CN105566127B - A kind of Triamine monomer and its preparation method and application - Google Patents

A kind of Triamine monomer and its preparation method and application Download PDF

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CN105566127B
CN105566127B CN201610117522.9A CN201610117522A CN105566127B CN 105566127 B CN105566127 B CN 105566127B CN 201610117522 A CN201610117522 A CN 201610117522A CN 105566127 B CN105566127 B CN 105566127B
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dianhydride
anhydride
triamine
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CN105566127A (en
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关绍巍
宋颖
关尔佳
祝世洋
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Jilin University
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    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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Abstract

The invention discloses a kind of Triamine monomer and its preparation method and application, and the invention belongs to the technical field of high polymer material.Triamine monomer provided by the present invention is N, N', N " three (4 aminophenyl) N, N', N " three (4 methoxyphenyl) 1,3,5 benzene triamine.Synthetic method divides three-step reaction, 4 methoxyl group 4' nitrodiphenylamines are made as raw material using P-nethoxyaniline and p-fluoronitrobenzene first, then with 4 methoxyl group 4' nitrodiphenylamines and 1,3,5 tribromo-benzenes are that N is made in raw material, N'; N " three (4 nitrobenzophenone) N, N', N " three (4 methoxyphenyl) 1; 3,5 benzene triamines；Target Triamine monomer finally is made with palladium carbon and hydration hydrazine reaction.The application of Triamine monomer is can to prepare terminated hyperbranched polyimides by core of this Triamine monomer, can realize the regulation and control to polyimides photoelectric properties by the species and quantity that control end-capping group, be advantageous to the exploitation and application of novel photoelectric functional material.

Description

A kind of Triamine monomer and its preparation method and application
Technical field
The invention belongs to technical field of polymer materials.
Background technology
Polyimide material is due to its various route of synthesis, good mechanical performance, excellent resistance to gentle chemical resistance Can, some row advantages such as outstanding dielectric properties and relatively simple processing technology, cause polymer material science circle Pay attention to.Under the effort of several generations scholar, polyimide material has been widely used in the high-tech such as space flight, aviation, microelectronics Field.Due to its excellent combination property and very strong molecular structure designability, photoelectric functional material in last decade Polyimide material is a dark horse in research.
Dissaving polymer can be described as the macromolecule with high levels of three-dimensional branched structure, he both with branched polymer not Together, also had any different with dendritic molecule.Closely rise during the last ten years and be quickly become the study hotspot of scientists extensive concern Highly branched three-dimensional molecular structure that super-branched polyimide has, good dissolubility energy, low solution viscosity, without chain entanglement The features such as, meanwhile, substantial amounts of end group is contained in the macromolecular chain periphery of dissaving polymer three-dimensional structure, by terminal groups The further chemical modification of group turns to exploitation new material with function and provides brand-new thinking.
Polyimides is widely used in the fields such as electricity, light, magnetic in recent years.In addition, with good light, electrical property triphen Amine derivant is widely used in organic photoelectric field as optical conductor, hole mobile material and luminescent material, therefore many Compound or polymer containing fluorine-triphenylamine structure are developed.Liu Guisheng teaches seminar (Novel high- performance polymer memory devices containing(OMe)2tetraphenyl‐p‐ Phenylenediamine moieties, J.Polym.Sci., Part A:Polym.Chem., 2011,49,3709) to triphen The polyimides of amine structure has done correlative study work.But up to the present, the research for polymer photoelectric material collects more In in linear polymeric material, contain a large amount of aromatic rings in molecular backbone under normal circumstances, the dissolubility of polymer can be caused very poor.
