CN105566127A - Triamine monomer and preparation method and application thereof - Google Patents
Triamine monomer and preparation method and application thereof Download PDFInfo
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- CN105566127A CN105566127A CN201610117522.9A CN201610117522A CN105566127A CN 105566127 A CN105566127 A CN 105566127A CN 201610117522 A CN201610117522 A CN 201610117522A CN 105566127 A CN105566127 A CN 105566127A
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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
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- 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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Abstract
The invention discloses a triamine monomer and a preparation method and application thereof. The triamine monomer provided by the invention is N,N',N''-tri-(4-amino-phenyl)-N,N',N''-tri-(4-methoxy-phenyl)-1,3,5-phenyltriamine. The synthesis method is divided into reactions of three steps and comprises the steps: firstly, preparing 4-methoxy-4'-nitrodiphenylamine from p-methoxyaniline and p-fluoronitrobenzene, and then, preparing N,N',N''-tri-(4-nitro-phenyl)-N,N',N''-tri-(4-methoxy-phenyl)-1,3,5-phenyltriamine from 4-methoxy-4'-nitrodiphenylamine and 1,3,5-tribromobenzene; finally, subjecting N,N',N''-tri-(4-nitro-phenyl)-N,N',N''-tri-(4-methoxy-phenyl)-1,3,5-phenyltriamine to a reaction with palladium-on-carbon and hydrazine hydrate, thereby preparing the target triamine monomer. According to the application of the triamine monomer, terminated hyperbranched polyimide can be prepared by taking the triamine monomer as a core, and the regulation and control on photoelectric properties of polyimide can be achieved through controlling types and quantity of terminating groups, so that the development and application of novel photoelectric functional materials are facilitated.
Description
Technical field
The invention belongs to technical field of polymer materials.
Background technology
Polyimide material is due to its various route of synthesis, and good mechanical property, excellent resistance to gentle chemical resistance, some row advantages such as outstanding dielectric properties and comparatively simple complete processing, cause the attention of polymer material science circle.Under the effort of several generations scholar, polyimide material is widely used in space flight, aviation, the high-tech areas such as microelectronics.Due to over-all properties and the very strong molecular structure designability of its excellence, in the research of the photoelectric functional material in nearly ten years, polyimide material is a dark horse.
Hyperbranched polymer can be described as the polymer with high levels of three-dimensional branched structure, and he is both different from branched polymer, also has any different with dendritic molecule.Near rise during the last ten years and the highly branched three-dimensional molecular structure becoming that the super-branched polyimide of the study hotspot of scientists extensive concern has very soon, good solubility energy, low solution viscosity, without features such as chain entanglements, simultaneously, the macromolecular chain periphery of hyperbranched polymer three-dimensional structure, containing a large amount of end group, is developed novel material provide brand-new thinking by being turned to the further chemical modification of end group and function.
Polyimide is widely used in the fields such as electricity, light, magnetic in recent years.In addition, have good optical, electrical performance triphenylamine analog derivative and be widely used in organic photoelectric field by as optical conductor, hole mobile material and luminescent material, therefore many compounds containing fluorine-triphenylamine structure or polymkeric substance are developed.The raw teach problem group of Liu Gui (Novelhigh ?performancepolymermemorydevicescontaining (OMe)
2tetraphenyl ?p ?phenylenediaminemoieties, J.Polym.Sci., PartA:Polym.Chem., 2011,49,3709) correlative study work has been done to the polyimide of fluorine-triphenylamine structure.But up to the present, the research for polymer photoelectric material focuses mostly in linear polymeric material, contain a large amount of aromatic ring in molecular backbone chain under normal circumstances, structure adaptability can be caused very poor.
