CN105037724A - Hyperbranched polyimide containing alkynyl group, and preparation method and application thereof - Google Patents
Hyperbranched polyimide containing alkynyl group, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides hyperbranched polyimide containing an alkynyl group, and a preparation method and application thereof, belonging to the technical field of viscosity conditioning agents for high-molecular materials. The invention aims to overcome the problem of reduction in mechanical properties after addition of a hyperbranched polymer into linear polyimide and provides the alkynyl group-containing hyperbranched polyimide which can be used as a viscosity conditioning agent for linear polyimide; and after addition of the alkynyl group-containing hyperbranched polyimide into linear polyimide, the alkynyl group undergoes crosslinking after high temperature treatment so as to form macro-molecules, thereby preventing reduction in mechanical properties of linear polyimide. According to the invention, the alkynyl group-containing hyperbranched polyimide is prepared by adding a step of carrying out dead-end polymerization on a precursor by using monomer containing an alkynyl group end-capping reagent into the conventional polyimide preparation process. The hyperbranched polyimide containing the alkynyl group in the invention has good dissolvability and reduces melt viscosity; after addition of the alkynyl group-containing hyperbranched polyimide into linear polyimide, melt viscosity is improved; and after high temperature treatment, thermal behavior and mechanical properties of a blend are enhanced.
Description
Technical field
The invention belongs to the technical field of macromolecular material, be specifically related to a kind of containing alkynyl super-branched polyimide and preparation method thereof and the application in viscosity modifier.
Background technology
Along with aerospace, dynamo-electric production and sophisticated technology, military development, to the demand of high strength, high-modulus, lightweight and high temperature material is more and more urgent and demand is also increasing.Polyimide has superior mechanical property and the high performance engineering plastics of thermostability.But there is the rigid structure such as phenyl ring, imide ring in polyimide, make its poor processability.The processing of polyimide is except can using injection moulding, and the processing for those fire resistant polyimide materials generally can only pass through hot pressing, and even more special, more complicated method machine-shaping, limits it and apply widely.
At present, the research about hyperbranched polymer more and more receives the concern of people, this mainly due to: the first, hyperbranched polymer has special physicochemical property, such as, the molecular structure of elliposoidal, good mobility, low chain entanglement, high resolution, low melt viscosity and multifunctionality etc.; The second, there is a large amount of end groups in the periphery of three-dimensional structure, and the end group of substantial amounts can be its further chemical modification and functionalization provides reflecting point; 3rd, hyperbranched polymer is easy to synthesis relative to line polymer.Based on these advantages, researchist conducts in-depth research it.Hyperbranched polymer is one of important application as the processing characteristics that viscosity modifier improves line polymer.
As far back as 1992, Kim and Webster pointed out, hyperbranched polymer can as the viscosity modifier of polymkeric substance.The hyperbranched polymer of a small amount of bromine end-blocking is joined in polystyrene blend system, the melt viscosity of polystyrene blend can be made greatly to reduce, and improve the thermostability of polystyrene.
But existing hyperbranched polymer due to molecular weight there will be when joining in linear polyimide mechanical property reduce problem.
Summary of the invention
In order to solve the problem that there will be mechanical property reduction when hyperbranched polymer joins in linear polyimide, the invention provides a kind of viscosity modifier use that can be used as linear polyimide containing alkynyl super-branched polyimide, joining after in linear polyimide, be cross-linked to form macromole through pyroprocessing alkynyl thus prevent its mechanical property from reducing.
The described molecular formula containing alkynyl super-branched polyimide is:
Wherein, x, y, z represent repeating unit quantity respectively, x, y, z=3 ~ 10 and x+y+z=15 ~ 20;
The described preparation method containing alkynyl super-branched polyimide is as follows:
Under protective atmosphere; by 1; 3; 5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene is dissolved in first part's meta-cresol; at room temperature by 4; 4 '-(3; 4-di carboxyl phenyloxy) diphenyl ether dianhydride is dissolved in the solution that second section meta-cresol formed and is added drop-wise to 1; 3; in the m-cresol solution of 5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene, preferably drip off within the time of 1.5 ~ 2h, stir while dropping; churning time is 36 ~ 48h, stirs after terminating and obtains polyamic acid presoma.
Add in described polyamic acid presoma containing alkynyl end-capping reagent monomer, after stirring 6 ~ 8h at 60 ~ 80 DEG C, drip the isoquinoline 99.9 being equivalent to meta-cresol total mass 0.5% ~ 0.7%, there is flocculent precipitate to being added in ethanol by the material taken out from reaction system in reaction under the condition of 180 ~ 200 DEG C, and described flocculent precipitate is namely containing alkynyl super-branched polyimide.
