CN107098913B - [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- and synthetic method and application - Google Patents
[4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- and synthetic method and application Download PDFInfo
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Abstract
The invention belongs to super-branched polyimides to synthesize field, relate generally to a kind of four amido porphyrin monomers, i.e., 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins being synthetically prepared and applying.The synthesis step of four amido porphyrin monomer of this kind is that 4- bromobenzaldehyde, acetic anhydride, propionic acid are added dropwise to when heating and being condensed back and new steam pyrroles, obtain 5,10,15,20- tetra--(4- bromophenyl) porphyrin, the product obtained later and 3- amino phenylacetylene are in PdCl2(PPh3)2Sonogashire reaction occurs under equal catalyst and generates target product 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin.This kind contains four amido porphyrin monomer of phenylacetylene and anhydride reaction, by controlling feed ratio, obtain the super-branched polyimide of amino-terminated or acid anhydrides sealing end, obtained polymer has very good mechanical properties, high thermal stability, chemical property, absorption property, can be applied to photoelectric material and gas absorption field.
Description
Technical field
The invention belongs to super-branched polyimide monomers to synthesize field.
Background technique
Polyimides has high thermal stability, excellent mechanical performance, photoelectric properties, chemical stability, as extraordinary work
The polyimide material of engineering plastics all has in aerospace, photoelectric device, gas storage material, field of batteries etc. and answers extensively
With.And highly branched super-branched polyimide is poly- because the space net structure of its multidimensional and end-capping group abundant more impart
Acid imide is in porous material, the application of field of photovoltaic materials.
Porphyrin ring is because having 26 electronics height conjugated systems, excellent chemical stability, thermal property etc. in solar-electricity
The fields such as pond, electroluminescent organic material, light-guide material, electricity storage all have extensive use.In addition, porphyrin is in porous material side
Face using long-standing, about porphyrin material in COF (covalently-organic framework material), MOF (metal-organic framework materials)
Aspect has lot of documents report.
But itself existing conjugated degree of the monomer of existing polyimides is lower, limits it in electroluminescence material
The application in the fields such as material, light-guide material, photoelectric material.
Summary of the invention
To solve the above-mentioned problems, the present invention quotes porphyrin system, and phenylacetylene group is added on porphyrin main chain, can pass through
The conjugated system of phenylacetylene group and porphyrin ring reinforces its charge transport properties, makes its application in terms of photoelectricity, and porphyrin
Different electric properties can be obtained by chelating different metals；This kind of main chain tetramine containing phenylacetylene porphyrin simultaneously can be with side
Dianhydride monomer reaction of the chain containing phenylacetylene generates super-branched polyimide, handles to obtain crosslink density using post-crosslinking different
Porous gas adsorbent material.
Present invention introduces phenylacetylene and porphyrin system, design has synthesized a kind of tetramine monomers of main chain group containing phenylacetylene,
It is named are as follows: 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin.
Specific step is as follows for synthetic method of the invention:
Step 1: under nitrogen protection, forming reaction system with 4- bromobenzaldehyde, acetic anhydride and propionic acid, being heated to condensing
Reflux, pyrroles is slowly added dropwise in reaction system, and flow back 2.5-3h, stops heating；60-70 DEG C is down to temperature of reaction system
When, methanol is added into system, stands；Crude product 5,10,15,20- tetra--(4- bromophenyl) porphyrin is obtained by filtration, with petroleum ether:
Methylene chloride volume obtains pure 5,10,15,20- tetra--after chromatographing and dry by column than the solvent prepared for 1:1 ratio
(4- bromophenyl) porphyrin；Wherein 4- bromobenzaldehyde and the molar ratio of pyrroles are 1.1-1.2:1, propionic acid, acetic anhydride, methanol body
Product is than being 10:0.5-1:10；
Step 2: under nitrogen protection and anhydrous condition, with obtained 5,10,15, the 20- pure tetra--(4- of the first step
Bromophenyl) porphyrin, triphenylphosphine, chloroform and n,N-dimethylacetamide anabolic reaction system, are stirred at normal temperature to anti-
After answering system to become clarification, bis-triphenylphosphipalladium palladium dichloride, 3- amino phenylacetylene and triethylamine is added, improves temperature of reaction system extremely
60 DEG C, CuI, triethylamine is added, then reaction system is warming up to 80 DEG C, reacts 12-14h, discharge in deionized water, spend from
Sub- water washing 3-4 times, vacuum drying obtains crude product, is the solvent of 1:1 proportional arrangement with petroleum ether: ethyl acetate volume ratio
By obtaining pure target product 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphin after column chromatography and drying
Quinoline；The wherein moles total number of bis-triphenylphosphipalladium palladium dichloride, triphenylphosphine and CuI and 5,10,15,20- tetra--(4- bromophenyl) porphin
The molar ratio of quinoline is 0.01-0.1:1；The molar ratio of 5,10,15,20- tetra--(4- bromophenyl) porphyrin and 3- amino phenylacetylene is 1:
4.2-4.4；The volume ratio of N, N- dimethyl acetamide, triethylamine and chloroform is 1:1.1-1.2:0.5-1.
