CN109053466A - A kind of function Triamine monomer and its preparation method and application centered on aniline structure - Google Patents
A kind of function Triamine monomer and its preparation method and application centered on aniline structure Download PDFInfo
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- C07C237/40—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a non-condensed six-membered aromatic ring of the carbon skeleton having the nitrogen atom of the carboxamide group bound to a carbon atom of a six-membered aromatic ring
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Abstract
The function Triamine monomer and its preparation method and application that the invention discloses a kind of centered on aniline structure.The present invention reacts single step reaction from the monomer containing an amino and two halogen atom substituted benzene rings, through Suzuki or prepares the function Triamine monomer centered on aniline structure through Suzuki reaction, reduction reaction two-step reaction.Function Triamine monomer provided in the present invention centered on aniline structure has good thermal stability, and synthesis and preparation process is simple, and synthetic ratio is high, and purifying is simple, thus is suitable for industrial production.Function Triamine monomer centered on aniline structure of the invention can be used for the polymer such as synthesis of super branched and functional poly amide, polyimides and polyesterimide, the thermal stability and mechanical performance of polymer can be improved, significantly improve its processing performance, can also improve its electricity and in terms of performance.
Description
Technical field
The present invention relates to material science and technology fields, more particularly, to a kind of function three centered on aniline structure
Amine monomers and its preparation method and application.
Background technique
Polyimides is due to its performance characteristics outstanding, such as excellent heat resistance, excellent resistance to low temperature, excellent machine
Tool performance, thermal expansion coefficient be low, hydrolysis, resistance to light radiation, excellent electrical property, fire-retardant, nontoxic and low volatility etc., make its by
More and more attention and application are arrived.
Currently, polyimides more typical on the market, that type is more is mostly linear polyimide, although linear polyimide
With excellent thermal stability and solvent resistance, also just because of this, so that its machine-shaping is more difficult.In practical applications,
The presoma polyamic acid of polyimides is generally first prepared, then by polyamic acid machine-shaping, then imidizate, obtains polyamides
Imines finished product.
In recent years, researcher find dissaving polymer have height branched structure, show it is many with it is linear
The different property of polymer.Since the molecular structure of dissaving polymer is 3 D stereo, so dissaving polymer
Fluid behavior expression go out be Newtonian fluid behavior.Therefore, dissaving polymer compares line polymer, and viscosity is small, molten
Xie Xing, mobility and good film-forming property.Super-branched polyimide (HBPIs) is because combining both dissaving polymer and polyimides
The advantages of, have the characteristics that high temperature resistant, high intensity, dissolubility are good, in recent years the concern by vast researcher.Mesh
Before, super-branched polyimide mainly uses dual MCU system method to synthesize, such as dianhydride and triamine or diamines and three acid anhydrides, wherein uses dianhydride
It is relatively conventional with Triamine monomer copolymerization HBPIs.Commercialized dianhydride type is more, and the type of triamine is seldom, and heat
Performance is unstable, and the super-branched polyimide thermal stability of synthesis is poor, and business necessary requirement is not achieved.Therefore, design synthesis
New function Triamine monomer and the preparation for being used for super-branched polyimide, this has the extensive use of super-branched polyimide
Significance.
The present invention designs Triamine monomer of the synthesis centered on aniline, and thermal stability is high, using such Triamine monomer system
Standby super-branched polyimide not only can be improved the heat resistance of polymer, and multiple rigid aromatic structures drawn by triamine
Enter to super-branched polyimide main chain, the distance between polymer chain can be expanded, increases the free volume of polymer, further
Improve its dissolubility and processing performance, improves its gas permeability.The hyperbranched polyamides prepared by Triamine monomer of the present invention is sub-
Amine has high thermal stability and excellent solubility property simultaneously, leads in the materials such as high temperature resistant field and gas permeability and separation film
Domain is with good application prospect.
