions such as nitrogen, helium or argon gas, at last, be used washing with acetone at rare gas element, and purification processes prepares the Terminal Acetylenes base imide compound of gained, and its structural formula is:
Figure G2009100452309D00061
Wherein:
A kind of in
Figure G2009100452309D00062
;
A kind of in
Figure G2009100452309D00063
;
(3) preparation polytriazoles imide
Two Terminal Acetylenes base imide compounds and two triazo-compounds with producing carry out 1 with equimolar amount in solvent, 3-dipole cycloaddition polyreaction, and polyreaction or employing heat polymerization, or adopt catalytic polymerization;
Described solvent is N, N '-N (DMF), N, one or more of N '-N,N-DIMETHYLACETAMIDE (DMAc), DMSO 99.8MIN. (DMSO) or N-Methyl pyrrolidone (NMP);
Described heat polymerization is: equimolar two Terminal Acetylenes base imide compounds and two triazo-compounds are joined in the there-necked flask; Add solvent; Be mixed with mass concentration and be 5～50% mixed solution (being preferably 15-30%), stir fully after, be warming up to 70～120 ℃ (being preferably 80～100 ℃); Stirring reaction 12～48 hours (being preferably 24～36 hours) obtains polymers soln; Be cooled to after the room temperature reaction soln poured in the ethanol and precipitate, obtain white product; Suction filtration, and with after the hot ethanol washing, spend the night at 100 ℃ of vacuum drying oven inner dryings, polytriazoles imide resin obtained;
Described catalytic polymerization is: will wait the Terminal Acetylenes base imide compound of mole number and two triazo-compounds to join in the there-necked flask; Add solvent DMF, DMAc, DMSO or N-Methyl pyrrolidone; Make reactant quality concentration reach 5～50% (being preferably 15～30%); After stirring fully, be warming up to 20～80 ℃ (being preferably 40～60 ℃); Add CuSO again 45H 2O and xitix sodium catalyst; Add-on is respectively 5% and 10% of alkynyl compounds mole number; Add the triethylamine complexing agent with Terminal Acetylenes base imide compound mole number equivalent simultaneously, stirring reaction 2～8 hours (being preferably 3～4 hours) obtains the heavy-gravity polymers soln under the constant temperature; Be cooled to after the room temperature with reaction mixture pour into get final product in the deionized water fibrous polytriazoles imide resin; With deionized water washing by soaking repeatedly, remove catalyzer and triethylamine, suction filtration simultaneously; And with after the hot ethanol washing; Dried overnight in 100 ℃ of vacuum drying ovens obtains the high-molecular weight polytriazoles imide, is dissolved in redeposition purification in N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or the N-Methyl pyrrolidone then; Obtain polytriazoles imide resin after the drying, its chemical equation is:
Figure G2009100452309D00071
n＝20～100，
In the formula:
Figure G2009100452309D00072
A kind of in
Figure G2009100452309D00073
;
A kind of in ;
A kind of in
Figure G2009100452309D00075
.
A kind of new polytriazoles imide resin of the present invention has the following advantages:
(1) triazole ring is incorporated in the backbone structure of polyimide, it is molten meltable that polytriazoles imide resin is prone to, and has good processing properties;
(2) has higher thermostability, its heat decomposition temperature T D5Reach 360 ℃, second-order transition temperature (T g) can be more than 200 ℃;
(3) both had the favorable mechanical performance, had good electric property again;
(4) have functional performances such as erosion resistance, high cohesive force, have wide practical use in fields such as Aeronautics and Astronautics, microelectronics, automobile, shipping industrys.