It uses propionic acid to add acetic anhydride as reaction dissolvent in the first step to be conducive to improve 5,10,15,20- tetra--(4- bromobenzene
Base) porphyrin yield；
[4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- is used to be used as tetramine monomers and two
Anhydride reactant prepares super-branched polyimide；
The wherein molecular structural formula such as formula (1) of the super-branched polyimide of acid anhydrides sealing end, amino-terminated hyperbranched polyamides
The molecular structural formula of imines such as formula (2).
In formula (1) and formula (2),
The specific reaction step of super-branched polyimide of acid anhydrides sealing end is as follows:
Dianhydride monomer is dissolved in N-Methyl pyrrolidone (NMP), then by 5,10,15,20- tetra- [4- [(3- aminophenyl)
Acetenyl] phenyl] porphyrin is dissolved in N-Methyl pyrrolidone (NMP) and is added dropwise in dianhydride monomer solution, 10-12h is reacted at room temperature,
Catalyst isoquinolin is added into reaction system, is warming up to 120 DEG C of reaction 4-5h, is continuously heating to 180 DEG C of reaction 14-16h, drops
Temperature discharging in dehydrated alcohol, and use ethanol washing, vacuum drying obtain acid anhydrides block super-branched polyimide.Wherein dianhydride
Molar ratio with 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is 3:1；
The dianhydride monomer be pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA),
1,4,5,8- naphthalene dianhydride (NTDA), 3,4,9,10- tetracarboxylic dianhydride (PTCDA), hexafluorodianhydride (6FDA) (6FDA), 3,3', 4,4'- bis-
Phenylsulfone tetrabasic carboxylic acid dicarboxylic anhydride (DSDA), 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA), two ether dianhydride of triphen
(TBDE), -4 '-phenylacetylene base biphenyl dianhydride of four benzene, three ether dianhydride (QBTE) or 2,5- bis- (3,4- di carboxyl phenyloxy)
(PEPHQDA)。
The reaction step of amino-terminated super-branched polyimide is as follows:
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is dissolved in N-Methyl pyrrolidone (NMP)
In obtain tetramine monomers solution, the dianhydride for being dissolved in N-Methyl pyrrolidone (NMP) is added dropwise in tetramine monomers solution, room temperature
10-12h is reacted, catalyst isoquinolin is added into reaction system, is warming up to 120 DEG C of reaction 4-5h, is continuously heating to 180 DEG C
14-16h is reacted, for cooling discharge in dehydrated alcohol, and with ethanol washing, vacuum drying obtains amino-terminated hyperbranched poly
Acid imide；Wherein the molar ratio of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- and dianhydride is 1:1；
The dianhydride monomer be pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA),
Isosorbide-5-Nitrae, 5,8- naphthalene dianhydrides (NTDA), 3,4,9,10- tetracarboxylic dianhydrides (PTCDA), hexafluorodianhydride (6FDA) (6FDA), 3,3', 4,4'- bis-
Phenylsulfone tetrabasic carboxylic acid dicarboxylic anhydride (DSDA), 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA), two ether dianhydride of triphen
(TBDE), four benzene, three ether dianhydride (QBTE) or 2, -4 '-phenylacetylene base biphenyl dianhydride of 5- bis- (3,4- di carboxyl phenyloxy)
(PEPHQDA)。
React former with capping monomer with 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin, dianhydride
The super-branched polyimide blocked with capping monomer is made in material, and specific synthesis step is as follows:
Dianhydride is dissolved in N-Methyl pyrrolidone (NMP) and obtains dianhydride monomer solution, is dissolved in N- crassitude
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins of ketone (NMP) are added dropwise in dianhydride monomer solution, room
Temperature reaction 10-12h, capping monomer is added into reaction system, reacts at room temperature 10-12h, isoquinolin is added into reaction system,
120 DEG C of reaction 4-5h are warming up to, 180 DEG C of reaction 14-16h are continuously heating to, cooling discharge is washed in dehydrated alcohol, and with ethyl alcohol
It washs 4-5 times, product 100 DEG C of vacuum dryings of vacuum drying oven；Wherein [4- [(3- aminophenyl) acetenyl] benzene of 5,10,15,20- tetra-
Base] porphyrin, dianhydride, capping monomer molar ratio be 1:3:2；
The dianhydride monomer be pyromellitic acid anhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA),
Isosorbide-5-Nitrae, 5,8- naphthalene dianhydrides (NTDA), 3,4,9,10- tetracarboxylic dianhydrides (PTCDA), hexafluorodianhydride (6FDA) (6FDA), 3,3', 4,4'- bis-
Phenylsulfone tetrabasic carboxylic acid dicarboxylic anhydride (DSDA), 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA), two ether dianhydride of triphen
(TBDE), four benzene, three ether dianhydride (QBTE) or 2, -4 '-phenylacetylene base biphenyl dianhydride of 5- bis- (3,4- di carboxyl phenyloxy)
(PEPHQDA)。
The capping monomer is 3- naphthalene acetylenylaniline, 3- phenylacetylene base aniline.
