CN108586403A - A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application - Google Patents

A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application Download PDF

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CN108586403A
CN108586403A CN201810351805.9A CN201810351805A CN108586403A CN 108586403 A CN108586403 A CN 108586403A CN 201810351805 A CN201810351805 A CN 201810351805A CN 108586403 A CN108586403 A CN 108586403A
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aminophenyls
dianhydride
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关绍巍
石凯祥
宋宁宁
关尔佳
祝世洋
张博
田野
王天娇
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Jilin University
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Abstract

The invention discloses a kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and applications, belong to polyimides and is synthetically prepared technical field, dianhydride monomer entitled 3 in the present invention, 3 ' two (3, 4 di carboxyl phenyloxies) 4, 4 ' tolans base biphenyl dianhydrides, dianhydride monomer of the side chain containing phenylacetylene in the present invention, based on biphenyl structural, with the crosslinkable groups containing phenylacetylene, the monomer can be applied to synthesizing linear and super-branched polyimide, it is handled by post-crosslinking and more excellent performance of polyimide material is made, and go controlled material structure by controlling crosslinked group content, promote the performance of polyimide material, the material has potential application in gas adsorption material.

Description

A kind of side chain dianhydride monomer containing phenylacetylene and its synthetic method and application
Technical field
The invention belongs to polyimides to synthesize field.
Background technology
Polyimides as a kind of special engineering plastics, the fields such as aerospace, seperation film, photoelectric information and coating all It is widely used.Super-branched polyimide has tridimensional network because its is highly branched, has preferable dissolubility, machinery The performances such as performance, thermo-chemical stability.The present invention designs and synthesizes a kind of acid anhydrides, introduces phenylacetylene group in side chain, probes into side The chain dianhydride monomer of group containing phenylacetylene carries out post-crosslinking processing in synthesis of polyimides material, and to polybenzazole precursor object, can show It writes and improves its performance, while widening polyimide polymer processing temperature, keep its application more extensive.
Guan Shaowei, Yao Hongyan et al. are in entitled one kind dianhydride monomer containing phenylacetylene base of application in 2014 and its synthesis side Method and the patent of invention of application (CN104478838A), and the SCI articles " Microporous that was delivered in 2017 polyimides networks constructed through a two-step polymerization approach, and their carbon dioxide adsorption performance”(Polym.Chem.,2017,8,1298- And " From a flexible hyperbranched polyimide to a microporous polyimide 1305) network:Microporous architecture and carbon dioxide adsorption”(Polymer,2017, 115:176-183)；Show polyimides prepared after introducing phenylacetylene base on the side chain of dianhydride monomer by being cross-linked to form Reticular structure can be used in the absorption of carbon dioxide, but its BET specific surface of experimental data surface is not high, and which has limited it The absorption property of carbon dioxide.And the reason of leading to the problem may be due to less for crosslinked site on its side chain, The degree of cross linking needs to be further improved.
Invention content
For the above problem, invention provides a kind of side chain dianhydride monomer containing phenylacetylene, the side chain phenylacetylene Dianhydride monomer, entitled 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, molecular structure Formula is as follows：
The synthetic route of its synthetic method of side chain dianhydride monomer containing phenylacetylene is,
It is as follows：
The first step：3,3 '-dihydroxybiphenyl amine are added in the there-necked flask equipped with nitrogen port and constant pressure funnel Sodium nitrite solution in deionized water by sodium nitrite dissolving is added dropwise to three mouthfuls by hydrogen bromide solution under -5~0 DEG C of environment The diazonium salt solution of 3,3 '-dihydroxybiphenyl amine is made in bottle；Again by the diazonium salt solution of 3,3 '-obtained dihydroxybiphenyl amine It is added dropwise in the there-necked flask equipped with hydrogen bromide solution and cuprous bromide, is warming up to 100 DEG C of 10~12h of reaction later, discharging is in going In ionized water, wash 3~4 times, with the mixed solvent of ethyl alcohol and water, volume ratio 1:1, it is recrystallized to give product 4,4 '-two is bromo- 3,3 '-'-biphenyl diphenols；3,3 ' in reaction-molar ratio of dihydroxybiphenyl amine, sodium nitrite and cuprous bromide is 1:2:(5~6)； Hydrogen bromide is for providing acid reaction environment.
Second step：It is bromo- it to be added 4,4 '-two in the there-necked flask equipped with nitrogen port, mechanical agitation, water-taker and condenser pipe 3,3 '-'-biphenyl diphenols, toluene, DMAc and Anhydrous potassium carbonate are heated to 120~130 DEG C of band 4~6h of water, are warming up to 140~150 DEG C residual toluene is steamed, reaction system is then cooled to 70~80 DEG C, 4- nitrophthalonitriles are added and continue 70~80 14~16h is reacted under the conditions of DEG C, is discharged in deionized water, is washed with deionized 3~4 times, with recrystallized from acetonitrile, obtains Crystal 70 DEG C of drying in vacuum drying oven obtain product 3,3 '-two (3,4- dimethoxy nitriles phenoxy group) -4,4 '-'-dibromobiphenyls；Wherein, 4,4 '-two bromo- 3,3 '-'-biphenyl diphenols, 4- nitrophthalonitriles molar ratio be 1:(2.2~2.5)；Anhydrous potassium carbonate is to urge Agent amount.
