CN101117365A - Siliceous alkynes fragrant polytriazoles resin and method for making same - Google Patents
Siliceous alkynes fragrant polytriazoles resin and method for making same Download PDFInfo
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Abstract
The invention relates to an aromatic poly-triazole containing silicon and alkyne and the preparation method, a novel aromatic poly-triazole containing silicon and alkyne which can be solidified with low temperature is prepared by the addition polymerization of the aryne resin containing silicon and the azide. The resin is of low viscosity (less than 1Pa.s) and good wetting quality for fiber, and can be solidified at low temperature such as 70 to 80 DEG C; the glass-transition temperature of the solidified resin is more than 300 DEG C, the solidified resin has good resistance to effect of heat; the common temperature bending strength of the composite material of the aromatic poly-triazole containing silicon and alkyne of unilateral carbon fiber reinforcement is 1800 MPa, the bending modulus is about 120 GPa, the retention rate of the bending strength achieves about 70 percent at 250 DEG C, the bending modulus is almost not changed, the aromatic poly-triazole containing silicon and alkyne has excellent mechanical property and resistance to effect of high temperature. As resin basal body of the composite material of high temperature resistance, the aromatic poly-triazole containing silicon and alkyne has extensive application prospect in the high technology field such as aeronautics, spaceflight, electron apparatus, and chemical industry, etc.
Description
Technical field
The present invention relates to a kind of siliceous alkynes fragrant polytriazoles resin and preparation method thereof, relate in particular to a kind of siliceous aryne resin and triazo-compound of utilizing by 1, the novel siliceous alkynes fragrant polytriazoles resin of 3-dipole cycloaddition polyreaction preparation, this resin has excellent machinability, good resistance toheat and mechanical mechanics property etc. can be used as the resin matrix of advanced composite material.
Background technology
Advantages such as polymer matrix composites have specific tenacity and specific modulus height, designability is strong, anti-fatigue performance good, corrosion resistance and good, also can obtain the matrix material of specific function by the composite design of material, therefore, matrix material obtains to use widely at industrial circles such as aerospace, becomes high-tech sector of paramount importance material with the fastest developing speed.
The low-temperature curing technology in recent years, is subjected to people's attention as an important development direction of advanced polymer matrix composites low-cost technologies.The resin system of the low-temperature curing matrix material of open report mainly is a Resins, epoxy both at home and abroad at present, and epoxy-resin systems has good processing performance, mechanical property etc.But the self structure of Resins, epoxy has limited it and has used under comparatively high temps.Therefore, development of new low temperature curing resin system becomes the research focus.
In the later stage sixties 20th century, Baldwin etc. discover the compound that has azido-and alkynyl in the molecular structure simultaneously, can take place 1, and 3-dipolar addition polyreaction generates the simple linear polymer that main chain contains triazole ring.Reaction can be at lesser temps as 70 ℃ even room temperature generation, and the polymkeric substance of formation has higher thermostability [Baldwin, M.G, et al., JPS:Polymer Letters, 1966,4,977～979; Johnson, K.E etal.; JPS:Polymer Letters.1967,5,803～805].The Du Lei of East China University of Science, Huang Farong etc. utilize that azido-and alkynyl take place under lower temperature 1, the 3-Dipolar Cycloaddition prepares and contains 1,4-two replacements and 1, and 5-two replaces-1,2, the polytriazoles resin of 3-triazole ring has successfully been developed the resin of the novel low-temperature curable of a class, and The experimental results shows that the polytriazoles resin has good processing characteristics, thermal characteristics and mechanical property [Luo Yonghong etc., SCI, 2006,27 (1), 170～173; Lian Xue, et al., Thermochimica Acta, 2006,448,147～153; Wan Liqiang, et al., J.Appl.Polym.Sci., 2007,104,1038～1042], second-order transition temperature Gao Zheke reaches 300 ℃, and heat decomposition temperature is about 350 ℃ in nitrogen; Polytriazoles polymer matrix composites system also shows favorable mechanical performance and better resistance toheat.But the resistance toheat of polytriazoles resin of mentioning in the prior art and matrix material thereof is still limited, and its high-temperature behavior retention rate is low, can't satisfy higher temperature as the service requirements more than 250 ℃.