The acid anhydrides synthesized with 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin, dianhydride, metal ion
Sealing end or amino-terminated metalloporphyrin super-branched polyimide, specific reaction are to block acid anhydrides obtained or amino-terminated
Super-branched polyimide and metal inorganic salt be dissolved in n,N-Dimethylformamide (DMF), in 100 DEG C of heating reaction 6-
8h discharges in deionized water, and product is washed with deionized 4-5 times, product 100 DEG C of vacuum dryings of vacuum drying oven；On
Stating the molar ratio of acid anhydrides sealing end or amino-terminated polymer and metal inorganic salt in reaction is 1:10.
The invention has the advantages that:
The present invention provides a kind of " synthesis sides of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin
Method and application ".Phenylacetylene group is introduced into porphyrin system, because the big conjugate ring of phenylacetylene group and porphyrin ring is formed altogether
Yoke, this is conducive to charge transmission, there is very big application prospect in optoelectronic materials technology；
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] big conjugated systems of porphyrin simultaneously form it into steady
Determine two-dimensional structure.5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin reacts generation with some dianhydride monomers
Spacial framework, obtained several super-branched polyimides generate duct after post treatment, are applied to field of porous materials.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin；
Fig. 2 is the hydrogen nuclear magnetic spectrogram of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin；
Fig. 3 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with equal benzene
Tetracarboxylic acid dianhydride (PMDA), 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA), Isosorbide-5-Nitrae, 5,8- naphthalene dianhydrides (NTDA), 3,4,9,
The TGA curve graph of the super-branched polyimide of 10- tetracarboxylic dianhydride (PTCDA) sealing end；
Fig. 4 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with hexafluoro
DSC curve of the dianhydride (6FDA) as the super-branched polyimide of sealing end；
Fig. 5 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with hexafluoro
Infrared spectrogram of the dianhydride (6FDA) as the super-branched polyimide of sealing end.
Fig. 6 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with 2,5-
The polymer chelated mineral lead of two (3,4- di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) sealing end simultaneously passes through
Polymer 77K nitrogen adsorption curve after crosslinking Treatment.
Fig. 7 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with 2,5-
The polymer chelated mineral lead of two (3,4- di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) sealing end simultaneously passes through
The pore size distribution curve of polymer 77K nitrogen adsorption after crosslinking Treatment.
Fig. 8 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with 2,5-
The polymer chelated mineral lead of two (3,4- di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) sealing end simultaneously passes through
Polymer scanning electron microscope image after crossing crosslinking Treatment.
Fig. 9 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with hexafluoro
Ultraviolet-visible spectrogram of the dianhydride (6FDA) as the super-branched polyimide of sealing end.
Figure 10 is to synthesize by polyamine of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- with 2,5-
Two (3,4- di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) sealing end super-branched polyimide it is ultraviolet
Visible light spectrogram.