Question response system cool to room temperature, then pours in ethanol and separates out throw out, finally use ethanol to be washed by throw out, obtain after drying pure in alkynyl super-branched polyimide.
Wherein, described 1,3,5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride, first part's meta-cresol, second section meta-cresol are 1:1:100 ~ 120:160 ~ 180:1.5 ~ 2 with the mol ratio containing alkynyl end-capping reagent monomer; Described is 4-phenylacetylene base Tetra hydro Phthalic anhydride or 4-(1-naphthalene ethynyl) Tetra hydro Phthalic anhydride containing alkynyl end-capping reagent monomer.
Described is used as viscosity modifier containing joining in linear polyimide according to the addition of massfraction 1% ~ 5% after the drying of alkynyl super-branched polyimide.
Beneficial effect of the present invention:
1, owing to having the trifluoromethyl of a large amount of ehter bond and large volume in polymer backbone, and the molecular structure of elliposoidal, containing alkynyl super-branched polyimide, there is good solvability and lower melt viscosity in the present invention.
2, after adding containing alkynyl super-branched polyimide, the melt viscosity of linear polyimide improves.And along with the increase of addition, temperature corresponding to minimum melt viscosity moves to low temperature, this lessens the process window of polymkeric substance, is conducive to save energy, reduce costs.
3, after pyroprocessing because phenylacetylene base occurs crosslinked, add the contact between molecular chain, limit the Relative sliding between molecular chain, the thermal characteristics of blend and mechanical property are improved.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of 4-phenylacetylene base Tetra hydro Phthalic anhydride end-blocking and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride.
Fig. 2 is the nuclear magnetic spectrogram of 4-phenylacetylene base Tetra hydro Phthalic anhydride end-blocking and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride.
Fig. 3 is dsc (DSC) test curve of 4-phenylacetylene base Tetra hydro Phthalic anhydride end-blocking and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride.
Fig. 4 is thermogravimetric analysis (TGA) test curve before and after 4-phenylacetylene base Tetra hydro Phthalic anhydride end-blocking and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide curing of Tetra hydro Phthalic anhydride.
Fig. 5 is the rheological behaviour test curve of 4-phenylacetylene base Tetra hydro Phthalic anhydride end-blocking and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride.
Fig. 6 is the flow curve of the terminated hyperbranched polyimide of 4-phenylacetylene base Tetra hydro Phthalic anhydride and linear polyimide blend.
Fig. 7 is dsc (DSC) test curve of the terminated hyperbranched polyimide of 4-phenylacetylene base Tetra hydro Phthalic anhydride and linear polyimide blend.
Fig. 8 is dsc (DSC) test curve after the terminated hyperbranched polyimide of 4-phenylacetylene base Tetra hydro Phthalic anhydride and linear polyimide blend pyroprocessing.
Embodiment
With the form of embodiment, technical scheme of the present invention is described in detail and is explained below.
The synthesis of the terminated hyperbranched polyimide of embodiment 1:4-phenylacetylene base Tetra hydro Phthalic anhydride (PE-HBPI)
In the there-necked flask being connected with nitrogen, by Triamine monomer (0.6034g, 1mmol) be dissolved in 13ml meta-cresol, dianhydride monomer (0.4944g is slowly dripped with constant pressure funnel, 1mmol) and the suspension liquid of 17ml meta-cresol, 1.5 ~ 2h drips off, and stirs while dropping, stir 48h at ambient temperature, obtain polyamic acid presoma.
In polyamic acid presoma, add 4-phenylacetylene base Tetra hydro Phthalic anhydride (0.3723g, 1.5mmol), after 80 DEG C of stirring 8h, drip 10 isoquinoline 99.9,200 DEG C of reaction 8h.After reaction system cool to room temperature, pour in ethanol, separate out polymkeric substance, washing with alcohol 5 times, 80 DEG C of vacuum-drying 12h, obtain faint yellow solid, the terminated hyperbranched polyimide of 4-phenylacetylene base Tetra hydro Phthalic anhydride (PE-HBPI) (1.211g, productive rate: 89.97%).