Summary of the invention
Hyperbranched poly-virtue has good solubility property, when synthesis of super branched polymkeric substance, has a large amount of functional groups and is retained.These functional groups are distributed in the skin of molecule, and these functional groups can be utilized with other to have the photoelectricity radical reaction of special construction or performance further, can realize the regulation and control to Polymer Optoelectronic performance by the kind and quantity controlling capping group.In order to solve existing polyimide as the many defects existed during photoelectric material, realize the regulation and control to polyimide photoelectric properties, the invention provides a kind of Triamine monomer for the preparation of terminated hyperbranched polyimide, IUPAC called after: N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N'; N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines; Its molecular formula is as follows:
Described Triamine monomer synthetic route is as follows:
Described Triamine monomer preparation method concrete steps are as follows:
Step one, be (1.1 ~ 1.5) by P-nethoxyaniline, p-fluoronitrobenzene and triethylamine according to mol ratio: 1:(1.2 ~ 1.5) feed intake, with N, dinethylformamide is solvent, under mechanical stirring and nitrogen protection, 80 ~ 85 DEG C are reacted 64 ~ 72 hours, discharging is in frozen water, deionized water repetitive scrubbing is to filtrate achromaticity and clarification, vacuum drying oven 60 ~ 80 DEG C of dryings, use anhydrous methanol recrystallization afterwards, obtain safran needle crystals 4-methoxyl group-4'-nitrodiphenylamine;
Step 2, be solvent by anhydrous orthodichlorobenzene, between tribromo-benzene, 4-methoxyl group-4'-nitrodiphenylamine, salt of wormwood, copper powder and 18-be preced with-6-ether 1:(4.2 ~ 4.5 in molar ratio): (12 ~ 14): (6 ~ 8): (0.3 ~ 0.6) feeds intake, under mechanical stirring protective atmosphere 160 ~ 180 DEG C reaction 24 ~ 32 hours; Removing copper powder, discharging is in anhydrous methanol, and anhydrous methanol washs, vacuum drying oven 50 ~ 70 DEG C of dryings, afterwards with sherwood oil and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains orange solid, N, N'; N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1; 3,5-benzene triamine;
Step 3, using tetrahydrofuran (THF) and ethanol in molar ratio (1 ~ 3): 1 for mixing is as solvent, by N, N', N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine and palladium/carbon add reflux in solvent, dropwise hydrazine hydrate is added in 1 ~ 2 hour, dropwise rear continuation reaction 8 ~ 12 hours, removing palladium/carbon and solvent, with ethyl acetate and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains target product N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine.
Wherein, in described palladium/carbon, the virtual mass mark of palladium is more than 10%, with the mole number of palladium/carbon described in the cubage of palladium; N, N'; N "-three-(4-nitro-phenyl)-N, N'; N "-three-(4-methoxyl group-phenyl)-1, the mol ratio of 3,5-benzene triamine, tetrahydrofuran (THF) 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 preparation further and has the A of acid anhydrides end-blocking, amido end-blocking
2+ B
3the A of type super-branched polyimide or acid anhydrides end-blocking
2+ B
2+ B
3type copolymerization super-branched polyimide.
Wherein, the A of acid anhydrides end-blocking
2+ B
3the 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-blocking
2+ B
3the preparation method of type super-branched polyimide is as follows:
Dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol and forms two anhydride solutions, at room temperature by N; N', N "-three-(4-methanesulfonylamino-phenyl)-N, N'; N "-three-(4-methoxyl group-phenyl)-1; 3,5-benzene triamine is dissolved in N,N-dimethylacetamide and forms triamine solution; triamine solution was slowly joined in 1 ~ 2 hour in described two anhydride solutions; after dropping terminates, stirring at normal temperature 12 ~ 24 hours under nitrogen protection
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains the A of acid anhydrides end-blocking
2+ B
3the super-branched polyimide of type;
Wherein, described N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines and dianhydride mol ratio be 1:2, triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3; Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (any one in NPDA) Huo perylene tetracarboxylic acid dianhydride (PTCDA).
The A of described amido end-blocking
2+ B
3the 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-blocking
2+ B
3the preparation method of type super-branched polyimide is as follows:
At room temperature by N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N'; N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines are dissolved in N, triamine solution is formed in N-N,N-DIMETHYLACETAMIDE, dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol and forms two anhydride solutions, two anhydride solutions were slowly joined in described triamine solution in 1 ~ 2 hour, after dropping terminates, stirring at normal temperature 12 ~ 24 hours under nitrogen protection;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
3the super-branched polyimide of type amido end-blocking;
Described N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines and dianhydride mol ratio be 1:1, triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3; Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (any one in NPDA) Huo perylene tetracarboxylic acid dianhydride (PTCDA).