Specific embodiment
Technical solution of the present invention is further explained and is illustrated in a manner of specific embodiment below
Embodiment 1 (synthesis of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin)
Synthetic route is as follows:
Its reaction step is in two steps, the specific steps are as follows:
Step 1: 4- bromobenzaldehyde, propionic acid, acetic anhydride are added in 1000mL there-necked flask, it is heated to flowing back, slowly drips
Add new steaming pyrroles, there-necked flask is heated to being condensed back 2.5-3h, stops heating, is down to 60-70 DEG C to system temperature, first is added
Alcohol is stood, and crude product is washed with deionized 3-4 times in filtering, and column chromatography obtains pure product, and column chromatography uses petroleum
Ether: methylene chloride 1:1, obtained product is in 70 DEG C of vacuum dryings of vacuum drying oven.Wherein mole of 4- bromobenzaldehyde and pyrroles
Ratio is 1.1-1.2:1, propionic acid, acetic anhydride, methanol volume ratio be 10:0.5-1:10；
Step 2: by 5,10,15,20- tetra--(4- bromophenyl) porphyrin, triphenylphosphine, chloroform and N, N- dimethyl second
Amide (DMAc) is added in there-necked flask, is clarified to solution, and bis-triphenylphosphipalladium palladium dichloride (PdCl is added into there-necked flask2
(PPh3) 2), 3- amino phenylacetylene, triethylamine, there-necked flask is heated to 60 DEG C, to reaction system be added cuprous iodide (CuI) with
Triethylamine is further continued for being warming up to 80 DEG C of reaction 12-14h later, there-necked flask is down to room temperature discharging in deionized water, and spend
Ion water washing crude product 3-4 times, column chromatography obtains pure product 5,10,15,20- tetra- [4- [(3- aminophenyl) acetylene
Base] phenyl] porphyrin, the volume ratio of solvent petroleum ether and ethyl acetate used in column chromatography is 1:1, obtained pure production
Object is in 70 DEG C of vacuum dryings of vacuum drying oven.Wherein bis-triphenylphosphipalladium palladium dichloride (PdCl2(PPh3)2), triphenylphosphine, iodate it is sub-
The molar ratio of copper (CuI) and 5,10,15,20- tetra--(4- bromophenyl) porphyrins is between 0.01-0.1:1, and 5,10,15,20-
The molar ratio of four-(4- bromophenyl) porphyrins and 3- amino phenylacetylene is 1:4.2-4.4, n,N-dimethylacetamide, triethylamine with
The volume ratio of chloroform is 1:1.1-1.2:0.5-1.
What Fig. 1 was provided is the infrared spectrogram of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
3354 and 3317cm-1Place respectively corresponds [4- [(3- aminophenyl) acetenyl] phenyl] the porphyrin amino of 5,10,15,20- tetra- and pyrroles
The characteristic absorption peak of ring, 2206cm-1Corresponding is the characteristic absorption peak of C ≡ C group；
What Fig. 2 was provided is the hydrogen nuclear magnetic spectrogram of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins, figure
The a of middle mark, b, c, d, e, f, g, h, the chemical shift of i 5,10,15,20- tetra- [4- [(3- aminophenyl) corresponding with integral area
Acetenyl] phenyl] porphyrin structure, can prove to have synthesized 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl]
Porphyrin.
Embodiment 2: the super-branched polyimide blocked with hexafluorodianhydride (6FDA) (6FDA)
The specific synthesis step of the super-branched polyimide of hexafluorodianhydride (6FDA) (6FDA) sealing end is as follows:
Hexafluorodianhydride (6FDA) (6FDA) is dissolved in the there-necked flask of N-Methyl pyrrolidone (NMP), is dissolved in N- methylpyrrole
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins of alkanone (NMP) are slowly added dropwise in there-necked flask, are added dropwise
Room temperature reaction 10-12h is finished, isoquinolin is added, is warming up to 120 DEG C of reaction 4-5h, it is further heated up to 180 DEG C of reaction 14-16h
Room temperature discharging is down in dehydrated alcohol, and with ethanol washing 4-5 times, obtained product is dried in 100 DEG C of vacuum of vacuum drying oven
It is dry；
Wherein mole of hexafluorodianhydride (6FDA) (6FDA) and 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin
Than for 3:1.
What Fig. 4 was provided is [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- and hexafluorodianhydride (6FDA)
The DSC curve figure of the polymer of (6FDA) synthesis, the glass transition temperature of the polymer is 302 DEG C as seen from the figure, explanation
The polymer has good thermal property.
[4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- that Fig. 5 is provided is that polyamine is synthesized with six
Infrared spectrogram of the fluorine dianhydride (6FDA) as the super-branched polyimide of sealing end, 3312 and 2206cm-1Respectively correspond polymer
The characteristic absorption peak of middle pyrrole ring and C ≡ C, 1785 and 1726cm-1Respectively correspond the asymmetric and symmetrical of imide group carbonyl
Stretching vibration absworption peak shows the polymer for having synthesized hexafluorodianhydride (6FDA) (6FDA) sealing end；
[4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- that Fig. 9 is provided is that polyamine is synthesized with six
Ultraviolet-visible spectrogram of the fluorine dianhydride (6FDA) as the super-branched polyimide of sealing end.Absorption peak near 300nm belongs to
π-π in polyimide backbone structure*Transition；422nm is the absorption peak of porphyrin S band；517nm, 552nm, 591nm, 647nm are porphin
The absorption peak of four Q bands of quinoline；All there is red shift in the S band and Q band of porphyrin, because of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetylene
Base] phenyl] porphyrin introduces phenylacetylene group and enhances the conjugated degree of this kind of monomer, and the presence of porphyrin ring enhances polymer
Whole conjugated degree is conducive to the photoelectric properties for promoting polymer, obtain so that polymer field of photovoltaic materials application.