The synthesis of embodiment 2:4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride (NE-HBPI)
In the there-necked flask being connected with nitrogen, Triamine monomer (0.6034g, 1mmol) is dissolved in 13ml meta-cresol, slowly drips dianhydride monomer (0.4944g with constant pressure funnel, 1mmol) and the suspension liquid of 17ml meta-cresol, about 1.5 ~ 2h drips off.Stirring at room temperature 48h, obtains polyamic acid presoma.
4-(1-naphthalene ethynyl) Tetra hydro Phthalic anhydride (0.4474g, 1.5mmol) is added, after 80 DEG C of stirring 8h in polyamic acid presoma.Drip 10 isoquinoline 99.9,200 DEG C of reaction 8h.After reaction system cool to room temperature, pour in ethanol, separate out polymkeric substance, washing with alcohol 5 times, 80 DEG C of vacuum-drying 12h, obtain yellow solid 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride (NE-HBPI) (1.271g, productive rate: 91.05%).
The preparation of the terminated hyperbranched polyimide of embodiment 3:4-phenylacetylene base Tetra hydro Phthalic anhydride (PE-HBPI) and 4-(1-naphthalene ethynyl) the terminated hyperbranched polyimide of Tetra hydro Phthalic anhydride (NE-HBPI) cure polymer
PE-HBPI and NE-HBPI is placed in vacuum drying oven, and under vacuum state, 370 DEG C of process 2h, obtain cure polymer, are designated as Cured-PE-HBPI and Cured-NE-HBPI respectively.
Fig. 1 gives the infrared spectrum of PE-HBPI and NE-HBPI, and testing tool is German BRUKER company Vector22 type fourier transform infrared spectroscopy instrument.1779cm can be seen
-1(the asymmetric stretching vibration peak of C=O), 1725cm
-1(the symmetrical stretching vibration peak of C=O) and 1374cm
-1(stretching vibration peak of C – N) is the typical characteristic peak of imide ring in polyimide.2213cm can also be seen
-1place C ≡ C stretching vibration absorption peak.
Fig. 2 gives the nuclear magnetic spectrogram of PE-HBPI and NE-HBPI, and testing tool is the Bruker510 type nuclear magnetic resonance analyser (300MHz) of German BRUKER company.Corresponding dianhydride benzene ring hydrogen between 7.69-7.98ppm can be found out, 7.11-7.53ppm between the peripheral benzene ring hydrogen of corresponding triamine, the inside benzene ring hydrogen of the corresponding triamine of 6.15 – 6.93ppm, on alkynyl capping monomer, the peak shift of H is between 7.58 – 7.69ppm.
The number-average molecular weight of PE-HBPI and NE-HBPI is respectively 16621g/mol and 11279g/mol, and weight-average molecular weight is respectively 45399g/mol and 32932g/mol, and dispersion coefficient is respectively 2.7 and 2.9.
PE-HBPI and NE-HBPI has good solvability, can be dissolved in intensive polar solvent, such as, methyl-sulphoxide (DMSO), N,N-DIMETHYLACETAMIDE (DMAc), dimethyl formamide (DMF) and N-Methyl pyrrolidone (NMP).Also can be dissolved in weak polar solvent, such as, tetrahydrofuran (THF) (THF) and chloroform (CHCl
3).Also a part of polymkeric substance can be dissolved even in acetone.Five kinds of polymkeric substance have excellent deliquescent reason to be had: the first, and branched structure and the weak chain entanglement effect of hyperbranched polymer self make it have good solubility; The second, we introduce flexible ehter bond and the trifluoromethyl of large volume in polymer backbone structure, there is synergistic effect and destroy the regularity of molecular chain and reduce intermolecular interaction between these groups.
Fig. 3 gives the DSC test curve of PE-HBPI and NE-HBPI, and testing tool is the DSC821 of Mettler-Toledo company of Switzerland
etype differential scanning calorimeter.Can find out two kinds of polymkeric substance first time scanning curves all to exist a more weak second-order transition temperature (T
g), T
gbe respectively 166 DEG C and 167 DEG C.The unconspicuous reason of second-order transition temperature there is a large amount of ehter bonds and weak chain entanglement effect in polymer backbone.In addition, trifluoromethyl serves the effect of internal plasticiztion in the polymer, and the geometric configuration of end group and free volume also very large on the impact of second-order transition temperature.Also there is an exothermic peak in PE-HBPI and NE-HBPI, two exothermic peaks start from 375 DEG C and 388 DEG C, are up to 413 DEG C and 430 DEG C.As can be seen from the figure the beginning of NE-HBPI exothermic peak, the highest and end temp is all lower than the exothermic peak of PE-HBPI, and this wants fast due to the solidification rate of naphthalene acetylene group relative to phenylacetylene group, can in relatively low temperature-curable.To the hyperbranched polymer of alkynyl end-blocking carry out second time scan time because alkynyl occurs crosslinked, comprise triple bond and open, chainpropagation, chain extension etc., the final crosslinking structure that formed limits sub-chain motion, in addition, because hyperbranched polymer exists a large amount of end group, cross-linking density is too high, so do not find T
g.Exothermic peak also disappears, and illustrates that first time scanning alkynyl is completely crosslinked.