Siliceous aryne resin is the novel polyyne resinoid of a class, is highly cross-linked structure after the curing, the resistance to elevated temperatures excellence.The introducing of element silicon not only makes aryne resin keep excellent thermotolerance, and possess good processing characteristics, mechanical property and pyroceramic voltinism can etc.The foreign study person has synthesized the siliceous aryne resin of multiple structure by Grignard reagent method, magnesium oxide catalytic dehydrogenation polymerization, metallic lithium and sodium method etc.Soviet Union Luneva in 1967 etc. utilize acetylene Grignard reagent and alkyl, aryl silicon, metal halide prepared in reaction siliceous aryne resin, heat decomposition temperature reaches 450～550 ℃ of [L.K.Luneva, et al., VysokomolekulyamyeSoedineniya, Seriya A, 1967,9 (4): 910～14.], structure is as follows:
People such as Japanese Itoh used magnesium oxide as catalyzer in 1994, synthesized siliceous hydrogen aryne resin-MSP resin, has excellent thermal characteristics after the curing, but because the fragility of material, cause the mechanical property of its matrix material not good [M.Itoh, et al., Journal of Materials Science, 2002,37:3795].Before and after 2000, French Buvat etc. have synthesized phenylacetylene-capped silane aryne resin (claiming the BLJ resin), can adopt the RTM moulding process to prepare heat-resisting BLJ polymer matrix composites; Cured resin 1000 ℃ of decomposition residual rates under argon gas are 80%, and glass transition [Pierrick Buvat., et al., SAMPE Symp., 2000,46,134～144] is not appearring in the DMA analysis revealed below 450 ℃.This resinoid can form highly cross-linked aromatize polymkeric substance by the reaction between addition reaction of hydrogen between acetylene bond and the silicon hydrogen group and alkynes alkynes, thereby gives the polymkeric substance excellent heat resisting.The research of siliceous aryne resin, the siliceous aryne resin [Yan Hao, Qi Huimin, Huang Farong, petrochemical complex, 2004,33 (9), 880～884 that have prepared multiple structure are taken in the yellow honor of East China Polytechnics in 2002 etc.; Huang Farong, Du Lei etc. Chinese invention patent, CN 1709928,2005; Fan Wang, et al., Polymer Bulletin, 2006,56,19～26], compare abroad roughly the same resin, made resin has obtained very big improvement at aspects such as processing performance, package stability, mechanical propertys.Its principal feature is: 1) be in a liquid state or easy molten eutectic solid-state, be easy to the forming process of matrix material; Not having volatile matter and low molecular weight by-products when 2) solidifying overflows; 3) pyrolysis carbon forming rate height; 4) cured resin is highly cross-linked structure usually, the resistance to elevated temperatures excellence; 5) introducing of element silicon not only makes aryl polyyne polymkeric substance keep excellent thermotolerance, and can make it have excellent high-temperature pottery voltinism energy, being to form stable pottery (as SiC or/and SiO2 etc.) structure under the condition of high temperature in this base polymer, is a kind of good ceramic forerunner material; 6) adhesive property with fiber is good.But the fragility of the siliceous aryne resin after the curing is still bigger than normal, and the cohesiveness of resin and fiber is still not really desirable.
In sum, siliceous aryne resin and polytriazoles resin respectively have advantage, and advantage how to bring into play polytriazoles resin and siliceous aryne resin performance will become the important technological problems that the present invention need solve.Combination of them not only can keep the resistance to elevated temperatures and the polytriazoles resin low-temperature curing characteristic of siliceous aryne resin, and can make in conjunction with product and possess good processing properties and mechanical property.
Summary of the invention
The invention provides a kind of siliceous alkynes fragrant polytriazoles resin and preparation method thereof.
The present invention is to be raw material with siliceous aryne resin and triazo-compound, siliceous aryne resin has acetylene group, can take place 1 with triazo-compound, the 3-Dipolar Cycloaddition, polymerization by siliceous aryne resin and triazo-compound makes novel siliceous alkynes fragrant polytriazoles resin, can be used as a kind of novel low-temperature curing high temperature and uses resin system to be used for the manufacturing of advanced polymer matrix composites.
When using two triazo-compound N
3-R
1-N
3During for raw material, the chemical structural formula of the siliceous alkynes fragrant polytriazoles resin that then makes schematically as follows:
R in the formula
1=
When using triazide
During for raw material, the chemical structural formula of the siliceous alkynes fragrant polytriazoles resin that then makes schematically as follows:
R in the formula
2=
The chemical structural formula of described siliceous aryne resin is as follows:
N=5-7 wherein;
R ' in the top structural formula and R " be 1) R '=CH
3, R "=CH
3(2) R '=C
6H
5, R "=C
6H
5(3) R '=CH
3, R "=C
6H
5(4) R '=CH
3, R "=H.
The preparation method of the siliceous alkynes fragrant polytriazoles of the high-performance resin that low-temperature curing high temperature of the present invention uses comprises three steps: (1) is raw material with sodiumazide and halogenated aryl hydrocarbon, prepares triazo-compound by nucleophilic substitution reaction; (2) by the synthetic siliceous aryne resin of Grignard reagent method; (3), prepare siliceous alkynes fragrant polytriazoles resin by siliceous aryne resin and triazo-compound dipolar addition polyreaction.