The preparing method's of a kind of polytriazoles imide resin of the present invention positively effect is:
(1) Click chemistry cycloaddition polymeric reaction condition gentleness is controlled, can under simple condition, carry out, and is insensitive to water and oxygen, need not protections such as nitrogen, helium or argon gas;
(2) Terminal Acetylenes base imide compound prepares easily, and high-temperature sub amination of polyimide synthetic and side reaction thereof have been avoided in imidization fully at a lower temperature;
(3) Click chemistry cycloaddition reaction has thoroughness and specificity; Addition reaction does not influence other functional group, has good compatibility, can in polytriazoles imide, introduce reactive reactive group easily through rational molecular designing; Like carboxyl, hydroxyl etc.;
(4) no small-molecule substance is emitted in the polymerization process, and no side reaction or by product produce, and is prone to the polyimide of synthetic macromolecule amount.
[embodiment]
Below through 9 embodiment preparation method of the present invention is described particularly, its purpose is better to understand content of the present invention, but protection scope of the present invention is not limited to following examples.
Experiment and checking below having carried out according to the preparing method's of above-described a kind of polytriazoles imide resin preparation process.
Embodiment 1
Synthetic (A1) of (1) 1,4-two azido-methyl benzene
In there-necked flask, add 1,4-xylylene dichlorides 50mmol, NaN 3150mmol, toluene 20ml and DMF 20ml under agitation are heated to 70～75 ℃, isothermal reaction 3h; Reaction is cooled to room temperature with reaction product after finishing, and pours in the 200ml deionized water, and hold over night is separated out the white plates crystal under freezing condition; Filter, the cakes with deionized water washing gets the white powder solid after the drying; Productive rate is 90.0%, mp.26.0～27.5 ℃.
(2) synthetic (B1) of two (N-ethynyl phenyl)-Bisphenol A Ether phthalic imidines
, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds bisphenol A-type dianhydride (BPADA) 20mmol in being housed, m-aminophenyl acetylene 40mmol, and adding 50ml acetone is solvent; Reflux adds the diacetyl oxide of 50ml again after 6 hours, and the triethylamine that adds 75ml makees catalyzer, refluxes 6 hours at 80 ℃; Postcooling, deposition have been reacted; Use washing with acetone again, suction filtration, the dry product that gets, productive rate is 92%; FTIR (cm -1): 3254 (≡ C-H), 1776 (the C=O unsymmetrically is flexible), 1714 (the C=O symmetry is flexible, imines I), 1384 (C-N-C, imines II), 748 (C=O); 1H-NMR (DMSO): 7.2～8.0 (Ar-H), 4.31 (≡ CH), 1.67 (CH 3), its structural formula is:
Figure G2009100452309D00091
(3) preparation of polytriazoles imide PTAI-A1-B1
With 1,4-two azido-methyl benzene 10mmol, two (N-ethynyl phenyl)-Bisphenol A Ether phthalic imidine 10mmol and DMAc 30ml add in the reactor drum, fully form transparent solution after the stirring and dissolving, are warming up to 60 ℃, add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1mmol and complexing agent triethylamine 10mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 2 hours; Slowly pour into reaction mixture in the deionized water after being cooled to room temperature; Promptly get thread polytriazoles imide, use the deionized water washing by soaking simultaneously three times, remove catalyzer and triethylamine; Suction filtration; And with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens gets white polytriazoles imide; Be dissolved in then and carry out reprecipitation purification, drying among the DMAc, obtain polytriazoles imide, FTIR (cm -1): 1777 (the C=O unsymmetrically is flexible), 1722 (the C=O symmetry is flexible, imines I), 1372 (C-N-C, imines II), 744 (C=O); 1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.62 (CH 2), 1.68 (CH 3); Its structural formula is:
Figure G2009100452309D00092
The number-average molecular weight Mn:35500 of the polymkeric substance that makes (GPC), Mw/Mn=2.78; Intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.42, water-intake rate is 1.71%; Polytriazoles imide PTAI-A2-B1 has good solubility, at room temperature is soluble in DMF, DMAc, DMSO and NMP equal solvent.