Fig. 4 gives the TGA test curve of PE-HBPI, NE-HBPI, Cured-PE-HBPI and Cured-NE-HBPI, and testing tool is the TGA-7 type high temperature calorimetry instrument of Perkin-Elmer company of the U.S..PE-HBPI and NE-HBPI synthesized under nitrogen atmosphere has good thermostability, and 5% thermal weight loss temperature is all more than 548 DEG C, and the thermal weight loss temperature of 10% is all more than 591 DEG C, and the Residual carbon of 800 DEG C is more than 58.8%.The 5% thermal weight loss temperature of Cured-PE-HBPI and Cured-NE-HBPI is all more than 600 DEG C, and the thermal weight loss temperature of 10% is all within the scope of 629-630 DEG C, and the Residual carbon of 800 DEG C, more than 65.2%, illustrates that the thermostability of crosslinked post-consumer polymer improves further.
Fig. 5 gives the rheological behaviour test curve of PE-HBPI and NE-HBPI, and testing tool is the plate rheometer of the PhysicaMCR300 type of German AntonPaar company.Can find out that PE-HBPI and NE-HBPI shows low melt viscosity, minimum melt viscosity is 13.3Pas (309 DEG C) and 12.6Pas (319 DEG C) respectively.Its reason is the molecular structure of the spheroid shape of hyperbranched polymer own, and large volume trifluoromethyl, the flexibly introducing of ehter bond and bulky end groups reduce further melt viscosity.When viscosity touches the bottom, when temperature continues to raise, the melt viscosity of alkynyl terminated polymer rises rapidly, and this is due to alkynyl generation crosslinking reaction, forms network structure, limits the motion of molecule.
The preparation of embodiment 4:PE-HBPI and linear polyimide blend
Linear polyimide is the Vespel polyimide thermoplastic property engineering resin that E.I.Du Pont Company produces, and unfilled matrix resin model is SP-1.Blended before by PE-HBPI and linear polyimide 100 DEG C of dry 12h in vacuum drying oven.Then the addition of super-branched polyimide according to massfraction 0%, 1%, 2%, 3%, 4%, 5% is joined in linear polyimide.Fully 10min is uniformly mixed with high speed Universalpulverizer (model: FW100, crushing quantity: 100g, rotating speed: 26000r/min, Beijing Zhong Xing great achievement Instrument Ltd.).Blend is numbered SP1/PE-0 (referring to containing super-branched polyimide 0%) respectively, SP1/PE-1 (referring to containing super-branched polyimide 1%), SP1/PE-2 (referring to containing super-branched polyimide 2%), SP1/PE-3 (referring to containing super-branched polyimide 3%), SP1/PE-4 (referring to containing super-branched polyimide 4%), SP1/PE-5 (referring to containing super-branched polyimide 5%).
Fig. 6 is the flow curve of PE-HBPI and linear polyimide blend, and the melt viscosity starting blend is as seen from Figure 6 higher, and then along with the rising polymer free volume of temperature becomes large, macromolecular chain thermal motion aggravates, and viscosity reduces gradually.About 350 DEG C time, the melt viscosity of polymkeric substance reaches minimum.
Table 1 is the rheological data of PE-HBPI and linear polyimide blend.
Table 1
Note: in table 1, η is lowest melt viscosity, T is temperature corresponding to lowest melt viscosity
As can be seen from Table 1 along with the increase of PE-HBPI addition, the minimum melt viscosity of blend reduces, the minimum melt viscosity of pure SP1 polymkeric substance is 5545Pas, after adding PE-HBPI, the minimum melt viscosity of blend is reduced to below 3285Pas, viscosity degradation 40.7%, the interpolation of visible PE-HBPI greatly reduces the melt viscosity of polymkeric substance, for processing brings convenience.Along with the increase of addition, the temperature reduction that minimum melt viscosity is corresponding, analyzing its reason may be, phenylacetylene base content increases, and more easily crosslinking reaction occurs, required temperature is lower.This makes process window move to low temperature, not only save energy, and reduces cost.