The first step, the preparation of triazo-compound
The present invention utilizes the nucleophilic substitution reaction of halogenated aryl hydrocarbon and sodiumazide to make triazo-compound: two triazo-compound N
3-R
1-N
3, or triazide
The preparation method of triazo-compound is referring to document (Luo Yonghong etc., SCI, 2006,27 (1), 170～173; Lian Xue, et al., Thermochimica Acta, 2006,448,147～153; Wan Liqiang, et al., J.Appl.Polym.Sci., 2007,104,1038～1042), the synthetic of triazo-compound carries out in solution, and solvent for use can be selected DMF, benzene, toluene, DMSO, tetrahydrofuran (THF) etc. or their mixed solvent etc.Add-on is that every moles of halogenated aromatic hydrocarbons adds 800～1500mL solvent; Halogenated aryl hydrocarbon is muriate, bromide or iodide, and the feed ratio of reaction raw materials sodiumazide and halogenated aryl hydrocarbon (equivalence ratio) is 1.0～3.0: 1.0, and temperature of reaction is 20～80 ℃, and the reaction times is 2～10h.
Second step, the preparation of siliceous aryne resin
The Grignard reagent method is adopted in siliceous aryne resin preparation of the present invention, referring to document (Yan Hao, Qi Huimin, Huang Farong, petrochemical complex, 2004,33 (9), 880～884; Huang Farong, Du Lei etc. Chinese invention patent, CN1709928,2005; Fan Wang, et al., Polymer Bulletin, 2006,56,19～26), specific embodiment is as follows: being raw material with magnesium and halogenated alkane at first, is solvent with anhydrous ethers reagent, preparation aliphatic hydrocarbon Grignard reagent; Secondly, be reactant with diacetylene aromatic hydrocarbons, make solvent with ethers reagent, alkynes activates under the effect of aliphatics Grignard reagent, forms the alkynes Grignard reagent; The 3rd, alkynes Grignard reagent and dihalide halosilanes reaction generate siliceous aryne resin.At last, carry out aftertreatment, obtain siliceous aryne resin.Used ether solvent can be ether, propyl ether, butyl ether, dioxane, tetrahydrofuran (THF) (THF) or crown ether.These operating process are all carried out under exsiccant inert atmosphere (as nitrogen, helium or argon gas etc.) protection.Described siliceous aryne resin has following structure:
N=5-7 wherein; (1) R '=CH
3, R "=CH
3(2) R '=C
6H
5, R "=C
6H
5(3) R '=CH
3, R "=C
6H
5(4) R '=CH
3, R "=H.
The 3rd step, the preparation of siliceous alkynes fragrant polytriazoles resin
Siliceous alkynes fragrant polytriazoles resin is to be raw material with siliceous aryne resin and triazo-compound, and by 1,3-dipole cycloaddition polyreaction makes.The azido group mole proportioning of the alkynyl of siliceous aryne resin and triazo-compound is 1.0～6.0: 1.0, is preferably 1.8～4.5: 1.0.Can adopt solution polymerization or mass polymerization to carry out polyreaction.
Solution polymerization: siliceous aryne resin and triazo-compound are dissolved in the solvent, and solvent is selected from acetone, ethylene dichloride, chloroform, butanone or tetrahydrofuran (THF) (THF) etc.Reaction times 0.5～20h, preferable 0.5～4h, 30～80 ℃ of temperature of reaction, preferable 60～80 ℃, after reaction finished, the solution distillation removes desolvated, and obtains the reddish-brown solid resin.
Mass polymerization: siliceous aryne resin and triazo-compound are reacted down at 30～80 ℃, preferable 50～80 ℃, reaction times 0.5～7h, more preferable 0.5～3h obtains solid resin.
Adopt different triazo-compounds, the siliceous alkynes fragrant polytriazoles resin that makes has different chemical structures:
The reaction of two triazo-compounds and siliceous aryne resin generates siliceous alkynes fragrant polytriazoles resin and curing reaction thereof schematically as follows:
The reaction of triazide and siliceous aryne resin generates siliceous alkynes fragrant polytriazoles resin and curing reaction thereof schematically as follows:
The curing of siliceous alkynes fragrant polytriazoles resin
50～100 ℃ of resin solidification temperature, set time 3～18h, preferable 4～12h; Being used for further improving the solidified temperature is 110～250 ℃, step curing, and set time is totally 2～10h; Again at 250～300 ℃ of after fixing 2～6h.
The resin matrix that the siliceous alkynes fragrant polytriazoles of the present invention resin can be used as high temperature resistant composite is applied to the preparation of high temperature resistant composite, the following describes the preparation method of matrix material:
Siliceous alkynes fragrant polytriazoles resin is added in the tetrahydrofuran (THF) equal solvent, be mixed with 30～40% solution.This solution of impregnated carbon fiber is made prepreg, control prepreg fugitive constituent＜1%, use composite material moulded moulding process such as compression molding commonly used, prepreg can be at 70～100 ℃, and curing molding under 0.5～5.0MPa heats up at 100～200 ℃ of substeps and suppresses, pressure 0.5～5.0MPa (or not pressurizeing), through 250～300 ℃ aftertreatment, behind the pressurization 0.5-5.0MPa (or not pressurizeing), make matrix material.