Embodiment 3: metalloporphyrin polymer obtained is blocked with hexafluorodianhydride (6FDA) (6FDA)
Its synthetic route is as follows
Its specific reaction step is as follows: by the obtained hyperbranched polyamides blocked with hexafluorodianhydride (6FDA) (6FDA) of embodiment 2
Imines is dissolved in n,N-Dimethylformamide (DMF), and metal inorganic salt, 100 DEG C of reaction 6-8h, discharging is added to reaction system
In deionized water, and product is washed with deionized 4-5 times, by product 100 DEG C of vacuum dryings of vacuum drying oven.Wherein hexafluoro
The super-branched polyimide of dianhydride (6FDA) sealing end and the molar ratio of metal inorganic salt are 1:10.
The metal inorganic salt of above-mentioned reaction includes: anhydrous plumbous acetate, anhydrous zinc acetate, cobalt chloride hexahydrate, six hydration chlorine
Change nickel, the metal inorganic salts such as Salicylaldoxime.
Embodiment 4: hexafluorodianhydride (6FDA) (6FDA) is substituted with 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides (DSDA), is repeated
Embodiment 2 and 3 obtains the super-branched polyimide and DSDA of 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydrides (DSDA) sealing end
The metalloporphyrin super-branched polyimide material of sealing end.
Embodiment 5: substituting hexafluorodianhydride (6FDA) (6FDA) with 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA), repeats real
Example 2 and 3 is applied, the dissaving polymer and BTDA sealing end of 3,3', 4,4'- benzophenone tetracarboxylic dianhydrides (BTDA) sealing end are obtained
Metalloporphyrin polymer.
Embodiment 6: the synthesis of the super-branched polyimide of pyromellitic dianhydride (PMDA) sealing end
Its specific synthesis step is as follows:
Pyromellitic dianhydride (PMDA) is dissolved in the there-necked flask of N-Methyl pyrrolidone (NMP), is dissolved in N- methyl
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins of pyrrolidones (NMP) are slowly added dropwise in there-necked flask,
Wait be added dropwise, 10-12h is reacted at room temperature, isoquinolin is added into there-necked flask, is warming up to 120 DEG C of reaction 4-5h, is continuously heating to
180 DEG C of reaction 14-16h, there-necked flask are down to room temperature discharging in dehydrated alcohol, and with ethanol washing product 4-5 times, will produce later
Object 100 DEG C of vacuum dryings of vacuum drying oven.Wherein pyromellitic dianhydride (PMDA) and [4- [(3- aminophenyl) of 5,10,15,20- tetra-
Acetenyl] phenyl] porphyrin molar ratio be 3:1.
Embodiment 7: substituting pyromellitic dianhydride (PMDA) with 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA), repeats real
Example 6 is applied, the dissaving polymer of 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides (BPDA) sealing end is obtained.
Embodiment 8: with Isosorbide-5-Nitrae, 5,8- naphthalene dianhydrides (NTDA) substitute pyromellitic dianhydride (PMDA), repeat embodiment 6, obtain
The dissaving polymer of 1,4,5,8- naphthalene dianhydride (NTDA) sealing end.
Embodiment 9: pyromellitic dianhydride (PMDA) is substituted with 3,4,9,10- tetracarboxylic dianhydrides (PTCDA), repeats embodiment
6, obtain the dissaving polymer of 3,4,9,10- tetracarboxylic dianhydrides (PTCDA) sealing end.
What Fig. 3 was provided is 5,10,15,20- tetra- in embodiment 6- embodiment 9 [4- [(3- aminophenyl) acetenyl] phenyl] porphin
The TGA curve graph of the dissaving polymer of acid anhydrides sealing end is made in quinoline and four kind of two anhydride reactant, and as can be seen from the figure these four are poly-
5% thermal weight loss temperature of object is closed between 484-535 DEG C, shows synthesized polymer thermal stability with higher.