Table 2
Table 2 is the stretching data of PE-HBPI and linear polyimide blend, and testing tool is the omnipotent mechanics machine of SHIMADZUAG-I type of Japanese Shimadzu Corporation.Can find out that after introducing PE-HBPI, blend is tensile modulus before pyroprocessing, and tensile strength and elongation at break, all with the increase of addition, present the phenomenon first raising and reduce afterwards.This is that mechanical property is improved, and after add-on is more than 2%, hyperbranched polymer serves diluting effect wherein, makes mechanical properties decrease again because the introducing of a small amount of super-branched polyimide can play the effect of physical crosslinking point.Again from the interpolation blend of PE-HBPI and comparing of pure SP1 polymkeric substance, tensile modulus raises, and elongation at break reduces, and serves the effect of enhancing.This is spheroid shape structure due to super-branched polyimide and has a large amount of end group, it add the surface work added in breaking-down process, the intensity of material is improved.Heat-treat blend, because phenylacetylene base occurs crosslinked after pyroprocessing, add the contact between molecular chain, limit the Relative sliding between molecular chain, the mechanical property of the SP1/PE-2 that addition is the most suitable is improved.
Fig. 7 gives the DSC test curve of PE-HBPI and linear polyimide blend, can find out between 226 ~ 211 DEG C, the DSC curve of blend presents a second-order transition temperature, and along with the increase T of addition
gmove to low temperature direction, this is because the free volume of PE-HBPI end group is comparatively large, and destroy the close-packed of linear polyimide molecule chain, therefore molecule segment motion is relatively easy, T
greduce.
Fig. 8 gives PE-HBPI and the DSC test curve of linear polyimide blend after pyroprocessing, and can find out that SP1/PE series of blends is after 370 DEG C of solidification 2h, phenylacetylene base is cross-linked, and limits the motion of molecular chain, T
gall be increased to 231 DEG C.
Table 3
Table 3 is PE-HBPI and the TGA data of linear polyimide blend before and after pyroprocessing, and can find out the front increase along with addition of process by table 3 data, 5% thermal weight loss temperature and 800 DEG C of carbon yields all slightly increase.After pyroprocessing, phenylacetylene base is cross-linked, and form network structure, thermostability significantly improves.5% thermal weight loss temperature is all more than 540 DEG C.
The present invention's utilization introduces alkynyl containing alkynyl end-capping reagent monomer on the molecule of super-branched polyimide makes super-branched polyimide be provided with crosslinkable character, what the present invention's difference with the prior art in synthetic method was mainly to select in the present invention is 4-phenylacetylene base Tetra hydro Phthalic anhydride or 4-(1-naphthalene ethynyl) Tetra hydro Phthalic anhydride containing alkynyl end-capping reagent monomer, the embodiment of the present invention 1 and embodiment 2 are the preferred embodiment of the present invention, when preparing polyamic acid presoma, stir 36h at ambient temperature, also polyamic acid presoma can be obtained, the productive rate obtaining two kinds of final products after reaction terminates is respectively 83.6% and 85.7%.In addition, when preparing polyimide, 60 ~ 80 DEG C stir 6 ~ 8h and by containing ratio control between alkynyl end-capping reagent monomer and other two kinds of monomers in the scope of 1.5 ~ 2:1:1 to ensure to contain alkynyl end-capping reagent monomer and polyamic acid presoma fully reacts, 180 ~ 200 DEG C of normally used temperature ranges of hot imidization when being synthesis of polyimides, therefore, except 200 DEG C that provide in embodiment 1 and embodiment 2, condition controls all can reach the technique effect identical with embodiment 2 with embodiment 1 within the scope of 180 ~ 200 DEG C.The general knowledge that when isoquinoline 99.9 synthesizes as polyimide, its usage quantity of one of custom catalysts is known to the skilled person, the present invention to its usage quantity done optimize to make in hot imidization process of the present invention more reasonable.
It should be noted that meta-cresol usage ratio has a certain impact to realizing the present invention, find easily gel phenomenon to occur when the total amount of meta-cresol lower than during ratio provided by the present invention through repetition test, polymericular weight then can be caused when the ratio of meta-cresol is too high too low on the contrary, and not reach technique effect of the present invention.Ratio between two portions meta-cresol used mainly determined according to the solvability of solute in meta-cresol, therefore those skilled in the art dissolve situation according to reality, adjust to reach the technique effect identical with the embodiment of the present invention within scope provided by the present invention.