Embodiment 2
Synthetic (A2) of (1) 4,4 '-two azido-methyl biphenyl
In there-necked flask, add 4,4 '-dichloromethyl biphenyl 50mmol, NaN 3150mmol, benzene 20ml and DMF 20ml under agitation are heated to 75 ℃, isothermal reaction 3h; Reaction is cooled to room temperature with reaction product after finishing, and pours in the 200ml deionized water hold over night into; Separate out white solid, filter, the cakes with deionized water washing; Get the white powder solid after the drying, productive rate is 89.0%, 67～71 ℃ of fusing points.
(2) preparation of polytriazoles imide PTAI-A2-B1
With 4,4 '-two azido-methyl biphenyl 10mmol, two (N-ethynyl phenyl)-Bisphenol A Ether phthalic imidine 10mmol and DMAc 40ml add in the reactor drum, form transparent solution, fully are warming up to 60 ℃ after the stirring and dissolving, add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1.0mmol and complexing agent triethylamine 10.0mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 4 hours; Slowly pour into reaction mixture in the deionized water after being cooled to room temperature; Promptly get thread polytriazoles imide, use the deionized water washing by soaking simultaneously three times, remove catalyzer and triethylamine; Suction filtration; And with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens, the polytriazoles imide of biphenyl type that must be white; Be dissolved in then and carry out the reprecipitation purification among the DMAc, drying obtains polytriazoles imide; FTIR (cm -1): 1777 (the C=O unsymmetrically is flexible), 1722 (symmetry of C=O is flexible, imines I), 1372 (C-N-C, imines II), 744 (C=O); 1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.62 (CH 2), 1.67 (CH 3), its structural formula is:
The number-average molecular weight Mn:13000 of the polymkeric substance that makes (GPC), Mw/Mn=1.73; Intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.36, its water-intake rate is 1.62%; Polytriazoles imide PTAI-A2-B1 at room temperature is soluble in DMF, DMAc, DMSO and NMP equal solvent.
Embodiment 3
Synthetic (A3) of (1) 4,4 '-two azido-methyl phenyl ether
In there-necked flask, add 4,4 '-dichloromethyl phenyl ether 50mmol, NaN 3150mmol, toluene 20ml and DMF 20ml under agitation are heated to 75 ℃, isothermal reaction 4h; Reaction is cooled to room temperature with reaction product after finishing, and pours in the 200ml deionized water hold over night into; Separate out white solid, filter, the cakes with deionized water washing; Get the white powder solid after the drying, productive rate is 85.0%.
(2) preparation of polytriazoles imide PTAI-A3-B1
With 4,4 '-two azido-methyl phenyl ether 10mmol, two (N-ethynyl phenyl)-Bisphenol A Ether phthalic imidine 10mmol and DMAc 40ml add in the reactor drum, form transparent solution, fully are warming up to 60 ℃ after the stirring and dissolving, add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1.0mmol and complexing agent triethylamine 10.0mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 8 hours; After being cooled to room temperature reaction mixture is slowly poured in the deionized water, promptly got thread polytriazoles imide; Aftertreatment is identical with instance 2, and drying obtains polytriazoles imide; FTIR (cm -1) with instance 2, its structural formula is:
Figure G2009100452309D00111
The polytriazoles imide PTAI-A3-B1 that makes is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl): 0.30, and second-order transition temperature is 200 ℃, 5% thermal weight loss temperature is 350 ℃ of (N 2).