- 4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of embodiment 10:2,5- bis- (3,4- di carboxyl phenyloxy) sealing end
The synthesis of super-branched polyimide
Its specific synthesis step is as follows:
- 4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of 2,5- bis- (3,4- di carboxyl phenyloxy) is dissolved in N- methylpyrrole
In the there-necked flask of alkanone (NMP), 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins are dissolved in N- methyl
It in pyrrolidones (NMP), is slowly added dropwise in there-necked flask, room temperature reaction 10-12h is added dropwise, isoquinoline is added into there-necked flask
Quinoline is warming up to 120 DEG C of reaction 4-5h, continues to be warming up to 180 DEG C of reaction 14-16h later, is cooled to room temperature discharging in dehydrated alcohol
In, and with ethanol washing product 4-5 times, by obtained product 100 DEG C of vacuum dryings of vacuum drying oven, wherein 2,5- bis- (3,4-
Di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) and [4- [(3- aminophenyl) acetylene of 5,10,15,20- tetra-
Base] phenyl] porphyrin molar ratio be 3:1；
- 4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of 2,5- bis- (3,4- di carboxyl phenyloxy) obtained above is blocked
Dissaving polymer be dissolved in n,N-Dimethylformamide (DMF), metal inorganic salt is added, and by reaction system 100
DEG C reaction 6-8h, is down to room temperature discharging in deionized water later, and is washed with deionized 4-5 times, with 100 DEG C of vacuum drying oven
Vacuum drying obtains -4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of 2,5- bis- (3,4- di carboxyl phenyloxy) sealing end metal porphin
The super-branched polyimide of quinoline, wherein 2,5- bis- (3,4- di carboxyl phenyloxy) -4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA)
The dissaving polymer of sealing end and the molar ratio of metal inorganic salt are 1:10.
The metal inorganic salt of above-mentioned reaction includes: anhydrous plumbous acetate, anhydrous zinc acetate, cobalt chloride hexahydrate, six hydration chlorine
Change nickel, the metal inorganic salts such as Salicylaldoxime.
- 4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of 2,5- bis- (3,4- di carboxyl phenyloxy) obtained above is blocked
Metalloporphyrin dissaving polymer in diphenyl sulphone (DPS) as solvent, 360 DEG C of high-temperature cross-linkings processing for 24 hours, obtain by crosslinking
Polymer after reason washs 48h, vacuum drying, the polyimides after obtaining crosslinking Treatment with Soxhlet extractor with acetone as solvent
Polymer.
It is using 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is polyamine with 2,5- that Fig. 6, which is provided,
Super-branched polyimide chelating of two (3,4- di carboxyl phenyloxy)-the 4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) as sealing end
Metallic lead and polymer 77K nitrogen adsorption curve Jing Guo crosslinking Treatment.Polymer after this kind of crosslinking Treatment, in 77K nitrogen
The attached BET specific surface of aspiration reaches 578m2g-1, show the super-branched polyimide material for successfully synthesizing this porous absorption；
It is using 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is polyamine with 2,5- that Fig. 7, which is provided,
Super-branched polyimide chelating of two (3,4- di carboxyl phenyloxy)-the 4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) as sealing end
Metallic lead and polymer 77K nitrogen adsorption pore-size distribution situation Jing Guo crosslinking Treatment, as can be seen from the figure by crosslinking
The pore-size distribution of polymer material after reason mainly at 0.38,0.46 and 0.59nm, shows this kind of polymer by crosslinking
Treated aperture is mainly based on the micropore size less than 1nm；
It is using 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is polyamine with 2,5- that Fig. 8, which is provided,
Super-branched polyimide chelating of two (3,4- di carboxyl phenyloxy)-the 4 '-phenylacetylene base biphenyl dianhydrides (PEPHQDA) as sealing end
The scanning electron microscope image of metallic lead and the polymer Jing Guo crosslinking Treatment, from image it can be seen that the accumulation of nanometer particle is formed
Cluster structure be conducive to form stable microcellular structure, be the gases such as the absorption nitrogen, carbon dioxide of this kind of porous adsorbing material
Principal element.
It is [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 5,10,15,20- tetra- is that polyamine is synthesized with 2 that Figure 10, which is provided,
The purple of the super-branched polyimide of -4 '-phenylacetylene base biphenyl dianhydride (PEPHQDA) of 5- bis- (3,4- di carboxyl phenyloxy) sealing end
Outer visible light spectrogram, the absorption peak near 300nm belong to π-π in polyimide backbone structure*Transition；422nm is porphyrin S
The absorption peak of band；517nm, 552nm, 591nm, 647nm are the absorption peak of four Q bands of porphyrin；The S band and Q band of porphyrin all occur
Red shift increases this kind of list because 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins introduce phenylacetylene group
The conjugated degree of body, and the presence of porphyrin ring enhances the conjugated degree of polymer entirety, is conducive to the photoelectricity for promoting polymer
Performance, obtain so that polymer field of photovoltaic materials application.