Third walks：Be added 3,3 '-two in the there-necked flask equipped with nitrogen port, mechanical agitation, condenser pipe and drying tube (3, 4- dimethoxy nitriles phenoxy group) -4,4 '-'-dibromobiphenyls and triphenylphosphine wait for 3,3 '-two (3,4- dimethoxy nitrile benzene oxygen using DMAc as solvent Base) -4, the use of triethylamine is that solvent dissolves PdCl after 4 '-'-dibromobiphenyls are fully dissolved in DMAc2(PPh3)2With phenylacetylene and add Enter in there-necked flask, when being warming up to 60 DEG C, the triethylamine solution of CuI be added, be warming up to 80~90 DEG C reaction 12~14h, discharging in It in deionized water, is washed with deionized 3~4 times, obtains crude product 3,3 '-two (3,4- dimethoxy nitrile phenoxy group) -4,4 '-hexichol Acetenyl biphenyl, with recrystallized from acetonitrile, obtained crystal is put in 70 DEG C of drying in vacuum drying oven；Wherein, 3,3 '-two (3,4- bis- Formonitrile HCN phenoxy group) -4,4 '-'-dibromobiphenyls, phenylacetylene and three kinds of catalyst PdCl2(PPh3)2, CuI and triphenylphosphine molar ratio Example is 1:(2.1~2.2):(0.01~0.1).
4th step：In the there-necked flask equipped with nitrogen port, mechanical agitation and condenser pipe, 3,3 '-two (3,4- diformazans are added Nitrile phenoxy group) -4,4 '-tolans base biphenyl, potassium hydroxide and deionized water, so that solution is in strong basicity (pH>14) it, heats To condensing reflux, 60~72h is reacted, discharges in the deionized water that pH is adjusted to acidity (pH=2~5), reuses neutrality Deionized water washing, obtained -4,4 '-tolans base biphenyl of product 3,3 '-two (3,4- di carboxyl phenyloxy) is put in 70 DEG C of drying in vacuum drying oven；
5th step：In the there-necked flask equipped with nitrogen port, mechanical agitation and condenser pipe, 3,3 '-two (3,4- dicarboxyls are added Phenoxy group) -4,4 '-tolans base biphenyl, acetic acid and acetic anhydride, be heated to condensing reflux, by reaction system heating reaction 3~ 6h, heat filtering, crystallisation by cooling obtain -4,4 '-tolans base biphenyl two of target product 3,3 '-two (3,4- di carboxyl phenyloxy) Acid anhydride, by target product in 70 DEG C of vacuum dryings of vacuum drying oven；The volume ratio of acetic acid and acetic anhydride is 1 in reaction:(2~2.2).
3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride is reacted with diamine monomer generates line Property polyimides, is as follows：
In molar ratio by 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride and diamine monomer Example 1:1 is added in there-necked flask, and using metacresol as solvent, 70~80 DEG C of 10~12h of reaction are warming up to 170~180 DEG C of reactions 20~for 24 hours, it discharges in absolute ethyl alcohol, is used in combination absolute ethyl alcohol to wash 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven obtain line Property polyimides；
Above-mentioned diamine monomer includes following：Benzidine, p-phenylenediamine, 3,3 '-dihydroxybiphenyl amine, 2,2 '-bis- (3- - 4 hydroxy phenyl of amino) hexafluoropropane, 2,2 '-two (3- amino-4-hydroxylphenyls) propane, 2,2 '-two (3- amino-4-hydroxies Phenyl) diphenyl sulphone (DPS), 3,3 '-two (2,3,5,6- tetra- fluoro- 4- vinyl benzenes oxygroups) -4,4 '-benzidines, 2,2 '-two [4- (2, Tetra- fluoro- 4- vinyl benzenes oxygroups of 3,5,6-) -3- aminophenyls] hexafluoropropane, 2,2 '-two [4- (tetra- fluoro- 4- ethylene of 2,3,5,6- Phenoxyl) -3- aminophenyls] propane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- amino] hexichol Sulfone, 4,4 '-diaminodiphenyl ethers, 1,3- bis- (1- amino -3- 4-trifluoromethylphenopendants) -5- (tetra- fluoro- 4- vinyl of 2,3,5,6- Phenoxy group) benzene and 1,3- diamino phenoxies -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene.
3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride presses molar ratio with polyamine Difference generates acid anhydrides sealing end or amino-terminated super-branched polyimide.
With the terminated hyperbranched polyimides specific experiment of acid anhydrides, steps are as follows：3,3 '-two (3,4- di carboxyl phenyloxies) -4, 4 '-tolans base biphenyl dianhydrides are dissolved in N-Methyl pyrrolidone (NMP) there-necked flask, and polyamine is dissolved in N- methylpyrroles It in the constant pressure funnel of alkanone (NMP), is slowly added dropwise in reaction system, reacts at room temperature 10~12h, it is different that 2~2.5mL is added Quinoline, be warming up to 120 DEG C reaction 4~5h, it is further heated up to 180 DEG C reaction 20~discharge in absolute ethyl alcohol afterwards for 24 hours, be used in combination Ethyl alcohol washs 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven.
3,3 '-two in above-mentioned acid anhydrides end capping reaction (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride with The molar ratio of polyamine is specifically determined according to contained amino number in polyamine, in the range of (2~3):1.
The synthesis step of amino-terminated super-branched polyimide is similar to the polyimides that acid anhydrides blocks, 3,3 '-two (3, 4- di carboxyl phenyloxies) the molar ratio example of -4,4 '-tolans base biphenyl dianhydrides and polyamine is 1:1.