The A of acid anhydrides end-blocking
2+ B
2+ B
3the structural formula of type copolymerization super-branched polyimide is as follows:
Wherein, n is chain hop count (2<n<200); R
3for
R
2for
X is
The A of acid anhydrides end-blocking
2+ B
2+ B
3the preparation method of type copolymerization super-branched polyimide is as follows:
With N, N-N,N-DIMETHYLACETAMIDE is solvent, by diamines and dianhydride according to mol ratio 1:(2 ~ 5) feed intake, mechanical stirring 6 ~ 8 hours under nitrogen protection, Triamine monomer is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, slowly drop in dianhydride and diamine reactant system, continue reflection 12 ~ 20 hours;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
2+ B
3the super-branched polyimide of type acid anhydrides end-blocking; Diamines, Triamine monomer and dianhydride mol ratio are 1:0.5 ~ 2:2 ~ 5; Triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3;
Described Triamine monomer is N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines;
Described diamines is 4,4'-diamino-4 "-methoxyl group triphenylamine and 4,4'-diamino-3 ", 5 " and one in-two trifluoromethyl triphenylamines;
Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (any one in NPDA) Huo perylene tetracarboxylic acid dianhydride (PTCDA).
Be that the structural formula of the end-sealed type super-branched polyimide of capping monomer is as follows with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and/or 3,4-perylene dicarboxylic acid anhydride:
Wherein,
for
for
in any one;
Zero is
in one or both.
Be that the preparation method of the super-branched polyimide of capping monomer is as follows with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and/or 3,4-perylene dicarboxylic acid anhydride:
Triamine monomer and dianhydride monomer are dissolved in N,N-dimethylacetamide or meta-cresol solvent respectively and form triamine solution and two anhydride solutions;
Two anhydride solutions are slowly added drop-wise in triamine solution, mechanical stirring 12 ~ 20 hours under nitrogen protection;
With N,N-dimethylacetamide or meta-cresol for dissolution with solvents capping monomer, and join in reaction system, continue reaction 8 ~ 10 hours;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtain with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride are the super-branched polyimide of capping monomer.
Described Triamine monomer is N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines, itself and dianhydride mol ratio are 1:1; Triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3; The molar weight of capping monomer is less than 1/3rd of Triamine monomer;
Described dianhydride monomer is any one in biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA); Described capping monomer is Tetra hydro Phthalic anhydride, one or both in 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride.
Beneficial effect of the present invention:
The invention provides N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene Triamine monomer and preparation method thereof, and with this Triamine monomer for raw material, synthesized a series of super-branched polyimide polymkeric substance.N, N'; N "-three-(4-methanesulfonylamino-phenyl)-N, N'; N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene Triamine monomer introduce the fluorine-triphenylamine structure with good optical, electrical performance and the methoxyl group electron-donating group with conjugation stability, with the polymkeric substance of this monomer synthesize, there are good photoelectric properties.Have wide practical use at photoelectric material and functional film material field.
Because the molecular structure degree of branching of terminated hyperbranched polyimide prepared in the present invention is high, the cavity of many Nano grades is there is at intramolecule, utilize these cavitys, by being incorporated in hyperbranched polymer to the influential nanoparticle of photoelectric properties tool, the development & application of novel photoelectric functional materials can be conducive to.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of Triamine monomer;
Fig. 2 is the A of hexafluoro acid anhydrides end-blocking
2+ B
3the nuclear magnetic spectrogram of type super-branched polyimide;
Fig. 3 is A
2+ B
2+ B
3the infrared spectrum of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-4 "-methoxyl group triphenylamine;
Fig. 4 is A
2+ B
2+ B
3the nuclear magnetic spectrogram of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-4 "-methoxyl group triphenylamine;
Fig. 5 is A
2+ B
2+ B
3the infrared spectrum of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-3 ", 5 "-two trifluoromethyl triphenylamines;
Fig. 6 is A
2+ B
2+ B
3the nuclear magnetic spectrogram of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-3 ", 5 "-two trifluoromethyl triphenylamines;
Fig. 7 is the nuclear magnetic spectrogram of phthalic anhydride as the super-branched polyimide of capping monomer;
Fig. 8 is the nuclear magnetic spectrogram of naphthalene acid anhydride as the super-branched polyimide of capping monomer;
Fig. 9 is the A of hexafluoro acid anhydrides end-blocking
2+ B
3the uv-vis spectra of type super-branched polyimide.