Embodiment 4
(1) synthetic (B2) of two (N-ethynyl phenyl phthalic imidine) ether
, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds 4 in being housed, the two Tetra hydro Phthalic anhydride 12.4g (0.04mol) of 4 '-oxygen, and m-aminophenyl acetylene 11.23g (0.096mol), adding 100ml acetone is solvent; Reflux adds the diacetyl oxide of 50ml again after 4 hours, and the triethylamine that adds 75ml makees catalyzer, refluxes 4 hours at 80 ℃, has reacted postcooling; Join in the ethanol of 200ml and precipitate, suction filtration is used washing with acetone, suction filtration again; The dry again product that gets, (in the ice-water bath) stirred 30 minutes at low temperatures, and suction filtration obtains white product; Use washing with alcohol again, vacuum-drying, productive rate is 96%; FTIR (cm -1): 3254 (≡ C-H), 1776 (the C=O unsymmetrically is flexible), 1714 (the C=O symmetry is flexible, imines I), 1384 (C-N-C, imines II), 1230 (O-), 748 (C=O); 1H-NMR (DMSO): 7.1～8.0 (Ar-H), 4.32 (≡ CH), its structural formula is:
Figure G2009100452309D00121
(2) preparation of polytriazoles imide PTAI-A1-B2
With 1,4-two azido-methyl benzene 10mmol, two (N-ethynyl phenyl phthalic imidine) ether 10mmol and DMSO 30ml add in the reactor drum, form muddy mixed solution, are warming up to 60 ℃ after fully stirring, and add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1.0mmol and complexing agent triethylamine 10.0mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 4 hours; After being cooled to room temperature reaction mixture is slowly poured in the deionized water of 500mL; Promptly get filamentous polytriazoles imide, use the deionized water washing by soaking simultaneously three times, remove catalyzer and triethylamine; Suction filtration; And with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens gets flaxen polytriazoles imide; Be dissolved in then and carry out reprecipitation purification, drying among the DMAc, obtain polytriazoles imide; FTIR (cm -1): 1777 (the C=O unsymmetrically is flexible), 1722 (symmetry of C=O is flexible, imines I), 1372 (C-N-C, imines II), 1230 (O-), 744 (C=O); 1H-NMR (DMSO): 8.52 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.61 (CH 2); Its structural formula is:
Figure G2009100452309D00122
The polytriazoles imide that makes at room temperature is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.46, and second-order transition temperature is 230 ℃, 5% thermal weight loss temperature is 360 ℃ of (N 2).
Embodiment 5
The preparation of polytriazoles imide PTAI-A2-B2
With 4,4 '-two azido-methyl biphenyl 10mmol, two (N-ethynyl phenyl phthalic imidine) ether 10mmol and NMP 50ml add in the reactor drum, form muddy mixed solution, are warming up to 60 ℃ after fully stirring, and add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1mmol and complexing agent triethylamine 10mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 4 hours; After being cooled to room temperature reaction mixture is slowly poured in the deionized water of 500ml; Promptly get filamentous polytriazoles imide, use the deionized water washing by soaking simultaneously three times, remove catalyzer and triethylamine; Suction filtration; And with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens gets flaxen polytriazoles imide; Dissolve then and carry out the reprecipitation purification among the NMP, drying obtains polytriazoles imide; FTIR (cm -1): 1777 (the C=O unsymmetrically is flexible), 1724 (symmetry of C=O is flexible, imines I), 1378 (C-N-C, imines II), 1232 (O-), 754 (C=O); 1H-NMR (DMSO): 8.5 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.6 (CH 2); Its structural formula is:
Figure G2009100452309D00131
The polytriazoles imide that makes at room temperature is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.35, and second-order transition temperature is 210 ℃, 5% thermal weight loss temperature is 358 ℃ of (N 2).