Above-mentioned polyamine includes as follows：Three (4- aminophenyls) amine, 1,3,5- tri- (4- aminophenyls) benzene, four (4- amino Phenyl) methane, 4,4 ', 4 ", 4 " '-tetramino phthalocyanines, 5,10,15,20- tetra- (4- aminophenyls) porphyrins, 5,10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrin, nickel, 4,4 ', 4 ", 4 " '-tetramino phthalocyanine of lead, iron or manganese-, nickel, lead, iron Or manganese -5,10,15,20- tetra- (4- aminophenyls) porphyrins, nickel, lead, iron or manganese -5,10,15,20- tetra- [4- [(3- aminophenyls) Acetenyl] phenyl] porphyrin, N, N ', N "-three-(4- amino-phenyls)-N, N ' N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine, 4,4 '-two (3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) phenoxy group) benzophenone, 4,4 '-two [3,5- bis- (2- tri- - 4 amino-benzene oxygen of methyl fluoride) phenoxy group] diphenyl sulphone (DPS).
The present invention can also further prepare the super-branched polyimide blocked using capping monomer on this basis, sealing end 3- naphthalenes acetylenylaniline, 3- phenylacetylene base aniline may be used in monomer.
The super-branched polyimide blocked using capping monomer, steps are as follows for specific experiment：In have nitrogen protection three 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, N-Methyl pyrrolidone is added in mouth bottle (NMP), the solution for being dissolved in N-Methyl pyrrolidone (NMP) polyamine is slowly added dropwise in there-necked flask, and room temperature reaction 10~ 12h, then reaction system is added in capping monomer, 10~12h is reacted at room temperature, 2~2.5mL isoquinolin is added, is warming up to 120 DEG C instead Answer 4~5h, it is further heated up to 180 DEG C reaction 20~for 24 hours, discharge in absolute ethyl alcohol, be used in combination absolute ethyl alcohol wash 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven；Dianhydride containing phenylacetylene, polyamine and capping monomer molar ratio are 3 in reaction:(1~1.5): (1.5~2).
The present invention handles in super-branched polyimide obtained by post-crosslinking to obtain the porous material of stabilizing network structure, It is as follows：Super-branched polyimide and diphenyl sulphone (DPS) prepared by the above method are added in there-necked flask, the two presses quality Than 1:40~60 feed intake, and are heated to 360 DEG C and maintain for 24 hours, to keep phenylacetylene full cross-linked under the high temperature conditions at this temperature, system Crosslinked polyimide material is obtained, this kind of material is closed by the porous organo polysilica that cross-linking reaction makes skeleton form stable reticular structure Object is widely used in terms of gas absorption.
Beneficial effects of the present invention：
Dianhydride monomer (PEPHQDA) provided in CN104478838A, there are one cross-linking in side chain tool for acid anhydrides Phenylacetylene group, the quantity (crosslink density) of phenylacetylene group becomes the limit that polymer is applied to sorbing material in crosslinking pore-forming Factor processed.The present invention on this basis, using biphenyl as construction unit, while increasing the quantity of phenyl ring, draws in biphenyl both sides Enter phenylacetylene group, a series of linear polyimide, acid anhydrides blocks or amino to be made for raw material for this dianhydride containing phenylacetylene The super-branched polyimide material of sealing end, crosslink density is high, is conducive to polymer and is formed in post-crosslinking processing procedure more Reticular structure, while increasing the specific surface area of sorbing material, while the aperture of controlled material, thermo-chemical stability, machinery Performance reaches the wider application of material with this.
Description of the drawings
Fig. 1 is the infrared spectrogram of 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride.
Fig. 2 is the hydrogen nuclear magnetic spectrogram of 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride.
Fig. 3 is the carbon nuclear magnetic spectrogram of 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride.
Fig. 4 is the amino-terminated hyperbranched poly synthesized as polyamine using (4- aminophenyls) porphyrins of 5,10,15,20- tetra- Acid imide and crosslinking Treatment post-consumer polymer DSC curve figure.
Fig. 5 is the amino-terminated hyperbranched poly synthesized as polyamine using (4- aminophenyls) porphyrins of 5,10,15,20- tetra- Acid imide and crosslinking Treatment post-consumer polymer TGA curve graphs.
Fig. 6 be using (4- aminophenyls) porphyrins of 5,10,15,20- tetra- as the amino-terminated crosslinking Treatment that polyamine synthesizes after Super-branched polyimide 77K nitrogen adsorptions and desorption curve figure.
Fig. 7 be using (4- aminophenyls) porphyrins of 5,10,15,20- tetra- as the amino-terminated crosslinking Treatment that polyamine synthesizes after Super-branched polyimide surface topography scanning electron microscope image.
Specific implementation mode
Technical solution of the present invention is further explained and is illustrated in a manner of specific embodiment below.
Embodiment 1
The present embodiment is synthetically prepared with 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride Step illustrates, specific as follows：
The first step：3,3 '-dihydroxybiphenyls are added in the 500mL there-necked flasks equipped with nitrogen port and constant pressure funnel Amine (A), hydrogen bromide solvent, in deionized water by sodium nitrite dissolving, under -5~0 DEG C of environment slowly by sodium nitrite solution It is added dropwise in there-necked flask and diazol is made, obtained diazonium salt solution is slowly added dropwise to equipped with hydrogen bromide solution and cuprous bromide In there-necked flask, it is warming up to 100 DEG C of 10~12h of reaction later, discharges in deionized water, washs 3~4 times, with ethyl alcohol and water weight Crystallization obtains 4,4 '-two bromo- 3,3 '-'-biphenyl diphenol (product B) of product.3,3 ' in reaction-dihydroxybiphenyl amine, sodium nitrite, The molar ratio of cuprous bromide is 1:2:5~6, and the reaction that diazol is made need to carry out in -5~0 DEG C of reaction environment.