Figure 10 is A
2+ B
2+ B
3the uv-vis spectra of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-4 "-methoxyl group triphenylamine, content is 30%;
Figure 11 is A
2+ B
2+ B
3the uv-vis spectra of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-3 ", 5 "-two trifluoromethyl triphenylamines, content is 30%;
Figure 12 is the uv-vis spectra of naphthalene acid anhydride as the super-branched polyimide of capping monomer.
Embodiment
In the mode of specific embodiment technical solution of the present invention be further explained below and illustrate.
Embodiment 1
N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines, its structural formula is as follows:
Its synthetic method is mainly divided into three steps, and its reaction scheme is as follows:
The first step is reacted: by P-nethoxyaniline, p-fluoronitrobenzene and triethylamine are that (anisidine and triethylamine are excessive use to 1.1:1:1.2 according to mol ratio, ratio maximum range is 1.1 ~ 1.5:1:1.2 ~ 1.5) feed intake, with dimethyl formamide (DMF) for solvent, under mechanical stirring and nitrogen protection, 80 ~ 85 DEG C are reacted 64 ~ 72 hours, discharging is in frozen water, deionized water repetitive scrubbing 4 ~ 5 times, until filtrate achromaticity and clarification, vacuum drying oven 80 DEG C of dryings, use anhydrous methanol recrystallization afterwards, obtain safran needle crystals 4-methoxyl group-4'-nitrodiphenylamine,
Second step reacts: with anhydrous orthodichlorobenzene for solvent, tribromo-benzene between inciting somebody to action, 4-methoxyl group-4'-nitrodiphenylamine, salt of wormwood, copper powder and 18-hat-6-ether in molar ratio 1:4.2:12:6:0.3 (described mol ratio maximum range is 1:4.2 ~ 4.5:12 ~ 14:6 ~ 8:0.3 ~ 0.6) feed intake, under mechanical stirring nitrogen protection, 160 ~ 180 DEG C are reacted 24 ~ 32 hours, cross and filter copper powder, discharging is in anhydrous methanol, anhydrous methanol repetitive scrubbing 5 ~ 6 times, vacuum drying oven 50 ~ 70 DEG C of dryings, afterwards with sherwood oil and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains orange solid, N, N', N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine,
Three-step reaction: using tetrahydrofuran (THF) and ethanol in molar ratio 1 ~ 3:1 for mixing is as solvent, by N, N', N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine and palladium/carbon add reflux in solvent, dropwise hydrazine hydrate is added in 1 ~ 2 hour, dropwise rear continuation reaction 8 ~ 12 hours, removing palladium/carbon and solvent, with ethyl acetate and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains target product N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine.
Wherein, in palladium/carbon, the virtual mass mark of palladium is 10%, with the mole number of palladium/carbon described in the cubage of palladium; N, N'; N "-three-(4-nitro-phenyl)-N, N'; N "-three-(4-methoxyl group-phenyl)-1, the mol ratio of 3,5-benzene triamine, tetrahydrofuran (THF) and alcohol mixed solvent, hydrazine hydrate, palladium/carbon is 1:180:9:0.04 (mol ratio maximum range is 1:150 ~ 200:8 ~ 12:0.04 ~ 0.06).
Embodiment 2
With N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines are reaction raw materials, preparation has the A of acid anhydrides end-blocking and amido end-blocking
2+ B
3type super-branched polyimide;
The A of described acid anhydrides end-blocking
2+ B
3its structural formula of type super-branched polyimide is as follows:
Wherein, n is chain hop count (2<n<200); R is
X is
Described A
2+ B
3the synthetic method of the super-branched polyimide polymkeric substance of type acid anhydrides end-blocking is:
Dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol, forms two anhydride solutions; at room temperature by N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N', N "-three-(4-methoxyl group-phenyl)-1,3; 5-benzene triamine is dissolved in N; in N-N,N-DIMETHYLACETAMIDE, the solution of formation slowly joined in described two anhydride solutions in 1 ~ 2 hour, dripped after terminating; stirring at normal temperature 12 ~ 24 hours under nitrogen protection
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing 4 ~ 5 times, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains the A of acid anhydrides end-blocking
2+ B
3the super-branched polyimide of type;
Wherein, described N, N'; N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1; 3,5-benzene triamine and dianhydride mol ratio are 1:2, and triethylamine and diacetyl oxide volume ratio are 1:3 (ratio is maximum can be 2:3); Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4, (NPDA) is with any one in perylene tetracarboxylic acid dianhydride (PTCDA) for 5,8-naphthalenetetracarbacidic acidic dianhydride.Fig. 2 is the nuclear magnetic spectrogram of the super-branched polyimide of hexafluorodianhydride end-blocking.