The super-branched polyimide preparation of embodiment 11:3- naphthalene acetylenylaniline sealing end
Steps are as follows for its specific experiment:
Hexafluorodianhydride (6FDA) (6FDA) is dissolved in the there-necked flask of N-Methyl pyrrolidone (NMP), is dissolved in N- methylpyrrole
The solution of alkanone (NMP) 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin, is slowly added dropwise into there-necked flask
In, be added dropwise, react at room temperature 10-12h, add 3- naphthalene acetylenylaniline, react at room temperature 10-12h, backward there-necked flask in
Isoquinolin is added, is warming up to 120 DEG C of holding 4-5h, then be warming up to 180 DEG C of reaction 14-16h, is down to room temperature discharging later in anhydrous
In ethyl alcohol, and with ethanol washing product 4-5 times, by obtained product 100 DEG C of vacuum dryings of vacuum drying oven.Wherein hexafluorodianhydride (6FDA)
(6FDA), 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin, 3- naphthalene acetylenylaniline molar ratio be
3:1:2；
The porphyrin dissaving polymer that 3- naphthalene acetylenylaniline obtained above blocks is dissolved in N, N- dimethyl formyl
Amine (DMF) is added metal inorganic salt, and reaction system is down to room temperature discharging in deionization in 100 DEG C of reaction 6-8h later
It in water, and is washed with deionized 4-5 times, by product 100 DEG C of vacuum dryings of vacuum drying oven, obtains 3- naphthalene acetylenylaniline envelope
The metalloporphyrin dissaving polymer at end.The wherein porphyrin dissaving polymer and metal inorganic salt of 3- naphthalene acetylenylaniline sealing end
Molar ratio be 1:10.
The metal inorganic salt of above-mentioned reaction includes: anhydrous plumbous acetate, anhydrous zinc acetate, cobalt chloride hexahydrate, six hydration chlorine
Change nickel, the metal inorganic salts such as Salicylaldoxime.
Embodiment 12: using 3- phenylacetylene base aniline substitution 3- naphthalene acetylenylaniline as capping monomer, embodiment 11 is repeated, is obtained
To using 3- phenylacetylene base aniline as the porphyrin dissaving polymer of end-capping group, and obtain corresponding metalloporphyrin hyperbranched poly
Acid imide.
Claims (10)
1.5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins, which is characterized in that molecular structural formula is as follows
Formula
2. the preparation side of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin as described in claim 1
Method, the specific steps are as follows:
Step 1: under nitrogen protection, reaction system is formed with 4- bromobenzaldehyde, acetic anhydride and propionic acid, is heated to being condensed back,
Pyrroles is slowly added dropwise in reaction system, flow back 2.5-3h, stops heating；When temperature of reaction system is down to 60-70 DEG C, to
Methanol is added in system, stands；Crude product 5,10,15,20- tetra--(4- bromophenyl) porphyrin is obtained by filtration, with petroleum ether: dichloro
Methane volumetric ratios are the solvent of 1:1 ratio preparation by obtaining pure 5,10,15,20- tetra--(4- after column chromatography and drying
Bromophenyl) porphyrin；Wherein 4- bromobenzaldehyde and the molar ratio of pyrroles are 1.1-1.2:1, the volume of propionic acid, acetic anhydride, methanol
Than for 10:0.5-1:10；
Step 2: under nitrogen protection and anhydrous condition, with obtained 5,10,15,20- tetra- pure-(the 4- bromobenzene of the first step
Base) porphyrin, triphenylphosphine, chloroform and n,N-dimethylacetamide anabolic reaction system, are stirred at normal temperature to reactant
After system becomes clarification, bis-triphenylphosphipalladium palladium dichloride, 3- amino phenylacetylene and triethylamine is added, improves temperature of reaction system to 60
DEG C, CuI, triethylamine is added, then reaction system is warming up to 80 DEG C, reacts 12-14h, discharge in deionized water, use deionization
Water washing 3-4 times, vacuum drying obtain crude product, are that the solvent of 1:1 proportional arrangement is logical with petroleum ether: ethyl acetate volume ratio
Pure target product 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphin is obtained after crossing column chromatography and drying
Quinoline；
The wherein moles total number of bis-triphenylphosphipalladium palladium dichloride, triphenylphosphine and CuI and 5,10,15,20- tetra--(4- bromophenyl)
The molar ratio of porphyrin is 0.01-0.1:1；5,10,15,20- tetra--(4- bromophenyl) porphyrin and the molar ratio of 3- amino phenylacetylene are
1:4.2-4.4；The volume ratio of n,N-dimethylacetamide, triethylamine and chloroform is 1:1.1-1.2:0.5-1.
3. a kind of 5,10,15,20- as described in claim 1 tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is used for
The purposes of super-branched polyimide is prepared as tetramine monomers and two anhydride reactants.