Second step：Equipped with nitrogen port, mechanical agitation, water-taker, condenser pipe 250mL there-necked flasks in be added product B, Toluene, DMAc, Anhydrous potassium carbonate are heated to 120~130 DEG C of band 4~6h of water, and it is further heated up to 140~150 DEG C to steam residue Then reaction system is cooled to 70~80 DEG C by toluene, 4- nitrophthalonitriles are added and react 14~16h, discharging in go from It in sub- water, and is washed with deionized 3~4 times, with recrystallized from acetonitrile, the 70 DEG C of drying in vacuum drying oven of obtained crystal obtain Product 3,3 '-two (3,4- dimethoxy nitriles phenoxy group) -4,4 '-'-dibromobiphenyls (product C).B, 4- nitrophthalonitrile in reaction Molar ratio is 1:2.2~2.5.
Third walks：Equipped with nitrogen port, mechanical agitation, condenser pipe, drying tube 250mL there-necked flasks in be added product C, Triphenylphosphine, DMAc wait for that product C all dissolves, PdCl are added2(PPh3)2With the triethylamine solution of phenylacetylene, by reaction system 60 DEG C are warming up to, the triethylamine solution of CuI is added, 80~90 DEG C of 12~14h of reaction is warming up to, discharges in deionized water, use Deionized water is washed 3~4 times, and (the production of -4,4 '-tolans base biphenyl of crude product 3,3 '-two (3,4- dimethoxy nitrile phenoxy group) is obtained Object D), with recrystallized from acetonitrile, obtained crystal is put in 70 DEG C of drying in vacuum drying oven.Product C, phenylacetylene are urged with three kinds in reaction Agent (PdCl2(PPh3)2, CuI and triphenylphosphine) molar ratio be 1:(2.1~2.2):(0.01~0.1).
4th step：Equipped with nitrogen port, mechanical agitation, condenser pipe 250mL there-necked flasks in, product D, hydroxide is added Potassium, deionized water, are heated to condensing reflux, react 60~72h, discharge in acid deionized water (pH=2~5), spend from Obtained -4,4 '-tolans base biphenyl (product E) of product 3,3 '-two (3,4- di carboxyl phenyloxy) is put in by sub- water washing 70 DEG C of drying in vacuum drying oven.Potassium hydroxide is that pH value is adjusted to strong basicity, pH for adjusting>14.
5th step：In the 250mL there-necked flasks equipped with nitrogen port, mechanical agitation, condenser pipe, product E, acetic acid, second is added Acid anhydrides is heated to condensing reflux, and by reaction system 3~6h of heating reflux reaction, heat filtering, crystallisation by cooling obtains target product 3, 3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, by target product in 70 DEG C of vacuum of vacuum drying oven Drying.The volume ratio of acetic acid and acetic anhydride is 1 in reaction:(2~2.2).
Synthetic reaction experimental procedure schematic diagram is as follows：
Fig. 1, Fig. 2 and Fig. 3 are 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride respectively Infrared spectrogram, hydrogen nuclear magnetic spectrogram and carbon nuclear magnetic spectrogram.2217cm in Fig. 1-1Corresponding phenylacetylene stretching vibration absworption peak, 1847cm-1And 1774cm-1For C=O stretching vibration absworption peaks in acid anhydrides.(3,4- di carboxyl phenyloxy) -4 3,3 '-two in Fig. 2, The hydrogen of 4 '-tolans base biphenyl dianhydrides has good corresponding with proton peak, there is very each carbon in the carbon nuclear magnetic spectrogram of Fig. 3 Good ownership, further determined the structure of 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydrides, Prove that we successfully synthesize this monomer.
Embodiment 2
The present embodiment is closed with 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride and diamine It is illustrated for the building-up process of linear polyimides.
Its synthetic route is as follows：
By taking 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, benzidine copolymerization as an example, 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, benzidine, metacresol are added to three mouthfuls Bottle in, 70~80 DEG C reaction 10~12h, be warming up to 170~180 DEG C reaction 20~for 24 hours, discharge in absolute ethyl alcohol, second is used in combination Alcohol washs 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven.
Above-mentioned diamines includes as follows：Benzidine, p-phenylenediamine, 3,3 '-dihydroxybiphenyl amine, 2,2 '-bis- (3- ammonia - 4 hydroxy phenyl of base) hexafluoropropane, 2,2 '-two (3- amino-4-hydroxylphenyls) propane, 2,2 '-two (3- amino-4-hydroxy benzene Base) diphenyl sulphone (DPS), 3,3 '-two (2,3,5,6- tetra- fluoro- 4- vinyl benzenes oxygroups) -4,4 '-benzidines, 2,2 '-two [4- (2,3, Tetra- fluoro- 4- vinyl benzenes oxygroups of 5,6-) -3- aminophenyls] hexafluoropropane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl of 2,3,5,6- Phenoxy group) -3- aminophenyls] propane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- amino] hexichol Sulfone, 4,4 '-diaminodiphenyl ethers, 1,3- bis- (1- amino -3- 4-trifluoromethylphenopendants) -5- (tetra- fluoro- 4- vinyl of 2,3,5,6- Phenoxy group) benzene, 1,3- diamino phenoxies -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene.
Embodiment 3
(3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride passes through with polyamine 3,3 '-two in the present invention Regulate and control rate of charge acid anhydrides sealing end or amino-terminated super-branched polyimide is made.