Embodiment 3
With N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines are reaction raw materials, prepare the A of amido end-blocking
2+ B
3type super-branched polyimide.
The A of described amido end-blocking
2+ B
3the structural formula of type super-branched polyimide is:
Wherein, n is chain hop count (2<n<200); R is
X is
Described A
2+ B
3the building-up process of the super-branched polyimide polymkeric substance of type amido end-blocking is:
At room temperature by N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N', N "-three-(4-methoxyl group-phenyl)-1,3; 5-benzene triamine is dissolved in N,N-dimethylacetamide, forms triamine solution; dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol, forms two anhydride solutions; two anhydride solutions were slowly joined in described triamine solution in 1 ~ 2 hour; after dropping terminates, stirring at normal temperature 12 ~ 24 hours under nitrogen protection
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing 4 ~ 5 times, in 80 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
3the super-branched polyimide of type amido end-blocking;
Described N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines and dianhydride mol ratio be 1:1, triethylamine and diacetyl oxide volume ratio are 1:3 (ratio is maximum can be 2:3);
Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (any one in NPDA) Huo perylene tetracarboxylic acid dianhydride (PTCDA).
Embodiment 4
With Triamine monomer (N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines), diamine monomer and dianhydride monomer are raw material, prepare the A of acid anhydrides end-blocking
2+ B
2+ B
3type copolymerization super-branched polyimide;
Described A
2+ B
2+ B
3its structure of type copolymerization super-branched polyimide is as follows:
Wherein, n is chain hop count (2<n<200); R
3for
R
2for
X is
The A of described acid anhydrides end-blocking
2+ B
2+ B
3its building-up process of type copolymerization super-branched polyimide is:
Take N,N-dimethylacetamide as solvent, diamines and dianhydride are fed intake according to mol ratio 1:2 ~ 5, mechanical stirring 6 ~ 8 hours under nitrogen protection;
Triamine monomer is dissolved in N,N-dimethylacetamide, slowly drops in dianhydride and diamine reactant system, continue reaction 12 ~ 20 hours;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing 4 ~ 5 times, in 80 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
2+ B
3the super-branched polyimide of type acid anhydrides end-blocking;
Wherein, diamines, Triamine monomer and dianhydride mol ratio are 1:0.5 ~ 2:2 ~ 5; Triethylamine and diacetyl oxide volume ratio are 1:3 (maximum ratio can be 2:3);
Described Triamine monomer is N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines;
Described diamines is 4,4'-diamino-4 "-methoxyl group triphenylamine and 4,4'-diamino-3 ", 5 " and one in-two trifluoromethyl triphenylamines;
Described dianhydride is biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarbacidic acidic dianhydride (any one in NPDA) Huo perylene tetracarboxylic acid dianhydride (PTCDA).
Fig. 3 is A
2+ B
2+ B
3the infrared spectrum of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-4 "-methoxyl group triphenylamine; Fig. 4 is A
2+ B
2+ B
3the nuclear magnetic spectrogram of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-4 "-methoxyl group triphenylamine; Fig. 5 is A
2+ B
2+ B
3the infrared spectrum of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-3 ", 5 "-two trifluoromethyl triphenylamines; Fig. 6 is A
2+ B
2+ B
3the nuclear magnetic spectrogram of type copolymerization super-branched polyimide, wherein A
2be 4,4'-diamino-3 ", 5 "-two trifluoromethyl triphenylamines.
Embodiment 5
With Triamine monomer (N in the present embodiment, N'; N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3; 5-benzene triamine) be raw material with dianhydride monomer; preparing with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and/or 3,4-perylene 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
in one or both.