Embodiment 6
(1) synthetic (B3) of two (N-ethynyl phenyl phthalic imidine) ketone
, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds 3,3 ', 4 in being housed, 4 '-benzophenone tetracarboxylic dianhydride 12.4g (0.04mol); M-aminophenyl acetylene 11.23g (0.096mol), adding 100ml acetone is solvent, reflux adds the diacetyl oxide of 50ml again after 4 hours; And add the 75ml triethylamine and make catalyzer, refluxed 4 hours at 80 ℃, reacted postcooling; Join in the ethanol of 200ml and precipitate, suction filtration is used washing with acetone again; Suction filtration, the dry again product that gets, productive rate is 96%; FTIR (cm -1): 3267 (≡ C-H), 1778 (the C=O unsymmetrically is flexible), 1720 (C=O, the flexible I of symmetry), 1640 (ketone group C=O), 1384 (C-N-C, II), 748 (C=O); 1H-NMR:7.2～8.0 (Ar-H), 4.3 (≡ CH), its structural formula is:
Figure G2009100452309D00132
(2) preparation of polytriazoles imide PTAI-A1-B3
With 1,4-two azido-methyl benzene 10mmol, two (N-ethynyl phenyl phthalic imidine) ketone 10mmol and DMAc 30ml add in the reactor drum, form muddy mixed solution, are warming up to 60 ℃ after fully stirring, and add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1mmol and complexing agent triethylamine 10mmol, and, obtain the heavy-gravity polymers soln 60 ℃ of following stirring reactions 3 hours; Post-treating method is identical with embodiment 4, obtains flaxen polytriazoles imide; FTIR (cm -1): 1779 (the C=O unsymmetrically is flexible), 1725 (symmetry of C=O is flexible, imines I), 1640 (ketone group C=O), 1374 (C-N-C, imines II), 752 (C=O); 1H-NMR (DMSO): 8.5 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.6 (CH 2); Its structural formula is:
Figure G2009100452309D00141
The polytriazoles imide that makes is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.40, and second-order transition temperature is 230 ℃, 5% thermal weight loss temperature is 355 ℃ of (N 2).
Embodiment 7
The preparation of polytriazoles imide PTAI-A2-B3
The preparation of preparation process and embodiment 6 polytriazoles imide PTAI-A1-B3 roughly the same but 60 ℃ of following stirring reactions 4 hours, obtains flaxen polytriazoles imide; FTIR (cm -1) with embodiment 6; Its structural formula is:
The polytriazoles imide that makes is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.30, and second-order transition temperature is 235 ℃, 5% thermal weight loss temperature is 360 ℃ of (N 2).
Embodiment 8
(1) synthetic (B4) of two (N-ethynyl phenyl phthalic imidine) different propane of hexafluoro
, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds 4 in being housed, 4 '-hexafluoroisopropyli,ene Tetra hydro Phthalic anhydride 40mmol, m-aminophenyl acetylene 96mmol; Adding 100ml acetone is solvent, and reflux adds the diacetyl oxide of 50ml again after 4 hours, and adding 75ml triethylamine is made catalyzer; Refluxed 4 hours at 80 ℃, join after having reacted in the deionized water of 500ml, stir deposition; Suction filtration obtains white product, uses washing with alcohol again; Vacuum-drying gets product, and productive rate is 90%; FTIR (cm -1): 1782 (the C=O unsymmetrically is flexible), 1724 (symmetry of C=O is flexible, imines I), 1384 (C-N-C, II imines), 1136 (CF 3), 753 (C=O); 1H-NMR (DMSO): 7.2～8.0 (Ar-H), 4.30 (≡ CH), its structural formula is:
Figure G2009100452309D00151
(2) preparation of polytriazoles imide PTAI-A1-B4
With 1,4-two azido-methyl benzene 10mmol, two different propane 10mmol of (N-ethynyl phenyl phthalic imidine) hexafluoro and DMF 30ml add in the reactor drum, form transparent solution, fully are warming up to 60 ℃ after the stirring and dissolving, add Catalysts Cu SO again 45H 2O 0.5mmol, sodium ascorbate 1mmol and complexing agent triethylamine 10mmol, and 60 ℃ of following stirring reactions 4 hours; Obtain the heavy-gravity polymers soln, reaction mixture is slowly poured in the deionized water of 500mL after being cooled to room temperature, promptly get thread polytriazoles imide; Use the deionized water washing by soaking simultaneously three times, remove catalyzer and triethylamine, suction filtration; And with hot ethanol washing back dried overnight in 100 ℃ of vacuum drying ovens; Obtain the polytriazoles imide of white, be dissolved in then and carry out the reprecipitation purification among the DMF, drying obtains polytriazoles imide; FTIR (cm -1): 1782 (the C=O unsymmetrically is flexible), 1724 (symmetry of C=O is flexible, imines I), 1375 (C-N-C, imines II), 1136 (CF 3), 752 (C=O); 1H-NMR (DMSO): 8.53 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.61 (CH 2), its structural formula is:
The polytriazoles imide that makes is dissolved in DMF, DMAc, DMSO and NMP equal solvent, intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.30, and second-order transition temperature is 235 ℃, 5% thermal weight loss temperature is 360 ℃ of (N 2).