The siliceous alkynes fragrant polytriazoles resin that the low-temperature curing high temperature of the present invention's preparation uses, viscosity in 60～110 ℃ of temperature ranges is less than 1Pa.s, this resin and fibre reinforced composites can be at 70～100 ℃ of curing moldings, through after 100～300 ℃ the curing, material has excellent physical and mechanical properties and thermal characteristics again.The present invention utilizes the siliceous alkynes fragrant polytriazoles resin of triazo-compound and the preparation of siliceous aryne resin, compares the second-order transition temperature height of cured resin, T with the polytriazoles resin of prior art report
gCan 〉=300 ℃, thermostability is better, and heat decomposition temperature can be satisfied with the requirement of using more than 250 ℃ up to 410 ℃.The performance of its fibre reinforced composites is higher, under the normal temperature unidirectional carbon fiber (T700) reinforced composite flexural strength up to 1800MPa, the about 120GPa of modulus in flexure, 250 ℃ of following flexural strength retention rates are up to about 70%, modulus in flexure is constant substantially.Have wide practical use in fields such as Aeronautics and Astronautics, electronics, chemical industry, automotive industrys.
The siliceous alkynes fragrant polytriazoles of the present invention resin has following advantage: 1) resin has good processing characteristics, less than 1Pa.s, dissolves in the THF equal solvent 60～100 ℃ of following viscosity, and solidification value is lower, can be in 70～100 ℃ of temperature ranges curing molding; 2) there is not small molecules to discharge in the resin curing process; 3) siliceous alkynes fragrant polytriazoles resin crosslinks is solidified and can be formed highly cross-linked polymkeric substance, has good thermotolerance.T
gCan be up to 300-325 ℃, T
D5Up to 410 ℃; 4) have good cohesiveness between resin and the fiber, matrix material demonstrates excellent mechanical property.Unidirectional carbon fiber dimension (T700) reinforced composite flexural strength is up to 1800MPa, and 250 ℃ of following strength retention ratios are up to about 70%; 5) after the moulding of matrix material low-temperature curing, can under stress-free condition, carry out after fixing.
Description of drawings
Fig. 1 A1-1 resin is at the infrared spectrum in different curing reaction stage
Among the figure: a) resin; B) 80 ℃/12h; C) 150 ℃/2h; D) 170 ℃/2h; E) 250 ℃/4h.
Embodiment
Below by embodiment the present invention is specifically described, but embodiment only is used for that the present invention is further described, protection domain of the present invention is not limited.
Embodiment 1 contains the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A1-1)
1.4,4 '-two azido-methyl biphenyl synthetic
In there-necked flask, add dichloromethyl biphenyl 12.55g (0.05mol), NaN
39.75g (0.15mol), benzene (20ml) and DMF (20ml), under agitation be heated to 70～75 ℃, isothermal reaction 3h, reaction is cooled to room temperature with reaction product after finishing, pour in the 200ml deionized water, standing over night is separated out white solid, filters, the filter cake deionized water wash, get white powder solid, productive rate 89.0%, 67～71 ℃ of fusing points after the drying.
2. the siliceous aryne resin of diformazan fundamental mode is synthetic
In being housed, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds 6.00g (0.247mol) magnesium powder and the 50ml THF that handled; logical nitrogen protection; slowly drip the mixing solutions of 21.6g (0.198mol) monobromethane and 50ml THF through constant pressure funnel; 1.5h dropwise; backflow 1.5h makes the ethyl Grignard reagent of grey black.Drip the mixing solutions of 11.35g (0.0900mol) diacetylene-benzene and 50ml THF under the ice-water bath cooling, reaction mixture becomes white by grey black gradually, dropwises in the 1h, then back flow reaction 2h.Under water-bath cooling, slowly add the mixing solutions of 9.29g (0.0720mol) dimethyldichlorosilane(DMCS) and 50ml THF by constant pressure funnel, the dropping time is about 1h.Dropwise,, obtain yellow-green soln at 70 ℃ of isothermal reaction 2h.After steaming solvent THF, be cooled to about 50 ℃, add 50ml toluene.Dropwise 5 % dilute hydrochloric acid solution in ice-water bath cooling downhill reaction flask is until separatory; Upper organic phase is transferred to the 250ml separating funnel, is washed to neutrality, isolate organic phase, add anhydrous Na with deionized water
2SO
4Dried overnight is filtered the back underpressure distillation except that desolvating, and obtains the thick resin 13.7g of reddish-brown, productive rate 88%.FTIR:3300cm
-1(≡ C-H), 2156cm
-1(C ≡ C);
1H-NMR (CDCl
3, TMS): 3.05 (≡ CH), 0.37 (Si-CH
3), 7.2-7.7 (Ar-H).