Described its building-up process of end-sealed type super-branched polyimide is:
Triamine monomer and dianhydride monomer are dissolved in N,N-dimethylacetamide or meta-cresol solvent respectively and obtain triamine solution and two anhydride solutions, two anhydride solutions are slowly added drop-wise in triamine solution, mechanical stirring 12 ~ 20 hours under nitrogen protection,
With N,N-dimethylacetamide or meta-cresol for dissolution with solvents capping monomer, and join in reaction system, continue reaction 8 ~ 10 hours,
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging in dehydrated alcohol, with absolute ethanol washing 4 ~ 5 times, in 80 DEG C of vacuum-dryings 4 ~ 8 hours after being filtered dry, obtain with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride are the super-branched polyimide of capping monomer.
Described Triamine monomer (N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamine) with dianhydride mol ratio be 1:1, triethylamine and diacetyl oxide volume ratio are 1:3 (ratio is maximum can be 2:3); The molar weight of capping monomer is 1/3rd of Triamine monomer;
Described dianhydride is any one in biphenyl dianhydride (BPDA), monoether dianhydride (ODPA), diphenyl sulfone dianhydride (DSDA), hexafluorodianhydride (6FDA), ketone acid anhydride (BTDA), pyromellitic dianhydride (PMDA); Described capping monomer is one or both in Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride.
Fig. 7 is the nuclear magnetic spectrogram of phthalic anhydride as the super-branched polyimide of capping monomer; Fig. 8 is the nuclear magnetic spectrogram of naphthalene acid anhydride as the super-branched polyimide of capping monomer.
Add triethylamine and diacetyl oxide in above embodiment all to use as catalyzer, those skilled in the art can according to reacting situation about carrying out with reference to existing polyimide synthetic method determination usage quantity.
Compliance test result
The A of hexafluoro acid anhydrides end-blocking as shown in Figure 9
2+ B
3the uv-vis spectra of type super-branched polyimide, maximum absorption band, near 300nm, belongs to the π-π of aromatic ring in polyimide molecule structure
*transition.Can also obtain initial absorption wavelength (λ onset) from absorption spectrum is 387nm, so, passes through formula: E
g opt=1240/ λ onset calculates optical band gap (E
g opt) be 3.20eV.
Maximum absorption band is near 300nm as shown in Figure 10, belongs to the π-π of aromatic ring in polyimide molecule structure
*transition.Can also obtain initial absorption wavelength (λ onset) from absorption spectrum is 401nm, so, and optical band gap (E
g opt) pass through formula: E
g opt=1240/ λ onset calculates optical band gap (E
g opt) be 3.09eV.
Maximum absorption band is near 300nm as shown in Figure 11, belongs to the π-π of aromatic ring in polyimide molecule structure
*transition.Can also obtain initial absorption wavelength (λ onset) from absorption spectrum is 405nm, so, and optical band gap (E
g opt) pass through formula: E
g opt=1240/ λ onset calculates optical band gap (E
g opt) be 3.06eV.
Maximum absorption band is near 300nm as shown in Figure 12, belongs to the π-π of aromatic ring in polyimide molecule structure
*transition.Can also obtain initial absorption wavelength (λ onset) from absorption spectrum is 390nm, so, and optical band gap (E
g opt) pass through formula: E
g opt=1240/ λ onset calculates optical band gap (E
g opt) be 3.18eV.
As can be seen from uv atlas, the super-branched polyimide uv atlas generation red shift of copoly type and end-sealed type, this is because diamine monomer and capping monomer introduce the interaction added between phenyl ring, improves conjugated degree and increases; Conjugated degree is larger, π and π
*energy difference less, namely also optical band gap is less; Therefore, introducing diamine monomer and capping monomer can increase the conjugated degree of polymeric system, for the regulation and control of Polymer Optoelectronic performance provide novel method.