Summary of the invention
The technical problem to be solved by the present invention is to the type for triamine in the prior art is seldom, the hyperbranched polyamides of synthesis
Imines cannot get both the deficiency of the technologies such as superior heat-stability and dissolubility, provide a kind of function three centered on aniline structure
It is poly- to can be used for polyamide, polyimides, polyamidoimide and polyesterimide of synthesis of super branched and functionalization etc. for amine monomers
Close object.
Another technical problem to be solved by the present invention is that providing a kind of above-mentioned function triamine list centered on aniline structure
The preparation method of body.
A present invention also technical problems to be solved are to provide a kind of above-mentioned function triamine list centered on aniline structure
The application of body.
Function Triamine monomer structure provided by the invention centered on aniline structure is as shown in general formula I:
Wherein Ar1Selected from any one of following structural:
Preferably, the Ar1It is selected from
Wherein Ar2Selected from any one of following structural:
Preferably, the Ar2It is selected from
One of.
Function Triamine monomer centered on aniline structure of the invention, which passes through, utilizes the Ar replaced containing two halogen atoms1
Monomer is by reacting single step reaction or through Suzuki reaction, the preparation of reduction reaction two-step reaction as shown in general structure through Suzuki
The function Triamine monomer centered on aniline structure.Specifically includes the following steps:
The Ar that will replace containing two halogen atoms1Monomer and the Ar replaced containing a boric acid and an amino2Monomer is added molten
In agent, reacted by Suzuki up to the function Triamine monomer as shown in general structure centered on aniline structure；
Or the Ar that S1. replaces two halogen atoms1Monomer and the Ar replaced containing a boric acid and a nitro2Monomer adds
Enter solvent, reacts to obtain monomer 1 by Suzuki；
S2. monomer 1 in step S1 is added in solvent, through reduction reaction to obtain the final product as shown in general structure with aniline
Function Triamine monomer centered on structure；
Further, monomer 1 has the following structure feature in the step S1:
Further, it needs to be added alkali in the Suzuki reaction process, stir and leads to protective gas, after heating, be added
Catalyst, it is purification after back flow reaction, dry；It needs to stir during the reduction reaction and logical protective gas, heating is added also
Former agent is purified after back flow reaction, is dried.
Further, Ar in the Suzuki reaction1Monomer and Ar2The feed ratio of monomer is 1 ︰, 1.5~1 ︰ 6；What alkali fed intake
Amount is Ar21~6 times of monomer dosage.
Preferably, Ar in the Suzuki reaction1Monomer and Ar2The feed ratio of monomer is 1 ︰, 2~1 ︰ 3；The amount that alkali feeds intake is
Ar22~4 times of monomer dosage.
Further, the mass ratio of the material that feeds intake of monomer 1 and reducing agent is 1 ︰, 2~1 ︰ 32 in the reduction reaction.
Preferably, the mass ratio of the material that feeds intake of monomer 1 and reducing agent is 1 ︰, 18~1 ︰ 25 in the reduction reaction.
Further, the protective gas is nitrogen, one of helium, neon, argon gas, Krypton, xenon, radon gas or several
Kind；
Further, the alkali is sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, normal-butyl
Lithium, potassium tert-butoxide, the tert-butyl alcohol receive, one or more of hexamethyldisilazide lithium；
Further, the solvent in the Suzuki reaction is dimethyl sulfoxide, n,N-Dimethylformamide, tetrahydro furan
Mutter, one or more of Isosorbide-5-Nitrae dioxane, toluene, dimethylbenzene, acetone, acetonitrile, water, solvent described in step S2 be ethyl alcohol,
Methanol, normal propyl alcohol, the tert-butyl alcohol, tert-pentyl alcohol, ethyl alcohol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N, N- diformazan
One or more of base formamide, ethyl acetate, toluene.
Further, the catalyst is Pd [PPh3]4、Pd(DPPF)Cl2、PdCl2(CH3CN)2、PdCl2、Pd(OAc)2、
Pd(PPh3)2Cl2One or more of.