The content of the invention
Hyperbranched poly- virtue has preferable solubility property, in synthesis of super branched polymer, has substantial amounts of functional group Retained.These functional groups are distributed in the outer layer of molecule, these functional groups can be utilized further to have spy with other The photoelectricity radical reaction of different structure or performance, can be realized electrical to polymer light by the species and quantity that control end-capping group The regulation and control of energy.In order to solve existing polyimides existing many defects when as photoelectric material, realize to polyimides The regulation and control of photoelectric properties, the invention provides a kind of Triamine monomer for being used to prepare terminated hyperbranched polyimides, IUPAC names For：N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine；Its molecular formula It is as follows：
The Triamine monomer synthetic route is as follows：
The Triamine monomer preparation method comprises the following steps that：
Step 1: according to mol ratio it is (1.1~1.5) by P-nethoxyaniline, p-fluoronitrobenzene and triethylamine:1:(1.2 ~1.5) feed intake, using DMF as solvent, 80~85 DEG C of reactions 64~72 under mechanical agitation and nitrogen protection Hour, discharge in frozen water, deionized water is washed to filtrate achromaticity and clarification, 60~80 DEG C of dryings of vacuum drying oven, Zhi Houyong repeatedly Absolute methanol recrystallizes, and obtains crocus needle crystals 4- methoxyl group -4'- nitrodiphenylamines；
Step 2: be solvent by anhydrous o-dichlorohenzene, a tribromo-benzene, 4- methoxyl group -4'- nitrodiphenylamines, potassium carbonate, copper Powder and 18- crown- 6- ethers in molar ratio 1:(4.2~4.5):(12~14):(6~8):(0.3~0.6) is fed intake, and mechanical agitation is protected 160~180 DEG C are reacted 24~32 hours under shield atmosphere；Copper powder is removed, is discharged in absolute methanol, absolute methanol washing, vacuum 50~70 DEG C of dryings of baking oven, afterwards with petroleum ether and dichloromethane in molar ratio 1:1 is made into solvent, and column chromatography obtains Chinese red Solid, N, N', N "-three-(4- nitro-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine；
Step 3: with tetrahydrofuran and ethanol in molar ratio (1~3):1 is used as solvent for mixing, by N, N', N "-three- (4- nitro-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine and palladium/carbon, which are added in solvent, to be heated back Stream, was added dropwise hydrazine hydrate in 1~2 hour, continues reaction after being added dropwise 8~12 hours, removed palladium/carbon and solvent, with Ethyl acetate and dichloromethane in molar ratio 1:1 is made into solvent, column chromatography obtain target product N, N', N "-three-(4- amino- Phenyl)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine.
Wherein, the effective mass fraction of palladium is more than 10% in the palladium/carbon, with palladium/carbon described in the cubage of palladium Molal quantity；N, N', N "-three-(4- nitro-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine, tetrahydrochysene The mol ratio of furans and alcohol mixed solvent, hydrazine hydrate and palladium/carbon is 1:(150~200):(8~12):(0.04~0.06).
Described Triamine monomer can be used for further preparing the A with acid anhydrides end-blocking, amido end-blocking2+B3The hyperbranched polyamides of type The A of imines or acid anhydrides end-blocking2+B2+B3Type is copolymerized super-branched polyimide.
Wherein, the A of acid anhydrides end-blocking2+B3The structural formula of type super-branched polyimide is
Wherein, n is chain hop count, and has 2<n<200；R is
X is
The A of acid anhydrides end-blocking2+B3The preparation method of type super-branched polyimide is as follows：
Dianhydride is dissolved in DMA or metacresol and forms two anhydride solutions, at room temperature by N, N', N "- Three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine is dissolved in DMA Middle formation triamine solution, triamine solution was slowly added into two anhydride solution in 1~2 hour, after completion of dropwise addition, nitrogen The lower stirring at normal temperature of protection 12~24 hours,
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain the A of acid anhydrides end-blocking2+B3The over-expense of type Change polyimides；
Wherein, the N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine is 1 with dianhydride mol ratio:2, triethylamine and acetic anhydride volume ratio are (1~2):3；The dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), any one in 1,4,5,8 naphthalenetetracarboxylic acid dianhydride (NPDA) or tetracarboxylic acid dianhydride (PTCDA).