Claims (8)
1. a Triamine monomer, is characterized in that, this Triamine monomer molecular formula is as follows:
2. a preparation method for Triamine monomer according to claim 1, concrete steps are as follows:
Step one, be (1.1 ~ 1.5) by P-nethoxyaniline, p-fluoronitrobenzene and triethylamine according to mol ratio: 1:(1.2 ~ 1.5) feed intake, with N, dinethylformamide is solvent, under mechanical stirring and protective atmosphere, 80 ~ 85 DEG C are reacted 64 ~ 72 hours, discharging in frozen water, deionized water wash to filtrate achromaticity and clarification, vacuum drying oven 60 ~ 80 DEG C of dryings, use anhydrous methanol recrystallization afterwards, obtain safran needle crystals 4-methoxyl group-4'-nitrodiphenylamine;
Step 2, be solvent by anhydrous orthodichlorobenzene, between tribromo-benzene, 4-methoxyl group-4'-nitrodiphenylamine, salt of wormwood, copper powder and 18-be preced with-6-ether 1:(4.2 ~ 4.5 in molar ratio): (12 ~ 14): (6 ~ 8): (0.3 ~ 0.6) feeds intake, under mechanical stirring protective atmosphere 160 ~ 180 DEG C reaction 24 ~ 32 hours; Removing copper powder, discharging is in anhydrous methanol, and anhydrous methanol washs, vacuum drying oven 50 ~ 70 DEG C of dryings, afterwards with sherwood oil and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains orange solid, N, N'; N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1; 3,5-benzene triamine;
Step 3, using tetrahydrofuran (THF) and ethanol in molar ratio (1 ~ 3): 1 for mixing is as solvent, by N, N', N "-three-(4-nitro-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine and palladium/carbon add reflux in solvent, dropwise hydrazine hydrate is added in 1 ~ 2 hour, dropwise rear continuation reaction 8 ~ 12 hours, removing palladium/carbon and solvent, with ethyl acetate and methylene dichloride in molar ratio 1:1 be made into developping agent, column chromatography obtains target product N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1, 3, 5-benzene triamine,
Wherein, in described palladium/carbon, the virtual mass mark of palladium is more than 10%, with the mole number of palladium/carbon described in the cubage of palladium; N, N'; N "-three-(4-nitro-phenyl)-N, N'; N "-three-(4-methoxyl group-phenyl)-1, the mol ratio of 3,5-benzene triamine, tetrahydrofuran (THF) and alcohol mixed solvent, hydrazine hydrate and palladium/carbon is 1:(150 ~ 200): (8 ~ 12): (0.04 ~ 0.06).
3. the purposes of a Triamine monomer according to claim 1 is the terminated hyperbranched polyimide of preparation.
4. the purposes of Triamine monomer according to claim 3, is characterized in that, described terminated hyperbranched polyimide is selected from
The A of acid anhydrides end-blocking
2+ B
3type super-branched polyimide, its structure is logical formula I;
The A of amido end-blocking
2+ B
3type super-branched polyimide, its structure is logical formula II;
The A of acid anhydrides end-blocking
2+ B
2+ B
3type copolymerization super-branched polyimide, its structure is logical formula III;
With the end-sealed type super-branched polyimide that Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and/or 3,4-perylene dicarboxylic acid anhydride are capping monomer, its structure is the one in logical formula IV;
In logical formula I, (II), n is chain hop count, and has 2<n<200; R is
In logical formula III, n is chain hop count, and 2<n<200; R
3for
R in logical formula III
2for
X in logical formula I, (II) and (III) is
In logical formula IV,
for
In logical formula IV,
for
in any one;
In logical formula IV, zero is
In one or both.
5. the purposes of Triamine monomer according to claim 4, is characterized in that, the A of described acid anhydrides end-blocking
2+ B
3preparation method's step of type super-branched polyimide is as follows:
Dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol and forms two anhydride solutions, at room temperature by N, N'; N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1; 3; 5-benzene triamine is dissolved in N,N-dimethylacetamide and forms triamine solution, triamine solution was slowly joined in 1 ~ 2 hour in described two anhydride solutions; drip after terminating, stirring at normal temperature 12 ~ 24 hours under protective atmosphere;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains the A of acid anhydrides end-blocking
2+ B
3the super-branched polyimide of type;
Wherein, described N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines and dianhydride mol ratio be 1:2, triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3; Described dianhydride is biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride, ketone acid anhydride, pyromellitic dianhydride, Isosorbide-5-Nitrae, any one in 5,8-naphthalenetetracarbacidic acidic dianhydride Huo perylene tetracarboxylic acid dianhydride.