Further, the reducing agent is hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, zinc
One or more of powder.
Further, the heating temperature is 50 DEG C~170 DEG C, and the reflux time is 10~48h, the vacuum
40 DEG C~120 DEG C of drying temperature, the drying time is 6~32h.
Preferably, the step S1 heating temperature is 70 DEG C~90 DEG C, and the step S2 heating temperature is 70 DEG C~90 DEG C,
The reflux time is 20~30h, and 80 DEG C~100 DEG C of the vacuum drying temperature, the drying time is 20~30h.
Compared with prior art, the invention has the following advantages:
The present invention prepares Triamine monomer, Ar from common phenyl ring2The structure for being included is all heterocycle or phenyl ring knot
Structure, these rigid structures introduce the thermal stability that Triamine monomer is remarkably improved monomer, and the polymer of its preparation also can be improved
Thermal stability and mechanical performance significantly improve its processing performance, can also improve its electricity and in terms of performance.
Starting components needed for prepared by the function Triamine monomer centered on aniline structure proposed by the invention are simple, close
It is simple and easy to control at mild reaction condition, it is environmentally protective.It is controlled by accurate preparation process, so that the product of preparation is easy
Purifying, impurity is less, and yield is higher, thus is suitable for large-scale industrial production.The Triamine monomer that the present invention researches and develops can be used for synthesizing
The polymer such as hyperbranched and functionalization polyamide, polyimides, polyamidoimide and polyesterimide.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of monomer obtained by Examples 1 to 9, in which:
A corresponds to [1,1':3', 1 "-terphenyl] -3,3 ", 5'-triamine；
B corresponds to [1,1':4', 1 "-terphenyl] -2', 3,3 "-triamine；
C corresponds to [1,1':3', 1 "-terphenyl] -2', 4,4 "-triamine；
D corresponds to [1,1':3', 1 "-terphenyl] -4,4', 4 "-triamine；
E corresponds to 5,5'- (5-amino-1,3-phenylene) bis (thiophen-2-amine)；
F corresponds to 6,6'- (5-amino-1,3-phenylene) bis (naphthalen-2-amine)；
G corresponds to N, and N'- (5'-amino- [1,1':3', 1 "-terphenyl] -4,4 "-diyl) bis (4-
aminobenzamide)；
H corresponds to N, and N'- (5'-amino- [1,1':3', 1 "-terphenyl] -4,4 "-diyl) bis (4-
aminobenzamide)；
I corresponds to 7,7'- (5-amino-1,3-phenylene) bis (2-amino-9H-fluoren-9-one).
It can see from infrared spectrogram, in 3500-3350cm-1In the range of there is-NH2Characteristic absorption peak,
In 3030cm-1There is the characteristic absorption frequency of Ar-H, 1508cm in place-1The phenyl ring skeleton stretching vibration that feature occurs in place is inhaled
Receive peak, 1062~700cm-1For the characteristic absorption peak of Ar-H stretching vibration, these all illustrate product synthesized by Examples 1 to 9
All there is the feature structure of fragrant triamine.
Specific embodiment
Present invention be described in more detail in the following with reference to the drawings and specific embodiments.Unless stated otherwise, the present invention is implemented
The various raw materials that example uses can be obtained by regular market purchase, or be prepared according to the conventional method of this field, used to set
Standby is experiment commonly used equipment.Unless otherwise defined or described herein, all professional and scientific terms used herein and this field
Meaning known to person skilled in the art is identical.
Embodiment 1
[1,1':3', 1 "-terphenyl] -3,3 ", the synthesis of 5'-triamine:
By 5.018 (0.02mol) 3,5-dibromoaniline and 8.671g (0.05mol) 3- aminobenzene boric acid hydrochloride
It is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), add the solution of potassium carbonate 75mL of 2mol/L, and add
Entering the aliquat336 of 0.5mL, 0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in magnetic agitation simultaneously logical argon gas, oil bath heating,
For 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of Precipitations.It is filtered with funnel, decompression boils off solvent.Product is with two
Chloromethanes: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is that stationary phase makees column chromatography purification, collects product and is spin-dried for,
Dry 20h, obtains target product 4.461g, yield 81% in 80 DEG C of vacuum.