Claims (8)
1., containing an alkynyl super-branched polyimide, it is characterized in that, its molecular formula is:
Wherein, x, y and z represent repeating unit quantity, and x, y and z are 3 ~ 10 and x+y+z=15 ~ 20;
R＝
2. the preparation method containing alkynyl super-branched polyimide according to claim 1, its concrete steps are as follows:
A, under protective atmosphere, by 1,3,5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene is dissolved in first part's meta-cresol, at room temperature by 4,4 '-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride is dissolved in the solution that second section meta-cresol formed and is added drop-wise to 1,3, in the m-cresol solution of 5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene, stir while dropping, churning time is 36 ~ 48h, stirs after terminating and obtains polyamic acid presoma;
B, add containing alkynyl end-capping reagent monomer in described polyamic acid presoma, after stirring 6 ~ 8h at 60 ~ 80 DEG C; Drip the isoquinoline 99.9 being equivalent to meta-cresol total mass 0.5% ~ 0.7%, there is flocculent precipitate to being added in ethanol by the material taken out from reaction system in reaction under the condition of 180 ~ 200 DEG C, and described flocculent precipitate is namely containing alkynyl super-branched polyimide;
Wherein, described 1,3,5-tri-(2-trifluoromethyl-4-aminophenoxyl) benzene, 4,4 '-(3,4-di carboxyl phenyloxy) diphenyl ether dianhydride, first part's meta-cresol, second section meta-cresol are 1:1:100 ~ 120:160 ~ 180:1.5 ~ 2 with the mol ratio containing alkynyl end-capping reagent monomer; Described is 4-phenylacetylene base Tetra hydro Phthalic anhydride or 4-(1-naphthalene ethynyl) Tetra hydro Phthalic anhydride containing alkynyl end-capping reagent monomer.
3. a kind of preparation method containing alkynyl super-branched polyimide according to claim 2, it is characterized in that, it also comprises:
After C, completing steps B, by reaction system cool to room temperature, then pour in ethanol and separate out throw out, finally use ethanol wash by described throw out, obtain after drying pure containing alkynyl super-branched polyimide.
4. a kind of preparation method containing alkynyl super-branched polyimide according to Claims 2 or 3, it is characterized in that, in steps A, churning time is 48 hours.
5. a kind of preparation method containing alkynyl super-branched polyimide according to Claims 2 or 3, is characterized in that, add and under 80 DEG C of conditions, stir 8h containing after alkynyl end-capping reagent monomer in step B.
6. a kind of preparation method containing alkynyl super-branched polyimide according to Claims 2 or 3, is characterized in that, under the condition of 200 DEG C react after dripping isoquinoline 99.9 in step B.
7. a kind of preparation method containing alkynyl super-branched polyimide according to Claims 2 or 3, is characterized in that, when steps A carries out dropping stirring, time for adding is 1.5 ~ 2h.
8. use according to claim 1 as viscosity modifier containing joining in linear polyimide according to the addition of massfraction 1% ~ 5% after the drying of alkynyl super-branched polyimide.
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| CN106519670A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type BDATHQ branched polyimide resin film and preparation method thereof |
| CN106519678A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type bisphenol A tetramine branched polyimide resin film and preparation method thereof |
| CN106519677A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type fluorine-containing branched polyimide resin film and preparation method thereof |
| CN106633869A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type BDATHQ branched polyimide resin thin film and preparation method thereof |
| CN107789677A (en) * | 2017-09-29 | 2018-03-13 | 湖北大学 | A kind of preparation method and application of super-branched polyimide anti-coagulation anti-bacterial material |
| CN109111416A (en) * | 2018-08-24 | 2019-01-01 | 吉林大学 | A kind of diether dianhydride monomer and the preparation method and application thereof of the side group containing phenylacetylene base |
| CN109232892A (en) * | 2018-08-24 | 2019-01-18 | 吉林大学 | A kind of cross-linking super-branched polyimide and the preparation method and application thereof |
| CN109232892B (en) * | 2018-08-24 | 2020-11-06 | 吉林大学 | Cross-linkable hyperbranched polyimide and preparation method and application thereof |
| CN109111416B (en) * | 2018-08-24 | 2022-03-29 | 吉林大学 | Diether dianhydride monomer with phenylethynyl-containing side group and preparation method and application thereof |
| CN111423607A (en) * | 2020-05-21 | 2020-07-17 | 西南科技大学 | Preparation method of double-branched sulfonated polyimide membrane |
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