29Si-NMR (CDCl
3, TMS) :-39.0 (C ≡ C-Si); Average molecular mass Mn: 750.Its structural representation is as follows:
3. contain the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A1-1)
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol, azido group 0.030mol), the siliceous aryne resin 6.48g of diformazan fundamental mode (0.0086mol, alkynyl 0.077mol) and 40ml THF add in the reactor, slowly be warming up to 70 ℃, stirring reaction 2 hours removes at last and desolvates, and obtains reddish-brown solid state resin.In 70～120 ℃ scope, resin viscosity is 0.5Pa.s; Temperature is higher than under 120 ℃ the condition, viscosity fast rise, beginning gel.
The infrared spectra of resin is at 3300cm
-1≡ C-H vibration peak, 2098cm appear in the place
-1And 2156cm
-1The place is appearance-N=N=N and C ≡ C vibration peak respectively.Resin carries out with reaction at different cure stage infrared spectras as shown in Figure 1, and ≡ C-H vibration peak weakens, at 2098cm
-1And 2156cm
-1Place-N=N=N and C ≡ C vibration absorption peak also weaken simultaneously, and at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains cured article is 302 ℃.5% weightless temperature of cured product is 410 ℃, and 800 ℃ residual rate is 80%, and siliceous alkynes fragrant polytriazoles resin has thermostability preferably.
Embodiment 2 contains the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A1-2)
The preparation of 4,4 '-two azido-methyl biphenyl and the siliceous aryne resin of diformazan fundamental mode is with embodiment 1.
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol azido group 0.030mol), the siliceous aryne resin 5.48g of diformazan fundamental mode (0.0073mol, alkynyl 0.065mol) and 30ml THF add in the reactor, stirring reaction 2h down refluxes, remove at last and desolvate, obtain reddish-brown solid state resin.In 70～110 ℃ scope, resin viscosity is 0.7Pa.s; Temperature is higher than under 120 ℃ the condition, viscosity fast rise, beginning gel.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1The place is appearance-N=N=N and C ≡ C vibration absorption peak respectively, at about 3140cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 312 ℃.
Embodiment 3 contains the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A1-3)
The preparation of 4,4 '-two azido-methyl biphenyl and the siliceous aryne resin of diformazan fundamental mode is with embodiment 1.
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol, azido group 0.030mol) and the siliceous aryne resin 5.48g of diformazan fundamental mode (0.0073mol, alkynyl 0.065mol) add in the reactor, at 80 ℃ of following stirring reaction 0.5h, obtain reddish-brown solid state resin.In 70～110 ℃ scope, resin viscosity is 0.9Pa.s; Temperature is higher than under 120 ℃ the condition, viscosity fast rise, beginning gel.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1Appearance-N=N=N of place and C ≡ C vibration absorption peak are at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 318 ℃.
Embodiment 4 contains the preparation of hexichol fundamental mode silicon alkynes fragrant polytriazoles resin (B1)
1.4,4 '-two azido-methyl biphenyl synthetic with embodiment 1
2. the siliceous aryne resin of hexichol fundamental mode is synthetic
In being housed, the 250ml four-hole boiling flask of stirring, constant pressure funnel and spherical condensation tube adds 6.00g (0.247mol) magnesium powder and the 50ml THF that handled; lead to nitrogen protection, slowly drip the mixing solutions of 21.6g (0.198mol) monobromethane and 50ml THF through constant pressure funnel.1.5h dropwise, backflow 1.5h makes the ethyl Grignard reagent of grey black.Drip the mixing solutions of 11.35g (0.0900mol) diacetylene-benzene and 50ml THF under the ice-water bath cooling, reaction mixture becomes white by grey black gradually, dropwises in the 1.0h, then back flow reaction 2.0h.Under water-bath cooling, slowly add the mixing solutions of 18.21g (0.0720mol) diphenyl dichlorosilane and 50ml THF by constant pressure funnel, the dropping time is about 1.0h.Dropwise,, obtain the yellow-green colour reaction soln at 70 ℃ of isothermal reaction 2.0h.After steaming solvent THF, be cooled to about 50 ℃, add 50ml toluene.Dropwise 5 .0% dilute hydrochloric acid solution in ice-water bath cooling downhill reaction flask, behind the separatory with upper strata organic solution phase transition to the 250ml separating funnel, be washed to neutrality with deionized water, isolate organic phase, add anhydrous Na
2SO
4Dried overnight is filtered the back underpressure distillation except that desolvating, and obtains reddish-brown resin 21.5g, productive rate 88%.FTIR:3300cm
-1(≡ C-H), 2156cm
-1(C ≡ C);
1H-NMR (CDCl
3, TMS): 3.05 (≡ CH), 7.2-8.0 (Ar-H); Average molecular mass Mn: 1805.。Characterize through infrared, NMR, its structural representation is as follows:
3. contain the preparation of hexichol fundamental mode silicon alkynes fragrant polytriazoles resin (B1)
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol, azido group 0.030mol), the siliceous aryne resin 10.65g of hexichol fundamental mode (0.0059mol, alkynyl 0.077mol) and the 30ml chloroform add in the reactor, stirring reaction 6h down refluxes, remove at last and desolvate, obtain reddish-brown solid state resin.In 80～120 ℃ scope, resin viscosity 1.0Pa.s.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1The place is appearance-N=N=N and C ≡ C vibration absorption peak respectively, at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 300 ℃.