The synthesis of polyimides:
Three mouthfuls of burnings are added in pyromellitic acid anhydride (PMDA) 0.4362g (2mmol) and N,N-dimethylformamide 36ml
In bottle, it is passed through argon gas, is warming up to 30 DEG C, by Triamine monomer [1,1':3', 1 "-terphenyl] -3,3 ", 5'-triamine
0.2754g (1mmol) is dissolved into 40ml N,N-dimethylformamide and is dropped evenly in 1~2h into three mouthfuls with constant pressure funnel
In flask, reaction 14h is then proceeded to, 6ml acetic anhydride and 2ml triethylamine is then added, is warming up to 45 DEG C the reaction was continued 10h, instead
It should terminate to discharge in ethanol after being cooled to room temperature, filter, washing is repeated 2~3 times, is finally placed in 80 DEG C of vacuum ovens
Drying for 24 hours, obtains the super-branched polyimide polymer of rufous, structural formula is as follows:
Embodiment 2
[1,1':4', 1 "-terphenyl] -2', the synthesis of 3,3 "-triamine:
By 5.018 (0.02mol) 2,5-dibromoaniline and 8.671g (0.05mol) 3- aminobenzene boric acid hydrochloride
It is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), add the solution of potassium carbonate 75mL of 2mol/L, and add
Entering the aliquat336 of 0.5mL, 0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in magnetic agitation simultaneously logical argon gas, oil bath heating,
For 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of Precipitations.It is filtered with funnel, decompression boils off solvent.Product is with two
Chloromethanes: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is that stationary phase makees column chromatography purification, collects product and is spin-dried for,
Drying for 24 hours, obtains target product 4.571g, yield 83% in 90 DEG C of vacuum.
The synthesis of polyimides:
Pyromellitic acid anhydride (PMDA) 0.4515g (2.07mmol) and DMAC N,N' dimethyl acetamide 15ml is added three mouthfuls
In flask, it is passed through argon gas, is warming up to 30 DEG C, by Triamine monomer [1,1':4', 1 "-terphenyl] -2', 3,3 "-triamine
0.2754g (1mmol) is dissolved into 16ml DMAC N,N' dimethyl acetamide and is dropped evenly in 1~2h into three mouthfuls with constant pressure funnel
In flask, reaction 16h is then proceeded to, 6.2ml acetic anhydride and 2.1ml triethylamine is then added, being warming up to 45 DEG C, the reaction was continued
16h, reaction terminate to discharge in ethanol after being cooled to room temperature, filter, and washing repeats 2~3 times, and it is dry to be finally placed in 80 DEG C of vacuum
Drying for 24 hours, obtains flaxen super-branched polyimide polymer, structural formula is as follows in dry case:
Embodiment 3
[1,1':3', 1 "-terphenyl] -2', the synthesis of 4,4 "-triamine:
By 5.018 (0.02mol) 2,6-dibromoaniline and 8.671g (0.05mol) p-aminophenyl boric acid hydrochloride
It is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), add the solution of potassium carbonate 75mL of 2mol/L, and add
Entering the aliquat336 of 0.5mL, 0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in magnetic agitation simultaneously logical argon gas, oil bath heating,
For 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of Precipitations.It is filtered with funnel, decompression boils off solvent.Product is with two
Chloromethanes: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is that stationary phase makees column chromatography purification, collects product and is spin-dried for,
Dry 30h, obtains target product 4.681g, yield 85% in 100 DEG C of vacuum.