The A of the amido end-blocking2+B3The structural formula of type super-branched polyimide is：
Wherein, n is chain hop count, and has 2<n<200；R is
X is
The A of amido end-blocking2+B3The preparation method of type super-branched polyimide is as follows：
At room temperature by N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- Benzene triamine, which is dissolved in DMA, forms triamine solution, and dianhydride is dissolved in into DMA or metacresol Two anhydride solutions of middle formation, two anhydride solutions were slowly added into the triamine solution in 1~2 hour, after completion of dropwise addition, nitrogen The lower stirring at normal temperature of protection 12~24 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain A2+B3Type amido blocks hyperbranched Polyimides；
The N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine It is 1 with dianhydride mol ratio:1, triethylamine and acetic anhydride volume ratio are (1~2):3；The dianhydride is biphenyl dianhydride (BPDA), list Ether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1, Any one in 4,5,8- naphthalenetetracarbacidic acidics dianhydride (NPDA) or tetracarboxylic acid dianhydride (PTCDA).
The A of acid anhydrides end-blocking2+B2+B3The structural formula of type copolymerization super-branched polyimide is as follows：
Wherein, n is chain hop count (2<n<200)；R3For
R2For
X is
The A of acid anhydrides end-blocking2+B2+B3The preparation method of type copolymerization super-branched polyimide is as follows：
Using DMA as solvent, by diamines and dianhydride according to mol ratio 1:(2~5) feed intake, nitrogen protection Lower mechanical agitation 6~8 hours, Triamine monomer is dissolved in DMA, is slowly added dropwise anti-to dianhydride and diamines Answer in system, continue reflection 12~20 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain A2+B2+B3The over-expense of type acid anhydrides end-blocking Change polyimides；Diamines, Triamine monomer and dianhydride mol ratio are 1:0.5~2:2~5；Triethylamine and acetic anhydride volume ratio are (1 ~2):3；
Described Triamine monomer is N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl)- 1,3,5- benzene triamines；
The diamines is 4,4'- diaminourea -4 "-methoxyl group triphenylamine and 4,4'- diaminourea -3 ", 5 "-two trifluoromethyls three One kind in aniline；
The dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8 naphthalenetetracarboxylic acid dianhydride (NPDA) or tetracarboxylic acid dianhydride (PTCDA) any one in.
Surpassed with phthalic anhydride, 1,8- naphthalic anhydrides and/or 3,4- dicarboxylic acid anhydride for the end-sealed type of capping monomer The structural formula of branched polyimide is as follows：
Wherein,For
For In any one；
Zero is One or both of.
With the hyperbranched poly that phthalic anhydride, 1,8- naphthalic anhydrides and/or 3,4- dicarboxylic acid anhydride are capping monomer Imido preparation method is as follows：
Triamine monomer and dianhydride monomer are dissolved separately in DMAC N,N' dimethyl acetamide or metacresol solvent and form triamine Solution and two anhydride solutions；
Two anhydride solutions are slowly dropped in triamine solution, the lower mechanical agitation of nitrogen protection 12~20 hours；
Capping monomer is dissolved as solvent using DMA or metacresol, and is added in reaction system, is continued Reaction 8~10 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain with phthalic anhydride, 1,8- naphthalene two Formic anhydride and the super-branched polyimide that 3,4- dicarboxylic acid anhydride are capping monomer.
The Triamine monomer is N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1, 3,5- benzene triamines, it is 1 with dianhydride mol ratio:1；Triethylamine and acetic anhydride volume ratio are (1~2):3；Mole of capping monomer Measure as less than 1/3rd of Triamine monomer；
The dianhydride monomer is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) Any one in (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA)；The capping monomer is phthalic anhydride, One or both of 1,8- naphthalic anhydride and 3,4- dicarboxylic acid anhydride.
Beneficial effect of the present invention：
The invention provides N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3, 5- benzene Triamine monomers and preparation method thereof, and using this Triamine monomer as raw material, synthesized a series of super-branched polyimide polymerizations Thing.The introducing of N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine monomer With good light, the fluorine-triphenylamine structure of electrical property and methoxyl group electron donating group with conjugation stability, with this list The polymer of body synthesis has good photoelectric properties.Have wide practical use in photoelectric material and functional film material field.
Because the molecular structure degree of branching of terminated hyperbranched polyimides prepared in the present invention is high, deposited in intramolecule In the cavity of many Nano grades, using these cavitys, the influential nano-particle of photoelectric properties tool will can be incorporated into In dissaving polymer, be advantageous to the exploitation and application of novel photoelectric functional material.