Its chemical equation is as follows：
The present embodiment with 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, 5,10,15, 20- tetra- (4- aminophenyls) porphyrin is specific experiment step for the amino-terminated super-branched polyimide material of Material synthesis It is rapid as follows：
(1) equipped with nitrogen port, mechanical agitation, drying tube 100mL there-necked flasks in, be added 5,10,15,20- tetra- (4- Aminophenyl) porphyrin is dissolved in N-Methyl pyrrolidone (NMP), it is dissolved in 3,3 '-two in N-Methyl pyrrolidone (NMP) (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride solution is slowly added dropwise in there-necked flask, and room temperature reaction 10~ 12h, into there-necked flask be added 2~2.5mL isoquinolin, be warming up to 120 DEG C reaction 4~5h, be continuously heating to 180 DEG C reaction 20~ For 24 hours, room temperature discharging is down in absolute ethyl alcohol, is used in combination ethyl alcohol to wash 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven.Wherein 3, 3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride and 5,10,15,20- tetra- (4- aminophenyls) porphins The molar ratio of quinoline is 1:1.
(2) amino-terminated polyimides obtained above is dissolved in n,N-dimethylacetamide (DMAc), to anti- It answers system that anhydrous plumbous acetate is added, is heated to 100 DEG C of 6~8h of reaction, discharges in deionized water, and be washed with deionized 4 ~5 times, in 100 DEG C of vacuum dryings of vacuum drying oven, obtain the super-branched polyimide of chelating lead porphyrin.
(3) porphyrin obtained above and metalloporphyrin polyimides are added with diphenyl sulphone (DPS) and carry nitrogen port and condenser pipe There-necked flask in, be heated to 360 DEG C and maintain for 24 hours, keep phenylacetylene full cross-linked under the high temperature conditions, be made crosslinked polyimide Material, this kind of material passes through the porous organic polymer that cross-linking reaction makes skeleton form stable reticular structure, in gas absorption side Face is widely used.
The over-expense of nickel, manganese, ferriporphyrin can be made in 3 step of embodiment (2) by the way that the water soluble salt of nickel, manganese or iron is added Change polyimides.
Fig. 4 and Fig. 5 is (4- aminophenyls) porphyrins of 5,10,15,20- tetra- and 3,3 '-two (3,4- dicarboxyl benzene oxygen respectively Base) -4,4 '-tolans base biphenyl dianhydrides reaction amino-terminated polyimide material obtained, and after 360 DEG C of crosslinking Treatments Polyimides DSC, TGA comparison diagram.It is crosslinked the disappearance of post-crosslinking exothermic peak in DSC figures, shows phenylacetylene in 360 DEG C of high temperature items Crosslinking is complete under part, is crosslinked the thermogravimetric curve of front and back polyimides in TGA figures by comparing, and polyimides is hot steady after crosslinking It is qualitative to be obviously improved.
Fig. 6 and Fig. 7 is corresponding 77K nitrogen adsorptions and desorption curve, the scanning electron microscope image of sample respectively.It is inhaled from nitrogen Attached curve learns that polyimide material Brunauer-Emmet-Teller (BET) specific surface area after crosslinking Treatment is 681m2g-1, it is that random nano-particle is piled up that scanning electron microscope image, which also shows sample, and polyimide material is rigid after crosslinking Treatment Property enhancing, duct is increased.Since side chain phenylacetylene is crosslinked pore-forming in polymer, polyimide material is made to be led applied to porous absorption Domain.
The super-branched polyimide synthetic method of acid anhydrides sealing end is similar to amino-terminated super-branched polyimide, and wherein 3, 3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride and 5,10,15,20- tetra- (4- aminophenyls) porphins The molar ratio of quinoline is 3:1.
Polyamine includes in the present embodiment：Three (4- aminophenyls) amine, 1,3,5- tri- (4- aminophenyls) benzene, four (4- ammonia Base phenyl) methane, 4,4 ', 4 ", 4 " '-tetramino phthalocyanines, 5,10,15,20- tetra- (4- aminophenyls) porphyrins, 5,10,15,20- Four [4- [(3- aminophenyls) acetenyl] phenyl] porphyrins, nickel, lead, iron, 4,4 ', 4 ", 4 " '-tetramino phthalocyanine of manganese-, nickel, lead, Iron, manganese -5,10,15,20- four (4- aminophenyls) porphyrin, nickel, lead, the iron, [4- [(3- aminophenyls) of manganese -5,10,15,20- four Acetenyl] phenyl] porphyrin, N, N ', N "-three-(4- amino-phenyls)-N, N ', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine, 4,4 '-two (3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) phenoxy group) benzophenone, 4,4 '-the two [(2- tri- of 3,5- bis- - 4 amino-benzene oxygen of methyl fluoride) phenoxy group] diphenyl sulphone (DPS).
Embodiment 4
Polyamide made from 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, polyamine Acid precursor and the hyperbranched polyamides that 3- naphthalenes acetylenylaniline, 3- phenylacetylene base aniline are that corresponding end-capping group sealing end is made in raw material Imines.
With 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, 5,10,15,20- tetra- (4- Aminophenyl) it porphyrin, illustrates for 3- naphthalene acetylenylanilines.