Embodiment 5 contains the preparation of methylbenzene fundamental mode silicon alkynes fragrant polytriazoles resin (C1)
1.4,4 '-two azido-methyl biphenyl synthetic with embodiment 1
2. the siliceous aryne resin of methylbenzene fundamental mode is synthetic
Come synthetic resins with the method that is analogous to embodiment 4, main raw material consumption 21.6g (0.198mol) monobromethane, 11.35g (0.0900mol) diacetylene-benzene, 13.75g (0.0720mol) dichloromethyl phenylsilane, obtain reddish-brown solid state resin 18.0g, productive rate 91%.FTIR:3300cm
-1(≡ C-H), 2156cm
-1(C ≡ C);
1H-NMR (CDCl
3, TMS): 3.05 (≡ CH), 0.37 (Si-CH
3), 7.2-8.0 (Ar-H); Average molecular mass Mn: 1471.Its structural representation is as follows:
3. contain the preparation of methylbenzene fundamental mode silicon alkynes fragrant polytriazoles resin (C1)
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol, azido group 0.030mol), the siliceous aryne resin 8.68g of methylbenzene fundamental mode (0.0059mol, alkynyl 0.077mol) and the 30ml ethylene dichloride add in the reactor, slowly be warming up to 80 ℃, stirring reaction 2h removes the back of desolvating and obtains the reddish-brown resin.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1Appearance-N=N=N of place and C ≡ C vibration absorption peak are at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 300 ℃.
Embodiment 6 contains the preparation of methyl type silicon alkynes fragrant polytriazoles resin (D2)
1.1,4-two azido-methyl benzene synthetic
In there-necked flask, add xylylene dichlorides 8.75g (0.05mol), NaN
39.75g (0.15mol), benzene (20ml) and DMF (20ml), under agitation be 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, standing over night is separated out the white plates crystal under freezing condition, filter, the filter cake deionized water wash gets the white powder solid after the drying, productive rate 90.0%, mp.26.0～27.5 ℃.
2. the siliceous aryne resin of methyl type is synthetic
Come synthetic resins with the method that is analogous to embodiment 1, main raw material consumption 21.6g (0.198mol) monobromethane, 11.35g (0.0900mol) diacetylene-benzene, 8.28g (0.0720mol) dimethyl dichlorosilane (DMCS), obtain the thick resin 12.5g of reddish-brown, productive rate 87%.FTIR:3300cm
-1(≡ C-H), 2156cm
-1(C ≡ C);
1H-NMR (CDCl
3, TMS): 3.05 (≡ CH), 0.37 (Si-CH
3), 4.60 (Si-H), 7.2-7.7 (Ar-H); Average molecular mass Mn: 964.。Its structural representation is as follows:
3. contain the preparation of methyl type silicon alkynes fragrant polytriazoles resin (D2)
With 1,4-two azido-methyl benzene 2.83g (0.015mol, azido group 0.030mol), the siliceous aryne resin 6.17g of methyl type (0.0061mol, alkynyl 0.073mol) and 30ml acetone add in the reactor, stirring reaction 15h under refluxing removes at last and desolvates, and obtains the sticking shape resin of reddish-brown.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1Appearance-N=N=N of place and C ≡ C vibration absorption peak are at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Prepared resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 310 ℃.
Embodiment 7 contains the preparation of hexichol fundamental mode silicon alkynes fragrant polytriazoles resin (B2)
1,4-two azido-methyl benzene are synthetic with embodiment 6, and the siliceous aryne resin of hexichol fundamental mode is synthetic with embodiment 4.
With 1,4-two azido-methyl benzene 2.83g (0.015mol azido group 0.030mol), the siliceous aryne resin 10.65g of hexichol fundamental mode ((0.0059mol, alkynyl 0.077mol) and 30ml THF add in the reactor, be warming up to 35 ℃, stirring reaction 18h, remove at last and desolvate, obtain reddish-brown solid state resin.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1The place is appearance-N=N=N and C ≡ C vibration absorption peak respectively, at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Prepared resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 300 ℃.
Embodiment 8 contains the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A3)
1.1,3,5-triple-lap n-formyl sarcolysine base-2,4, the preparation of 6-Three methyl Benzene
1,3,5-triple-lap n-formyl sarcolysine base-2,4, the preparation of 6-Three methyl Benzene: in there-necked flask, add 1,3,5-trisbromomethyl-2,4,6-Three methyl Benzene 159.6g (0.4mol), NaN
393.6g (1.44mol), benzene (250ml) and DMF (250ml), under agitation be heated to 70～75 ℃, isothermal reaction 5h, reaction is cooled to room temperature with reaction product after finishing, pour in the 2000ml deionized water, standing over night is separated out white solid, filters, filter cake with deionized water wash repeatedly, get white powder solid, productive rate 83%, 60～62 ℃ of fusing points after the drying.