Brief description of the drawings
Fig. 1 is the nuclear magnetic spectrogram of Triamine monomer；
Fig. 2 is the A of hexafluoro acid anhydrides end-blocking2+B3The nuclear magnetic spectrogram of type super-branched polyimide；
Fig. 3 is A2+B2+B3Type is copolymerized the infrared spectrum of super-branched polyimide, wherein A2For 4,4'- diaminourea -4 "-first Epoxide triphenylamine；
Fig. 4 is A2+B2+B3Type is copolymerized the nuclear magnetic spectrogram of super-branched polyimide, wherein A2For 4,4'- diaminourea -4 "-first Epoxide triphenylamine；
Fig. 5 is A2+B2+B3Type is copolymerized the infrared spectrum of super-branched polyimide, wherein A2For 4,4'- diaminourea -3 ", 5 " - Two trifluoromethyl triphenylamines；
Fig. 6 is A2+B2+B3Type is copolymerized the nuclear magnetic spectrogram of super-branched polyimide, wherein A2For 4,4'- diaminourea -3 ", 5 " - Two trifluoromethyl triphenylamines；
Fig. 7 is nuclear magnetic spectrogram of the phthalic anhydride as the super-branched polyimide of capping monomer；
Fig. 8 is nuclear magnetic spectrogram of the naphthalene anhydride as the super-branched polyimide of capping monomer；
Fig. 9 is the A of hexafluoro acid anhydrides end-blocking2+B3The uv-vis spectra of type super-branched polyimide.
Figure 10 is A2+B2+B3Type is copolymerized the uv-vis spectra of super-branched polyimide, wherein A2For 4,4'- diaminourea- 4 "-methoxyl group triphenylamine, content 30%；
Figure 11 is A2+B2+B3Type is copolymerized the uv-vis spectra of super-branched polyimide, wherein A2For 4,4'- diaminourea- 3 ", 5 "-two trifluoromethyl triphenylamines, content 30%；
Figure 12 is uv-vis spectra of the naphthalene anhydride as the super-branched polyimide of capping monomer.
Embodiment
Technical solution of the present invention is further explained and illustrated in a manner of specific embodiment below.
Embodiment 1
N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine, it is tied Structure formula is as follows：
Its synthetic method is broadly divided into three steps, and its reaction scheme is as follows：
The first step is reacted：By P-nethoxyaniline, p-fluoronitrobenzene and triethylamine according to mol ratio be 1.1:1:1.2 (first To be excessively used, ratio maximum magnitude is 1.1~1.5 for epoxide aniline and triethylamine:1:1.2~1.5) feed intake, with dimethyl methyl Acid amides (DMF) is solvent, and 80~85 DEG C are reacted 64~72 hours under mechanical agitation and nitrogen protection, are discharged in frozen water, are gone Ionized water washs 4~5 times repeatedly, until filtrate achromaticity and clarification, 80 DEG C of dryings of vacuum drying oven, is recrystallized afterwards with absolute methanol, Obtain crocus needle crystals 4- methoxyl group -4'- nitrodiphenylamines；
Second step reacts：Using anhydrous o-dichlorohenzene as solvent, tribromo-benzene, 4- methoxyl group -4'- nitrodiphenylamines, carbon by between Sour potassium, copper powder and 18- crown- 6- ethers in molar ratio 1:4.2:12:6:0.3 (the mol ratio maximum magnitude be 1:4.2~4.5:12 ~14:6~8:0.3~0.6) feed intake, lower 160~180 DEG C of mechanical agitation nitrogen protection is reacted 24~32 hours, is filtered to remove copper Powder, discharge in absolute methanol, absolute methanol washs 5~6 times repeatedly, 50~70 DEG C of dryings of vacuum drying oven, afterwards with petroleum ether With dichloromethane in molar ratio 1:1 is made into solvent, and column chromatography obtains Chinese red solid, N, N', N "-three-(4- nitros-benzene Base)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine；
Three-step reaction：With tetrahydrofuran and ethanol in molar ratio 1~3:1 is used as solvent for mixing, by N, N', N "-three- (4- nitro-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine and palladium/carbon, which are added in solvent, to be heated back Stream, was added dropwise hydrazine hydrate in 1~2 hour, continues reaction after being added dropwise 8~12 hours, removed palladium/carbon and solvent, with Ethyl acetate and dichloromethane in molar ratio 1:1 is made into solvent, column chromatography obtain target product N, N', N "-three-(4- amino- Phenyl)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine.