Embodiment 9
Thermopolymerization prepares polytriazoles imide PTAI '-A1-B1
With 1; 4-two azido-methyl benzene 10mmol, two (N-ethynyl phenyl)-Bisphenol A Ether phthalic imidine 10mmol and DMAc 30ml add in the reactor drum, fully form transparent solution after the stirring and dissolving, are warming up to 100 ℃; And, obtain polymers soln 100 ℃ of following stirring reactions 24 hours; Be cooled to after the room temperature reaction mixture poured in the ethanol of 200ml and precipitate, promptly obtain white product, suction filtration, and with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens obtains polytriazoles imide; FTIR (cm -1): 1777 (the C=O unsymmetrically is flexible), 1722 (the C=O symmetry is flexible, imines I), 1372 (C-N-C, imines II), 1150 (CH 3), 744 (C=O); 1H-NMR (DMSO): 8.4～8.5 (H on the triazole ring), 7.2～8.0 (Ar-H), 5.62 (CH 2), 1.68 (CH 3), its structural formula is:
Polytriazoles imide the PTAI '-A1-B1 that makes has good solubility, at room temperature is soluble in DMF, DMAc, DMSO and NMP equal solvent; Intrinsic viscosity (the DMAc solution of 30 ℃ of following 0.5g/dl) 0.28; Second-order transition temperature is 180 ℃, and 5% thermal weight loss temperature is 360 ℃ of (N 2).

Claims (5)

1. a polytriazoles imide resin is characterized in that, its chemical structural formula is:
Figure FSB00000681214200011
n＝20～100，
In the formula,
Figure FSB00000681214200012
A kind of in
Figure FSB00000681214200013
;
A kind of in ;
A kind of in
Figure FSB00000681214200015
.
2. the preparation method of a polytriazoles imide resin as claimed in claim 1; It is characterized in that; Prepare polytriazoles imide with Terminal Acetylenes base imide compound and triazo-compound through the chemical cycloaddition polyreaction of the Click of alkynes-nitrine, its preparation process is:
(1) preparation triazo-compound
With sodiumazide and halohydrocarbon is raw material; Prepare triazo-compound through nucleophilic substitution reaction; Its preparation process is: in solution, carry out the synthetic of triazo-compound, solvent is selected N for use, N '-N, benzene, toluene, DMSO 99.8MIN. or THF; In reaction kettle, add toluene and N, the mixed solvent of N '-N, both volume ratios are toluene: DMF=1: 1～2, add-on is that every moles of halogenated hydrocarbon adds 800～1500mL mixed solvent; Add halohydrocarbon, halohydrocarbon is muriate, bromide or iodide; The equivalence ratio that feeds intake of reaction raw materials sodiumazide and halohydrocarbon is 1.0～3.0: 1.0, and temperature of reaction is 20～80 ℃, and the reaction times is 2～10h, and its structural formula is:
Figure FSB00000681214200021
Wherein,
Figure FSB00000681214200022
A kind of in
Figure FSB00000681214200023
;
(2) preparation Terminal Acetylenes base imide compound
Through the amine compound reaction of acid anhydrides with the band alkynyl, again with the diacetyl oxide cyclodehydration, synthetic Terminal Acetylenes base imide compound, its preparation process is reacted in two steps and is carried out:
The first step is reacted aromatic anhydride and the aromatic amine of being with alkynyl to the generation amido acid in organic solvent;
Second step was that catalyzer carries out cyclodehydration with diacetyl oxide as dewatering agent, triethylamine, generated Terminal Acetylenes base imide compound;
Use washing with acetone at last, purification processes makes Terminal Acetylenes base imide compound, and its structural formula is:
Figure FSB00000681214200024
Wherein:
A kind of in
Figure FSB00000681214200025
;
A kind of in
Figure FSB00000681214200026
;