2. the siliceous aryne resin of diformazan fundamental mode is synthetic with embodiment 1.
3. contain the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A3)
With 1,3,5-triple-lap n-formyl sarcolysine base-2,4,6-Three methyl Benzene 2.85g (0.010mol, azido group 0.030mol), the siliceous aryne resin 6.48g of diformazan fundamental mode (0.0086mol, alkynyl 0.077mol), tetrahydrofuran (THF) 30ml adds in the reactor, slowly be warming up to tetrahydrofuran (THF) and reflux stirring reaction 2 hours, remove at last and desolvate, obtain the sticking shape resin of reddish-brown.In 70～110 ℃ scope, resin viscosity is 0.4Pa.s; Temperature is higher than under 120 ℃ the condition, viscosity fast rise, beginning gel.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1The place is appearance-N=N=N and C ≡ C vibration absorption peak respectively, at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains cured article is 325 ℃.
Embodiment 9 contains the preparation of diformazan fundamental mode silicon alkynes fragrant polytriazoles resin (A1-4)
The preparation of 4,4 '-two azido-methyl biphenyl and the siliceous aryne resin of diformazan fundamental mode is with embodiment 1.
With 4,4 '-two azido-methyl biphenyl 3.96g (0.015mol, azido group 0.030mol), the siliceous aryne resin 10.12g of diformazan fundamental mode (0.0073mol, alkynyl 0.120mol) and the 30ml butanone add in the reactor, at 80 ℃ of following stirring reaction 4.0h, remove at last and desolvate, obtain reddish-brown solid state resin.In 80～110 ℃ scope, resin viscosity is 0.5Pa.s; Temperature is higher than under 120 ℃ the condition, viscosity fast rise, beginning gel.Infrared spectra: 3300cm
-1The place exists ≡ C-H vibration peak, 2098cm
-1And 2156cm
-1Appearance-N=N=N of place and C ≡ C vibration absorption peak are at about 3150cm
-1C-H vibration absorption peak on the triazole ring appears in the place.
Resin solidifies and 250 ℃ of aftertreatment 4h through 80 ℃/12h, 120 ℃/2h, 150 ℃/2h, 170 ℃/2h, 210 ℃/2h, and the second-order transition temperature that obtains resin cured matter is 325 ℃.
The preparation of embodiment 10 siliceous alkynes fragrant polytriazoles polymer matrix composites
A1-1 in the foregoing description or A1-2 resin are added in the tetrahydrofuran (THF), be mixed with 40% solution.The carbon fibre makes prepreg around this solution of dipping, control prepreg fugitive constituent＜1%, mold pressing compacting matrix material on platen-press.Pressing process condition: I, 80 ℃/12h, pressure 1.5MPa; II, 80 ℃/12h+120 ℃/2h+170 ℃/2h+210 ℃/2h+250 ℃/4h, pressure 1.5MPa; III, 80 ℃/12h, pressure 1.5MPa, does not have and presses by 120 ℃ of after fixing/2h+170 ℃/2h+210 ℃/2h+250 ℃/4h.The performance of composites that obtains is referring to table 1 and table 2.As seen matrix material has good normal temperature, high-temperature behavior, can be used as the resin matrix of heat-stable advanced composite material, is used for high-tech sectors such as Aeronautics and Astronautics, electronic apparatus, chemical industry.
Table 1 molding technological condition strengthens siliceous alkynes fragrant polytriazoles resin composite materials Effect on Performance to the T700 unidirectional fibre
*
| Resin | Moulding process | Flexural strength (MPa) | Modulus in flexure (GPa) |
| A1-1 | I II III | 1829.7 1833.3 1860.6 | 118.8 125.5 117.4 |
| A1-2 | I II III | 1705.5 1732.6 1651.4 | 137.3 143.9 146.5 |
*Testing standard adopts GB/T3356-1999
Table 2 T700 unidirectional fibre strengthens siliceous alkynes fragrant polytriazoles resin composite materials performance
*
| Resin a) | Test condition | Flexural strength (MPa) | Modulus in flexure (GPa) |
| A1-1 | 25℃ 200℃ 250℃ | 1833.3 1475.9(80.5％) 1278.2(69.6％) | 125.5 126.5 128.5 |
*Testing standard adopts GB/T3356-1999.A) prepare matrix material by moulding technology II.
Claims (10)
1. siliceous alkynes fragrant polytriazoles resin is characterized in that it is that polyaddition reaction by siliceous aryne resin and triazo-compound makes, and the azido group mole proportioning of the alkynyl of siliceous aryne resin and triazo-compound is 1.0-6.0: 1.0,
When using two triazo-compound N
3-R
1-N
3The time, the chemical structural formula of the siliceous alkynes fragrant polytriazoles resin that makes schematically as follows:
In the formula
When using triazide
The time, the chemical structural formula of the siliceous alkynes fragrant polytriazoles resin that makes schematically as follows:
In the formula
The chemical structural formula of described siliceous aryne resin is as follows:
N=5-7 wherein;
R ' in the top structural formula and R " be 1) R '=CH
3, R "=CH
3(2) R '=C
6H
5, R "=C
6H
5(3) R '=CH
3, R "=C
6H
5(4) R '=CH
3, R "=H.