Wherein, the effective mass fraction of palladium is 10% in palladium/carbon, with the molal quantity of palladium/carbon described in the cubage of palladium；N, N', N "-three-(4- nitro-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine, tetrahydrofuran and ethanol Mixed solvent, hydrazine hydrate, the mol ratio of palladium/carbon are 1:180:9:0.04 (mol ratio maximum magnitude be 1:150~200:8~12: 0.04~0.06).
Embodiment 2
With N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine are Reaction raw materials, prepare the A with acid anhydrides end-blocking and amido end-blocking2+B3Type super-branched polyimide；
The A of the acid anhydrides end-blocking2+B3Its structural formula of type super-branched polyimide is as follows：
Wherein, n is chain hop count (2<n<200)；R is
X is
The A2+B3The synthetic method of super-branched polyimide polymer of type acid anhydrides end-blocking is：
Dianhydride is dissolved in DMA or metacresol, forms two anhydride solutions, at room temperature by N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine is dissolved in N, N- dimethylacetamides In amine, the solution of formation was slowly added into 1~2 hour in two anhydride solution, after completion of dropwise addition, the lower normal temperature of nitrogen protection Stirring 12~24 hours,
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed 4~5 times with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain the A of acid anhydrides end-blocking2+B3Type Super-branched polyimide；
Wherein, the N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine is 1 with dianhydride mol ratio:2, triethylamine and acetic anhydride volume ratio are 1:3 (ratio maximum can be 2:3)；The dianhydride is connection Benzene dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), equal benzene four Any one in formic anhydride (PMDA), 1,4,5,8 naphthalenetetracarboxylic acid dianhydride (NPDA) and tetracarboxylic acid dianhydride (PTCDA).Fig. 2 For the nuclear magnetic spectrogram of the super-branched polyimide of hexafluorodianhydride (6FDA) end-blocking.
Embodiment 3
With N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine are Reaction raw materials, prepare the A of amido end-blocking2+B3Type super-branched polyimide.
The A of the amido end-blocking2+B3The structural formula of type super-branched polyimide is：
Wherein, n is chain hop count (2<n<200)；R is
X is
The A2+B3The building-up process of super-branched polyimide polymer of type amido end-blocking is：
At room temperature by N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- Benzene triamine is dissolved in DMA, forms triamine solution, dianhydride is dissolved in into DMA or a first In phenol, two anhydride solutions are formed, two anhydride solutions were slowly added into the triamine solution in 1~2 hour, after completion of dropwise addition, The lower stirring at normal temperature of nitrogen protection 12~24 hours,
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed 4~5 times with absolute ethyl alcohol, be filtered dry after 80 DEG C of vacuum drying, obtain A2+B3Type amido blocks hyperbranched Polyimides；
The N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine It is 1 with dianhydride mol ratio:1, triethylamine and acetic anhydride volume ratio are 1:3 (ratio maximum can be 2:3)；
The dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8 naphthalenetetracarboxylic acid dianhydride (NPDA) or tetracarboxylic acid dianhydride (PTCDA) any one in.