(3) preparation polytriazoles imide
Terminal Acetylenes base imide compound and triazo-compound with producing carry out 1 with equimolar amount in solvent, 3-dipole cycloaddition polyreaction, and polyreaction adopts catalysis or heat polymerization; Described solvent is N, N '-N, N, one or more of N '-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or N-Methyl pyrrolidone;
Described heat polymerization is: equimolar Terminal Acetylenes base imide compound and triazo-compound are joined in the there-necked flask, add said solvent N, N '-N, N; One or more of N '-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or N-Methyl pyrrolidone; Be mixed with mass concentration and be 5～50% mixed solution, stir fully after, be warming up to 70～120 ℃; Stirring reaction 12～48 hours obtains polymers soln; Be cooled to after the room temperature reaction soln poured in the ethanol and precipitate, obtain white product; Suction filtration, and with after the hot ethanol washing, spend the night at 100 ℃ of vacuum drying oven inner dryings, obtaining polytriazoles imide resin, reaction equation is:
Thermopolymerization:
Figure FSB00000681214200031
Catalyzed polymerization:
Figure FSB00000681214200032
In the formula:
Figure FSB00000681214200033
A kind of in ;
A kind of in
Figure FSB00000681214200035
;
A kind of in
Figure FSB00000681214200036
.
3. the preparation method of polytriazoles imide resin according to claim 2; It is characterized in that; In the heat polymerization of preparation polytriazoles imide, the mass concentration of liquid mixture prepared is 15～30%, is warming up to 80～100 ℃ after the stirring fully; Stirring reaction 24～36 hours obtains polymers soln.
4. the preparation method of polytriazoles imide resin according to claim 2 is characterized in that, the polyreaction of preparation polytriazoles imide adopts catalytic polymerization; Described catalytic polymerization is: will wait the Terminal Acetylenes base imide compound of mole number and triazo-compound to join in the there-necked flask; Add solvent N, N '-N, N, one or more of N '-N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or N-Methyl pyrrolidone; Make reactant quality concentration reach 5～50%; After stirring fully, be warming up to 20～80 ℃, add CuSO again 45H 2O and xitix sodium catalyst; Add-on is respectively 5% and 10% of Terminal Acetylenes base imide compound mole number; Add the triethylamine complexing agent with Terminal Acetylenes base imide compound mole number equivalent simultaneously, stirring reaction is 2～8 hours under the constant temperature, obtains the heavy-gravity polymers soln; Be cooled to after the room temperature with reaction mixture pour into get final product in the deionized water fibrous polytriazoles imide resin, with deionized water washing by soaking repeatedly, remove catalyzer and triethylamine simultaneously; Suction filtration; And with after the hot ethanol washing, dried overnight in 100 ℃ of vacuum drying ovens obtains the high-molecular weight polytriazoles imide; Be dissolved in redeposition purification in N,N-DIMETHYLACETAMIDE, DMSO 99.8MIN. or the N-Methyl pyrrolidone then, obtain polytriazoles imide resin after the drying.
5. the preparation method of polytriazoles imide resin according to claim 4 is characterized in that, in the catalytic polymerization of preparation polytriazoles imide, reactant quality concentration is 15～30%, is warming up to 40～60 ℃ after the stirring fully; The time of stirring reaction is 3～4 hours under the constant temperature, obtains the heavy-gravity polymers soln.
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