6. the purposes of Triamine monomer according to claim 4, is characterized in that, the A of described amido end-blocking
2+ B
3preparation method's step of type super-branched polyimide is as follows:
At room temperature by N, N', N "-three-(4-methanesulfonylamino-phenyl)-N; N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamine is dissolved in N, form triamine solution in N-N,N-DIMETHYLACETAMIDE, dianhydride is dissolved in N,N-dimethylacetamide or meta-cresol, form two anhydride solutions, two anhydride solutions were slowly joined in described triamine solution in 1 ~ 2 hour, drips after terminating, stirring at normal temperature 12 ~ 24 hours under protective atmosphere;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
3the super-branched polyimide of type amido end-blocking;
Described N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines and dianhydride mol ratio be 1:1, triethylamine and diacetyl oxide volume ratio are 1 ~ 2:3; Described dianhydride is biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride, ketone acid anhydride, pyromellitic dianhydride, Isosorbide-5-Nitrae, any one in 5,8-naphthalenetetracarbacidic acidic dianhydride Huo perylene tetracarboxylic acid dianhydride.
7. the purposes of Triamine monomer according to claim 4, is characterized in that, the A of described acid anhydrides end-blocking
2+ B
2+ B
3preparation method's step of type copolymerization super-branched polyimide is as follows:
With N, N-N,N-DIMETHYLACETAMIDE is solvent, by diamines and dianhydride according to mol ratio 1:(2 ~ 5) feed intake, mechanical stirring 6 ~ 8 hours under protective atmosphere, Triamine monomer is dissolved in N, in N-N,N-DIMETHYLACETAMIDE, slowly drop in dianhydride and diamine reactant system, continue reflection 12 ~ 20 hours;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging, in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtains A
2+ B
2+ B
3the super-branched polyimide of type acid anhydrides end-blocking; Diamines, Triamine monomer and dianhydride mol ratio are 1:(0.5 ~ 2): (2 ~ 5); Triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3;
Described diamines is 4,4'-diamino-4 "-methoxyl group triphenylamine and 4,4'-diamino-3 ", 5 " and one in-two trifluoromethyl triphenylamines;
Described dianhydride is biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride, ketone acid anhydride, pyromellitic dianhydride, Isosorbide-5-Nitrae, any one in 5,8-naphthalenetetracarbacidic acidic dianhydride Huo perylene tetracarboxylic acid dianhydride.
8. the purposes of Triamine monomer according to claim 4, is characterized in that, is that the preparation method of the super-branched polyimide of capping monomer is as follows with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and/or 3,4-perylene dicarboxylic acid anhydride:
Triamine monomer and dianhydride monomer are dissolved in N,N-dimethylacetamide or meta-cresol solvent respectively and form triamine solution and two anhydride solutions;
Two anhydride solutions are slowly added drop-wise in triamine solution, mechanical stirring 12 ~ 20 hours under protective atmosphere;
With N,N-dimethylacetamide or meta-cresol for dissolution with solvents capping monomer, and join in reaction system, continue reaction 8 ~ 10 hours;
Add triethylamine and diacetyl oxide, be heated to 60 ~ 80 DEG C of reactions 6 ~ 8 hours, obtain polymers soln, discharging in dehydrated alcohol, with absolute ethanol washing, in 80 ~ 100 DEG C of vacuum-dryings after being filtered dry, obtain with Tetra hydro Phthalic anhydride, 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride are the super-branched polyimide of capping monomer;
Described Triamine monomer is N, N', N "-three-(4-methanesulfonylamino-phenyl)-N, N', N "-three-(4-methoxyl group-phenyl)-1,3,5-benzene triamines, itself and dianhydride mol ratio are 1:1; Triethylamine and diacetyl oxide volume ratio are (1 ~ 2): 3; The molar weight of capping monomer is less than 1/3rd of Triamine monomer;
Described dianhydride monomer is any one in biphenyl dianhydride, monoether dianhydride, diphenyl sulfone dianhydride, hexafluorodianhydride, ketone acid anhydride, pyromellitic dianhydride; Described capping monomer is Tetra hydro Phthalic anhydride, one or both in 1,8-naphthalic anhydride and 3,4-perylene dicarboxylic acid anhydride.
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