Embodiment 4
With Triamine monomer (N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- Benzene triamine), diamine monomer and dianhydride monomer are raw material, prepare the A of acid anhydrides end-blocking2+B2+B3Type is copolymerized super-branched polyimide；
Described A2+B2+B3Its structure of type copolymerization super-branched polyimide is as follows：
Wherein, n is chain hop count (2<n<200)；R3For
R2For
X is
The A of described acid anhydrides end-blocking2+B2+B3Type copolymerization super-branched polyimide its building-up process is：
Using DMA as solvent, by diamines and dianhydride according to mol ratio 1:2~5 feed intake, under nitrogen protection Mechanical agitation 6~8 hours；
Triamine monomer is dissolved in DMA, is slowly added dropwise into dianhydride and diamine reactant system, after Continuous reaction 12~20 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed 4~5 times with absolute ethyl alcohol, be filtered dry after 80 DEG C of vacuum drying, obtain A2+B2+B3Type acid anhydrides end-blocking surpasses Branched polyimide；
Wherein, diamines, Triamine monomer and dianhydride mol ratio are 1:0.5~2:2~5；Triethylamine and acetic anhydride volume ratio are 1:3 (maximum ratio can be 2:3)；
Described Triamine monomer is N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl)- 1,3,5- benzene triamines；
The diamines is 4,4'- diaminourea -4 "-methoxyl group triphenylamine and 4,4'- diaminourea -3 ", 5 "-two trifluoromethyls three One kind in aniline；
The dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8 naphthalenetetracarboxylic acid dianhydride (NPDA) or tetracarboxylic acid dianhydride (PTCDA) any one in.
Fig. 3 is A2+B2+B3Type is copolymerized the infrared spectrum of super-branched polyimide, wherein A2For 4,4'- diaminourea -4 "-first Epoxide triphenylamine；Fig. 4 is A2+B2+B3Type is copolymerized the nuclear magnetic spectrogram of super-branched polyimide, wherein A2For 4,4'- diaminourea -4 " - Methoxyl group triphenylamine；Fig. 5 is A2+B2+B3Type is copolymerized the infrared spectrum of super-branched polyimide, wherein A2For 4,4'- diaminourea- 3 ", 5 "-two trifluoromethyl triphenylamines；Fig. 6 is A2+B2+B3Type is copolymerized the nuclear magnetic spectrogram of super-branched polyimide, wherein A2For 4, 4'- diaminourea -3 ", 5 "-two trifluoromethyl triphenylamines.
Embodiment 5
With Triamine monomer (N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-benzene in the present embodiment Base) -1,3,5- benzene triamines) with dianhydride monomer be raw material, prepare with phthalic anhydride, 1,8- naphthalic anhydrides and/or 3,4- Dicarboxylic acid anhydride is the end-sealed type super-branched polyimide of capping monomer；
Described its structural formula of end-sealed type super-branched polyimide is：
Wherein,For
For In any one；
Zero is One or both of.
Described its building-up process of end-sealed type super-branched polyimide is：
Triamine monomer and dianhydride monomer are dissolved separately in DMAC N,N' dimethyl acetamide or metacresol solvent and obtain triamine Solution and two anhydride solutions, two anhydride solutions are slowly dropped in triamine solution, the lower mechanical agitation of nitrogen protection 12~20 hours,
Capping monomer is dissolved as solvent using DMA or metacresol, and is added in reaction system, is continued Reaction 8~10 hours,
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in nothing In water-ethanol, washed 4~5 times with absolute ethyl alcohol, be filtered dry and be dried in vacuo 4~8 hours after 80 DEG C, obtained with phthalic acid Acid anhydride, 1,8- naphthalic anhydride and 3,4- dicarboxylic acid anhydride are the super-branched polyimide of capping monomer.
The Triamine monomer (N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3, 5- benzene triamine) with dianhydride mol ratio be 1:1, triethylamine and acetic anhydride volume ratio are 1:3 (ratio maximum can be 2:3)；End-blocking is single The mole of body is 1/3rd of Triamine monomer；
The dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA) Any one in (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA)；The capping monomer be phthalic anhydride, One or both of 1,8- naphthalic anhydride and 3,4- dicarboxylic acid anhydride.
Fig. 7 is nuclear magnetic spectrogram of the phthalic anhydride as the super-branched polyimide of capping monomer；Fig. 8 is naphthalene anhydride as capping monomer Super-branched polyimide nuclear magnetic spectrogram.
Add triethylamine and acetic anhydride in above example to use as catalyst, those skilled in the art can basis The situation that reaction is carried out determines usage amount with reference to existing polyimides synthetic method.