4. the purposes of according to claim 35,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
It is characterized in that, the super-branched polyimide is the super-branched polyimide or amino-terminated hyperbranched poly of acid anhydrides sealing end
Acid imide；The molecular structural formula such as formula (1) of the super-branched polyimide of the acid anhydrides sealing end, amino-terminated hyperbranched polyamides are sub-
The molecular structural formula of amine such as formula (2)；
In formula (1) and formula (2),
5. the purposes of according to claim 45,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
It is characterized in that, the specific reaction step of super-branched polyimide of acid anhydrides sealing end is as follows:
Dianhydride monomer is dissolved in N-Methyl pyrrolidone, then by 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl]
Phenyl] porphyrin is dissolved in N-Methyl pyrrolidone and is added dropwise in dianhydride monomer solution, 10-12h is reacted at room temperature, into reaction system
Catalyst isoquinolin is added, is warming up to 120 DEG C of reaction 4-5h, is continuously heating to 180 DEG C of reaction 14-16h, cooling discharge is in anhydrous
In ethyl alcohol, and with ethanol washing, vacuum drying obtains the super-branched polyimide of acid anhydrides sealing end；Wherein dianhydride and 5,10,15,
The molar ratio of 20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is 3:1.
6. the purposes of according to claim 45,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
It is characterized in that, the reaction step of amino-terminated super-branched polyimide is as follows:
5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin is dissolved in N-Methyl pyrrolidone and obtains four
Amine monomers solution, the dianhydride for being dissolved in N-Methyl pyrrolidone are added dropwise in tetramine monomers solution, react at room temperature 10-12h, to
Catalyst isoquinolin is added in reaction system, is warming up to 120 DEG C of reaction 4-5h, is continuously heating to 180 DEG C of reaction 14-16h, cools down
It discharges in dehydrated alcohol, and with ethanol washing, vacuum drying obtains amino-terminated super-branched polyimide；Wherein 5,10,
The molar ratio of [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin of 15,20- tetra- and dianhydride is 1:1.
7. the purposes of according to claim 35,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
It is characterized in that, the super-branched polyimide is the super-branched polyimide blocked with capping monomer.
8. the purposes of according to claim 75,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins,
It is characterized in that, specific as follows with the synthesis step of the super-branched polyimide of capping monomer sealing end:
Dianhydride, which is dissolved in N-Methyl pyrrolidone, obtains dianhydride monomer solution, is dissolved in the 5 of N-Methyl pyrrolidone, and 10,
15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins are added dropwise in dianhydride monomer solution, react at room temperature 10-12h,
Capping monomer is added into reaction system, reacts at room temperature 10-12h, isoquinolin is added into reaction system, is warming up to 120 DEG C instead
4-5h to be answered, 180 DEG C of reaction 14-16h are continuously heating to, cooling discharge is in dehydrated alcohol, and with ethanol washing 4-5 times, product
With 100 DEG C of vacuum dryings of vacuum drying oven；Wherein 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin, two
Acid anhydride, capping monomer molar ratio be 1:3:2；
The dianhydride monomer be pyromellitic acid anhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 1,4,5,8- naphthalene dianhydride, 3,
4,9,10- tetracarboxylic dianhydride, hexafluorodianhydride (6FDA), 3,3', 4,4'- diphenyl sulfone tetrabasic carboxylic acid dicarboxylic anhydride, 3,3', 4,4'- benzophenone
Tetracarboxylic acid dianhydride, two ether dianhydride of triphen, four benzene, three ether dianhydride or (3,4- di carboxyl phenyloxy)-the 4 '-phenylacetylene bases of 2,5- bis- connection
Benzene dianhydride；
The capping monomer is 3- naphthalene acetylenylaniline, 3- phenylacetylene base aniline.
9. a kind of purposes of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin described in claim 1,
It is characterized in that, with dianhydride, metal ion and with 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin systems
Standby acid anhydrides sealing end or the acid anhydrides sealing end or amino-terminated containing metal ion of amino-terminated super-branched polyimide preparation
Super-branched polyimide.
10. the use of 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrin according to claim 9
On the way, it is characterised in that: with 5,10,15,20- tetra- [4- [(3- aminophenyl) acetenyl] phenyl] porphyrins preparation acid anhydrides sealing end or
Amino-terminated super-branched polyimide and metal inorganic salt is dissolved in n,N-Dimethylformamide, is reacted in 100 DEG C of heating
6-8h discharges in deionized water, and product is washed with deionized 4-5 times, product 100 DEG C of vacuum dryings of vacuum drying oven；
Acid anhydrides sealing end or amino-terminated super-branched polyimide containing metal ion；The described acid anhydrides sealing end is amino-terminated poly-
The molar ratio for closing object and metal inorganic salt is 1:10.
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