2. siliceous alkynes fragrant polytriazoles resin as claimed in claim 1 is characterized in that the alkynyl of described siliceous aryne resin and the azido group mole proportioning of triazo-compound are 1.8～4.5: 1.0.
3. the preparation method of the described siliceous alkynes fragrant polytriazoles resin of claim 1 is characterized in that comprising three steps:
(1) by sodiumazide and halogenated aryl hydrocarbon prepared in reaction raw material triazo-compound;
(2) be equipped with the siliceous aryne resin of raw material by the Grignard reagent legal system;
(3) preparation of siliceous alkynes fragrant polytriazoles resin
Triazo-compound and siliceous aryne resin pass through polyaddition reaction, make siliceous alkynes fragrant polytriazoles resin, the azido group mole proportioning of the alkynyl of siliceous aryne resin and triazo-compound is 1.0～6.0: 1.0, adopt solution polymerization or mass polymerization to react: solution polymerization is that siliceous aryne resin and triazo-compound are dissolved in the solvent, temperature of reaction is 30～80 ℃, and the reaction times is 0.5～20h, after reaction finishes, distillation removes and desolvates, and gets solid resin; Mass polymerization is reaction under temperature is 30-80 ℃ with siliceous aryne resin and triazo-compound, and the reaction times is 0.5～7h, gets solid resin.
4. preparation method as claimed in claim 3 is characterized in that the alkynyl of described siliceous aryne resin and the azido group mole proportioning of triazo-compound are 1.8～4.5: 1.0.
5. preparation method as claimed in claim 3, the temperature of reaction that it is characterized in that described solution polymerization is 60～80 ℃, the reaction times is 0.5～4 h.
6. preparation method as claimed in claim 3 is characterized in that the solvent of described solution polymerization is selected from acetone, ethylene dichloride, chloroform, butanone or tetrahydrofuran (THF).
7. preparation method as claimed in claim 3, the temperature of reaction that it is characterized in that mass polymerization is 50～80 ℃, the reaction times is 0.5～3h.
8. preparation method as claimed in claim 3 is characterized in that gained resin solidification temperature is 50～100 ℃, and be 3～18h set time; Being used for further improving the solidified temperature is 110～250 ℃, step curing, and set time is totally 2～10h; Again at 250～300 ℃ of after fixing 2～6h.
9. preparation method as claimed in claim 8 is characterized in that the gained resin solidification time is 4-12h.
10. the application of the described siliceous alkynes fragrant polytriazoles resin of claim 1 is characterized in that described siliceous alkynes fragrant polytriazoles resin is applied to the preparation of high temperature resistant composite as the resin matrix of high temperature resistant composite.
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| CN102153748A (en) * | 2010-12-07 | 2011-08-17 | 浙江大学 | Hyperbranched polytriazole with aggregation induced light-emitting performance and preparation method and application of hyperbranched polytriazole |
| CN102153748B (en) * | 2010-12-07 | 2012-11-07 | 浙江大学 | Hyperbranched polytriazole with aggregation induced light-emitting performance and preparation method and application of hyperbranched polytriazole |
| CN102443171A (en) * | 2011-10-21 | 2012-05-09 | 浙江大学 | Hyperbranched polytriazole with self-repairing performance as well as preparation method and application thereof |
| CN102443171B (en) * | 2011-10-21 | 2013-07-24 | 浙江大学 | Hyperbranched polytriazole with self-repairing performance as well as preparation method and application thereof |
| CN103087671A (en) * | 2011-11-08 | 2013-05-08 | 华东理工大学 | High temperature-resistant damp heat-resistant polytriazole resin adhesive and preparation method and application |
| CN104151840A (en) * | 2014-07-21 | 2014-11-19 | 华东理工大学 | Silicon-alkyne resin-modified polyborosilazane composite material and preparation method thereof |
| CN104371206A (en) * | 2014-11-07 | 2015-02-25 | 上海交通大学 | Crosslinked polystyrene material as well as preparation method and use |
| CN104371206B (en) * | 2014-11-07 | 2017-06-13 | 上海交通大学 | Crosslinked polystyrene material and preparation method thereof, purposes |
| CN105237772A (en) * | 2015-10-08 | 2016-01-13 | 华东理工大学 | Phenylethynyl-terminated silicon-containing polytriazole resins and preparation method thereof |
| CN111548497A (en) * | 2020-05-29 | 2020-08-18 | 华东理工大学 | Silyne hybrid resin, cured product, ceramic material, composite material and preparation method |
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