(1) steps are as follows for specific experiment：3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride It is dissolved in the there-necked flask of N-Methyl pyrrolidone (NMP), 5,10,15,20- tetra- (4- aminophenyls) porphyrins is dissolved in N- first Base pyrrolidones (NMP) prevents gel from need to control rate of addition and is slowly added dropwise in there-necked flask, after reacting at room temperature 10~12h, adds Enter 3- naphthalene acetylenylanilines, react at room temperature 10~12h, 2~2.5mL of isoquinolin is added, is warming up to 120 DEG C of 4~5h of reaction, followed by It is continuous to be warming up to 180 DEG C of reactions 20~for 24 hours, room temperature discharging is down in absolute ethyl alcohol, is used in combination ethyl alcohol to wash 4~5 times, vacuum drying oven 100 DEG C of vacuum dryings.Wherein 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, 5,10,15, The molar ratio that 20- tetra- (4- aminophenyls) porphyrin, 3- naphthalene acetylenylanilines are added is 3:1:2.
(2) polyimides that 3- naphthalenes acetylenylaniline obtained above blocks is dissolved in DMAC N,N' dimethyl acetamide (DMAc) in, anhydrous plumbous acetate is added to reaction system, is heated to 100 DEG C of 6~8h of reaction, discharges in deionized water, be used in combination Deionized water is washed 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven, obtains the super-branched polyimide of chelating lead porphyrin.
(3) porphyrin obtained above and metalloporphyrin polyimides are added with diphenyl sulphone (DPS) and carry nitrogen port and condenser pipe There-necked flask in, be heated to 360 DEG C and maintain for 24 hours, keep phenylacetylene full cross-linked under the high temperature conditions, be made crosslinked polyimide Material, this kind of material make skeleton form the porous organic polymer of stable reticular structure, are applied to gas and inhale by cross-linking reaction Subsidiary formula face.
The over-expense of nickel, manganese, ferriporphyrin can be made in 4 step of embodiment (2) by the way that the water soluble salt of nickel, manganese or iron is added Change polyimides.
With 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, 5,10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrin, 3- naphthalene acetylenylanilines be that raw material is made and is blocked with 3- naphthalene acetylenylanilines Super-branched polyimide.
Above-mentioned polyamine includes as follows：Three (4- aminophenyls) amine, 1,3,5- tri- (4- aminophenyls) benzene, four (4- amino Phenyl) methane, 4,4 ', 4 ", 4 " '-tetramino phthalocyanines, 5,10,15,20- tetra- (4- aminophenyls) porphyrins, 5,10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrin, nickel, lead, iron, 4,4 ', 4 ", 4 " '-tetramino phthalocyanine of manganese-, nickel, lead, iron, Manganese -5,10,15,20- four (4- aminophenyls) porphyrin, nickel, lead, iron, [4- [(3- aminophenyls) second of manganese -5,10,15,20- four Alkynyl] phenyl] porphyrin, N, -1,3,5- benzene three of N ', N "-three-(4- amino-phenyls)-N, N ', N "-three-(4- methoxyl groups-phenyl) Amine, 4,4 '-two (3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) phenoxy group) benzophenone, 4,4 '-two [(the 2- trifluoros of 3,5- bis- - 4 amino-benzene oxygen of methyl) phenoxy group] diphenyl sulphone (DPS).
Similarly, it using 3- phenylacetylene bases aniline as capping monomer, repeats embodiment 4 and obtains the super of corresponding end-capping group sealing end Branched polyimide.

Claims (10)

1. a kind of side chain dianhydride monomer containing phenylacetylene, which is characterized in that the side chain phenylacetylene dianhydride monomer, entitled 3, 3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride, molecular structural formula are as follows：
2. the synthetic method of side chain dianhydride monomer containing phenylacetylene as described in claim 1, is as follows：
The first step：The bromination of 3,3 '-dihydroxybiphenyl amine is added in the there-necked flask equipped with nitrogen port and constant pressure funnel Sodium nitrite solution in deionized water by sodium nitrite dissolving is added dropwise in there-necked flask under -5~0 DEG C of environment by hydrogen solution The diazonium salt solution of 3,3 '-dihydroxybiphenyl amine is made；The diazonium salt solution of 3,3 '-obtained dihydroxybiphenyl amine is added dropwise again Enter in the there-necked flask equipped with hydrogen bromide solution and cuprous bromide, is warming up to 100 DEG C of 10~12h of reaction later, discharges in deionization It in water, washs 3~4 times, the volume ratio with the mixed solvent of ethyl alcohol and water, second alcohol and water is 1:1, it is recrystallized to give product 4, 4 '-two bromo- 3,3 '-'-biphenyl diphenols；3,3 ' in reaction-molar ratio of dihydroxybiphenyl amine, sodium nitrite and cuprous bromide is 1: 2:(5~6)；Hydrogen bromide is for providing acid reaction environment；
Second step：4,4 '-two bromo- 3 are added in the there-necked flask equipped with nitrogen port, mechanical agitation, water-taker and condenser pipe, 3 '-'-biphenyl diphenols, toluene, DMAc and Anhydrous potassium carbonate are heated to 120~130 DEG C of band 4~6h of water, are warming up to 140~150 DEG C Residual toluene is steamed, reaction system is then cooled to 70~80 DEG C, 4- nitrophthalonitriles are added and continue at 70~80 DEG C Under the conditions of react 14~16h, discharge in deionized water, be washed with deionized 3~4 times, with recrystallized from acetonitrile, obtained crystalline substance Body 70 DEG C of drying in vacuum drying oven obtain product 3,3 '-two (3,4- dimethoxy nitriles phenoxy group) -4,4 '-'-dibromobiphenyls；Wherein, 4, 4 '-two bromo- 3,3 '-'-biphenyl diphenols, 4- nitrophthalonitriles molar ratio be 1:(2.2~2.5)；Anhydrous potassium carbonate is catalysis Dosage.