Compliance test result
The A of hexafluoro acid anhydrides end-blocking as shown in Figure 92+B3The uv-vis spectra of type super-branched polyimide, absorption maximum Peak belongs to the π-π of aromatic ring in polyimide molecule structure near 300nm*Transition.It can also be originated from absorption spectrum Absorbing wavelength (λ onset) is 387nm, then, pass through formula：Eg opt=1240/ λ onset calculate optical band gap (Eg opt) be 3.20eV。
Maximum absorption band belongs to the π-π of aromatic ring in polyimide molecule structure near 300nm as shown in Figure 10*Jump Move.It is 401nm that initial absorption wavelength (λ onset) can also be obtained from absorption spectrum, then, optical band gap (Eg opt) pass through public affairs Formula：Eg opt=1240/ λ onset calculate optical band gap (Eg opt) it is 3.09eV.
Maximum absorption band belongs to the π-π of aromatic ring in polyimide molecule structure near 300nm as shown in Figure 11*Jump Move.It is 405nm that initial absorption wavelength (λ onset) can also be obtained from absorption spectrum, then, optical band gap (Eg opt) pass through public affairs Formula：Eg opt=1240/ λ onset calculate optical band gap (Eg opt) it is 3.06eV.
Maximum absorption band belongs to the π-π of aromatic ring in polyimide molecule structure near 300nm as shown in Figure 12*Jump Move.It is 390nm that initial absorption wavelength (λ onset) can also be obtained from absorption spectrum, then, optical band gap (Eg opt) pass through public affairs Formula：Eg opt=1240/ λ onset calculate optical band gap (Eg opt) it is 3.18eV.
As can be seen that the generation of the super-branched polyimide uv atlas of copoly type and end-sealed type is red from uv atlas Move, because diamine monomer and capping monomer introduce the interaction added between phenyl ring, improve conjugated degree increasing； Conjugated degree is bigger, π and π*Energy difference it is just smaller, namely optical band gap is smaller；Therefore, diamine monomer and end-blocking are introduced Monomer can increase the conjugated degree of polymeric system, and the regulation and control for polymer light electrical property provide new method.

Claims (5)

1. a kind of terminated hyperbranched polyimides applied to photoelectric field, it is characterised in that the terminated hyperbranched polyamides is sub- Amine is selected from
The A of acid anhydrides end-blocking2+B3Type super-branched polyimide, its structure are formula (I)；
The A of amido end-blocking2+B3Type super-branched polyimide, its structure are formula (II)；
The A of acid anhydrides end-blocking2+B2+B3Type is copolymerized super-branched polyimide, and its structure is formula (III)；
It is hyperbranched for the end-sealed type of capping monomer with phthalic anhydride, 1,8- naphthalic anhydrides and/or 3,4- dicarboxylic acid anhydride Polyimides, its structure are one kind in formula (IV)；
In formula (I), (II), n is chain hop count, and has 2<n<200；R is
In formula (III), n is chain hop count, and 2<n<200；R3For
R in formula (III)2For
X in formula (I), (II) and (III) is
In formula (IV),For
In formula (IV),For
In any one；
In formula (IV), zero is
One or both of.
A kind of 2. A of acid anhydrides end-blocking according to claim 12+B3The preparation method of type super-branched polyimide, specific step It is rapid as follows：
Dianhydride is dissolved in DMA or metacresol and forms two anhydride solutions, at room temperature by N, N', N "-three- (4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine is dissolved in shape in DMA Into triamine solution, triamine solution was slowly added into two anhydride solution in 1~2 hour, after completion of dropwise addition, protective atmosphere Lower stirring at normal temperature 12~24 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in anhydrous second In alcohol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain the A of acid anhydrides end-blocking2+B3The hyperbranched poly of type Acid imide；
Wherein, the N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine It is 1 with dianhydride mol ratio:2, triethylamine and acetic anhydride volume ratio are (1~2):3；The dianhydride be biphenyl dianhydride, monoether dianhydride, In diphenyl sulfone dianhydride, hexafluorodianhydride (6FDA), ketone acid anhydride, pyromellitic dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride or tetracarboxylic acid dianhydride Any one.