Third walks：3,3 '-two (3,4- bis- are added in the there-necked flask equipped with nitrogen port, mechanical agitation, condenser pipe and drying tube Formonitrile HCN phenoxy group) -4,4 '-'-dibromobiphenyls and triphenylphosphine wait for 3,3 '-two (3,4- dimethoxy nitrile phenoxy groups)-using DMAc as solvent The use of triethylamine is that solvent dissolves PdCl after 4,4 '-'-dibromobiphenyls are fully dissolved in DMAc2(PPh3)2With phenylacetylene and addition three In mouthful bottle, when being warming up to 60 DEG C, the triethylamine solution of CuI is added, is warming up to 80~90 DEG C of 12~14h of reaction, discharging in go from It in sub- water, is washed with deionized 3~4 times, obtains crude product 3,3 '-two (3,4- dimethoxy nitrile phenoxy group) -4,4 '-tolans Base biphenyl (D), with recrystallized from acetonitrile, obtained crystal is put in 70 DEG C of drying in vacuum drying oven；Wherein, 3,3 '-two (3,4- diformazans Nitrile phenoxy group) -4,4 '-'-dibromobiphenyls, phenylacetylene and three kinds of catalyst PdCl2(PPh3)2, CuI and triphenylphosphine molar ratio It is 1:(2.1~2.2):(0.01~0.1).
4th step：In the there-necked flask equipped with nitrogen port, mechanical agitation and condenser pipe, 3,3 '-two (3,4- dimethoxy nitrile benzene are added Oxygroup) -4,4 '-tolans base biphenyl, potassium hydroxide and deionized water, so that solution is in pH>14 strong basicity is heated to cold Solidifying reflux, reacts 60~72h, discharges in being adjusted to pH in acid deionized water, pH=2~5, reuse it is neutral go from Obtained -4,4 '-tolans base biphenyl of product 3,3 '-two (3,4- di carboxyl phenyloxy) is put in vacuum and dried by sub- water washing 70 DEG C of drying in case；
5th step：In the there-necked flask equipped with nitrogen port, mechanical agitation and condenser pipe, 3,3 '-two (3,4- dicarboxyl benzene oxygen are added Base) -4,4 '-tolans base biphenyl, acetic acid and acetic anhydride, it is heated to condensing reflux, reaction system is heated into 3~6h of reaction, Heat filtering, crystallisation by cooling obtain -4,4 '-tolans base biphenyl dianhydride of target product 3,3 '-two (3,4- di carboxyl phenyloxy), By target product in 70 DEG C of vacuum dryings of vacuum drying oven；The volume ratio of acetic acid and acetic anhydride is 1 in reaction:(2~2.2).
3. side chain dianhydride monomer containing phenylacetylene as described in claim 1 prepares linear polyimides for being reacted with diamine monomer Or the purposes of super-branched polyimide is prepared with polyamine monomer reaction；The dianhydride monomer and polyamine by dianhydride monomer with it is polynary Acid anhydrides is different from the molar ratio of amino in amine, respectively obtains acid anhydrides sealing end or amino-terminated super-branched polyimide；
The diamine monomer is benzidine, p-phenylenediamine, 3,3 '-dihydroxybiphenyl amine, 2,2 '-bis- (- 4 hydroxy benzenes of 3- amino Base) hexafluoropropane, 2,2 '-two (3- amino-4-hydroxylphenyls) propane, 2,2 '-two (3- amino-4-hydroxylphenyls) diphenyl sulphone (DPS)s, 3,3 '-two (2,3,5,6- tetra- fluoro- 4- vinyl benzenes oxygroups) -4,4 '-benzidines, 2,2 '-two [4- (2,3,5,6- tetra- fluoro- 4- Vinyl benzene oxygroup) -3- aminophenyls] hexafluoropropane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- Aminophenyl] propane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- amino] diphenyl sulphone (DPS)s, 4,4 '-diaminos Yl diphenyl ether, 1,3- bis- (1- amino -3- 4-trifluoromethylphenopendants) -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene and One or more combinations in 1,3- diamino phenoxies -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene；
The polyamine is tertiary amine or quaternary amine, specially three (4- aminophenyls) amine, 1,3,5- tri- (4- aminophenyls) Benzene, four (4- aminophenyls) methane, 4,4 ', 4 ", 4 " '-tetramino phthalocyanines, 5,10,15,20- tetra- (4- aminophenyls) porphyrins, 5, 10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrins, R-4,4 ', 4 ", 4 " '-tetramino phthalocyanines, R-5,10, 15,20- tetra- (4- aminophenyls) porphyrin, R-5,10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrin, N, - 1,3,5- benzene triamines of N ', N "-three-(4- amino-phenyls)-N, N ', N "-three-(4- methoxyl groups-phenyl), 4,4 '-two (3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) phenoxy group) benzophenone, 4,4 '-two [3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) Phenoxy group] one or more combinations in diphenyl sulphone (DPS)；Wherein, R=nickel, lead, iron or manganese.
4. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 3, which is characterized in that the dianhydride monomer and two Amine monomers reaction prepares linear polyimides and is as follows：
By 3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride and diamine monomer example 1 in molar ratio: 1 is added in there-necked flask, using metacresol as solvent, 70~80 DEG C reaction 10~12h, be warming up to 170~180 DEG C reaction 20~ For 24 hours, discharging is used in combination absolute ethyl alcohol to wash 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven are linearly gathered in absolute ethyl alcohol Acid imide；
The diamine monomer is benzidine, p-phenylenediamine, 3,3 '-dihydroxybiphenyl amine, 2,2 '-bis- (- 4 hydroxy benzenes of 3- amino Base) hexafluoropropane, 2,2 '-two (3- amino-4-hydroxylphenyls) propane, 2,2 '-two (3- amino-4-hydroxylphenyls) diphenyl sulphone (DPS)s, 3,3 '-two (2,3,5,6- tetra- fluoro- 4- vinyl benzenes oxygroups) -4,4 '-benzidines, 2,2 '-two [4- (2,3,5,6- tetra- fluoro- 4- Vinyl benzene oxygroup) -3- aminophenyls] hexafluoropropane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- Aminophenyl] propane, 2,2 '-two [4- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) -3- amino] diphenyl sulphone (DPS)s, 4,4 '-diaminos Yl diphenyl ether, 1,3- bis- (1- amino -3- 4-trifluoromethylphenopendants) -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene and One or more combinations in 1,3- diamino phenoxies -5- (tetra- fluoro- 4- vinyl benzenes oxygroups of 2,3,5,6-) benzene.
5. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 3, which is characterized in that acid anhydrides blocks or amino The preparation method of the super-branched polyimide of sealing end is as follows：
3,3 '-two (3,4- di carboxyl phenyloxy) -4,4 '-tolans base biphenyl dianhydride is dissolved in N-Methyl pyrrolidone, And be transferred in there-necked flask, while polyamine being dissolved in N-Methyl pyrrolidone, and be transferred in constant pressure funnel, lead to It crosses constant pressure funnel polyamine is added dropwise in reaction system, reacts 10~12h at room temperature, it is different that 2~2.5mL is then added Quinoline is warming up to 120 DEG C of 4~5h of reaction as catalyst, and it is further heated up to 180 DEG C of reactions 20~discharged afterwards in anhydrous for 24 hours In ethyl alcohol, it is used in combination ethyl alcohol to wash 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven；
The molar ratio of dianhydride and polyamine is (2~3):It is generated with the terminated hyperbranched polyimides of acid anhydrides when 1；Work as molar ratio It is 1:It is generated with amino-terminated hyperbranched polyimides when 1；
The polyamine is tertiary amine or quaternary amine, specially three (4- aminophenyls) amine, 1,3,5- tri- (4- aminophenyls) Benzene, four (4- aminophenyls) methane, 4,4 ', 4 ", 4 " '-tetramino phthalocyanines, 5,10,15,20- tetra- (4- aminophenyls) porphyrins, 5, 10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrins, R-4,4 ', 4 ", 4 " '-tetramino phthalocyanines, R-5,10, 15,20- tetra- (4- aminophenyls) porphyrin, R-5,10,15,20- tetra- [4- [(3- aminophenyls) acetenyl] phenyl] porphyrin, N, - 1,3,5- benzene triamines of N ', N "-three-(4- amino-phenyls)-N, N ', N "-three-(4- methoxyl groups-phenyl), 4,4 '-two (3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) phenoxy group) benzophenone, 4,4 '-two [3,5- bis- (- 4 amino-benzene oxygen of 2- trifluoromethyls) Phenoxy group] one or more combinations in diphenyl sulphone (DPS)；Wherein, R=nickel, lead, iron or manganese.
6. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 3, which is characterized in that the dianhydride monomer with it is more First amine reaction prepares super-branched polyimide, then the super-branched polyimide for preparing and being blocked with end-capping group is reacted with capping monomer Purposes, the capping monomer be 3- naphthalenes acetylenylaniline or 3- phenylacetylene base aniline.
7. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 6, which is characterized in that the end-capping group envelope The super-branched polyimide at end, specific preparation process are as follows：
The side chain dianhydride monomer containing phenylacetylene and N-Methyl pyrrolidone are added in the there-necked flask for having nitrogen protection, by side Chain dianhydride monomer containing phenylacetylene is dissolved in N-Methyl pyrrolidone, while polyamine being dissolved in N-Methyl pyrrolidone, And be transferred in constant pressure funnel, polyamine is added dropwise in reaction system by constant pressure funnel, at ambient temperature 10~12h is reacted, then reaction system is added in capping monomer, reacts at room temperature 10~12h, 2~2.5mL isoquinolin, heating is added To 120 DEG C reaction 4~5h, it is further heated up to 180 DEG C reaction 20~for 24 hours, discharge in absolute ethyl alcohol, be used in combination absolute ethyl alcohol to wash It washs 4~5 times, 100 DEG C of vacuum dryings of vacuum drying oven；Dianhydride containing phenylacetylene, polyamine and capping monomer molar ratio are 3 in reaction: (1~1.5):(1.5~2).
8. the purposes of side chain dianhydride monomer containing phenylacetylene according to any one of claim 3~7, which is characterized in that The linear polyimides or super-branched polyimide obtain crosslinked linear polyimides or over-expense after crosslinking Treatment Change polyimides.
9. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 8, which is characterized in that the step of crosslinking Treatment It is specific as follows：By super-branched polyimide obtained and diphenyl sulphone (DPS) in mass ratio 1:40~60 are added in there-necked flask, are heated to 360 DEG C and maintain for 24 hours, to keep phenylacetylene full cross-linked under the high temperature conditions at this temperature, crosslinked polyimide material is made.
10. the purposes of side chain dianhydride monomer containing phenylacetylene according to claim 8, which is characterized in that crosslinked linear poly- Acid imide or super-branched polyimide are applied to gas absorption as porous material.
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