A kind of 3. A of amido end-blocking according to claim 12+B3The preparation method of type super-branched polyimide, specific step It is rapid as follows：At room temperature by N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene Triamine, which is dissolved in DMA, forms triamine solution, and dianhydride is dissolved in into DMA or metacresol In, two anhydride solutions are formed, two anhydride solutions were slowly added into the triamine solution in 1~2 hour, after completion of dropwise addition, are protected Protect stirring at normal temperature 12~24 hours under atmosphere；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in anhydrous second In alcohol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain A2+B3The hyperbranched polyamides of type amido end-blocking Imines；
The N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- benzene triamine and two Acid anhydride mol ratio is 1:1, triethylamine and acetic anhydride volume ratio are 1~2:3；The dianhydride is biphenyl dianhydride, monoether dianhydride, diphenyl sulphone (DPS) It is any one in dianhydride, hexafluorodianhydride (6FDA), ketone acid anhydride, pyromellitic dianhydride, 1,4,5,8 naphthalenetetracarboxylic acid dianhydride or tetracarboxylic acid dianhydride Kind.
A kind of 4. A of acid anhydrides end-blocking according to claim 12+B2+B3Type is copolymerized the preparation method of super-branched polyimide, Comprise the following steps that：Using DMA as solvent, by diamines and dianhydride according to mol ratio 1:(2~5) feed intake, protection Mechanical agitation 6~8 hours, Triamine monomer is dissolved in DMA under atmosphere, is slowly added dropwise to dianhydride and two In amine reaction system, continue reflection 12~20 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in anhydrous second In alcohol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain A2+B2+B3The hyperbranched poly of type acid anhydrides end-blocking Acid imide；Diamines, Triamine monomer and dianhydride mol ratio are 1:(0.5~2):(2~5)；Triethylamine and acetic anhydride volume ratio are (1 ~2):3；
The diamines is 4,4'- diaminourea -4 "-methoxyl group triphenylamine and 4,4'- diaminourea -3 ", 5 "-two trifluoromethyl triphenylamines In one kind；
The dianhydride is biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride (6FDA), ketone acid anhydride, pyromellitic dianhydride, 1,4,5, Any one in 8- naphthalenetetracarbacidic acidics dianhydride or tetracarboxylic acid dianhydride.
It is 5. a kind of according to claim 1 with phthalic anhydride, 1,8- naphthalic anhydrides and/or 3,4- dicarboxylic acid anhydride For the preparation method of the end-sealed type super-branched polyimide of capping monomer, comprise the following steps that：
Triamine monomer and dianhydride monomer are dissolved separately in DMAC N,N' dimethyl acetamide or metacresol solvent and form triamine solution With two anhydride solutions；
Two anhydride solutions are slowly dropped in triamine solution, mechanical agitation 12~20 hours under protective atmosphere；
Capping monomer is dissolved as solvent using DMA or metacresol, and is added in reaction system, continues reaction 8 ~10 hours；
Triethylamine and acetic anhydride are added, 60~80 DEG C is heated to and reacts 6~8 hours, obtain polymer solution, discharge in anhydrous second In alcohol, washed with absolute ethyl alcohol, be filtered dry after 80~100 DEG C of vacuum drying, obtain with phthalic anhydride, 1,8- naphthalenedicarboxylic acid Acid anhydride and/or the super-branched polyimide that 3,4- dicarboxylic acid anhydride are capping monomer；
The Triamine monomer is N, N', N "-three-(4- methanesulfonylamino-phenyls)-N, N', N "-three-(4- methoxyl groups-phenyl) -1,3,5- Benzene triamine, it is 1 with dianhydride mol ratio:1；Triethylamine and acetic anhydride volume ratio are (1~2):3；The mole of capping monomer is Less than/3rd of Triamine monomer；
The dianhydride monomer is in biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride (6FDA), ketone acid anhydride, pyromellitic dianhydride Any one；The capping monomer is phthalic anhydride, 1,8- naphthalic anhydride and one kind in 3,4- dicarboxylic acid anhydride or Two kinds.
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