The synthesis of polyimides:
By [1,1':3', 1 "-terphenyl] -2', 4,4 "-triamine 0.2574g (1mmol) and N, N- dimethyl
Formamide 50ml is added in three-necked flask, is passed through argon gas, is warming up to 30 DEG C, by diphenyl ether tetraformic dianhydride (ODPA) 0.2575g
(0.83mmol) is dissolved into 50ml N,N-dimethylformamide to be dropped evenly with constant pressure funnel in 1~2h to be burnt into three mouthfuls
In bottle, reaction 18h is then proceeded to, 6ml acetic anhydride and 2ml triethylamine is then added, is warming up to 45 DEG C the reaction was continued 10h, reaction
End discharges in ethanol after being cooled to room temperature, filters, and washing repeats 2~3 times, is finally placed in 80 DEG C of vacuum ovens and does
Dry to obtain flaxen super-branched polyimide polymer for 24 hours, structural formula is as follows:
Embodiment 4
[1,1':3', 1 "-terphenyl] -4,4', the synthesis of 4 "-triamine:
By 5.018 (0.02mol) 2,4-dibromoaniline and 8.671g (0.05mol) p-aminophenyl boric acid hydrochloride
It is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), add the solution of potassium carbonate 75mL of 2mol/L, and add
Entering the aliquat336 of 0.5mL, 0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in magnetic agitation simultaneously logical argon gas, oil bath heating,
For 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of Precipitations.It is filtered with funnel, decompression boils off solvent.Product is with two
Chloromethanes: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is that stationary phase makees column chromatography purification, collects product and is spin-dried for,
Drying for 24 hours, obtains target product 4.516g, yield 82% in 90 DEG C of vacuum.
The synthesis of polyimides:
[1,1':3', 1 "-terphenyl] -4,4', 4 "-triamine 0.5508g (2mmol) and tetrahydrofuran 2ml add
Enter in three-necked flask, be passed through argon gas, be warming up to 30 DEG C, cyclobutanetetracarboxylic dianhydride (CBDA) 0.4706g (2.4mmol) is dissolved
It is dropped evenly in three-necked flask with constant pressure funnel in 1~2h into 2ml tetrahydrofuran, then proceedes to reaction 22h.By institute
It obtains super-branched polyimide acid glue blade coating to be placed in vacuum drying oven on the glass plate of dried and clean, then by glass plate, take out true
Sky, 80 lower dry 3h, constant temperature whole process 2h after then raising temperature to 120 DEG C, from 120 DEG C be warming up to 200 DEG C after the entire mistake of constant temperature
Journey 2h is warming up to 350 DEG C of constant temperature whole process 1h from 200 DEG C, and super-branched polyimide film is taken out in cooling, and structural formula is as follows:
Embodiment 5
The synthesis of 5,5'- (5-amino-1,3-phenylene) bis (thiophen-2-amine):
By 5.018 (0.02mol) 3,5-dibromoaniline and 7.149g (0.05mol) (5-aminothiophen-
2-yl) boronic acid is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), is added the carbon of 2mol/L
Sour potassium solution 75mL, and the aliquat336 of 0.5mL is added, magnetic agitation simultaneously logical argon gas, oil bath heating are added to after 75 DEG C
For 24 hours, reaction solution is poured into water for 0.020g tetra-triphenylphosphine palladium, back flow reaction, there is a large amount of Precipitations.It is filtered, is subtracted with funnel
Pressure boils off solvent.Product is using methylene chloride: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is mentioned as stationary phase as column chromatography
It is pure, it collects product and is spin-dried for, drying for 24 hours, obtains target product 4.311g, yield 75% in 90 DEG C of vacuum.
The synthesis of polyimides:
By 3,3', 4,4'-- bibenzene tetracarboxylic dianhydride (BPDA) 0.4413g (1.5mmol) and N-Methyl pyrrolidone 10ml
It is added in three-necked flask, is passed through argon gas, is warming up to 30 DEG C, by Triamine monomer 5,5'- (5-amino-1,3-phenylene) bis
(thiophen-2-amine) 0.2874g (1mmol) is dissolved into 8ml N-Methyl pyrrolidone constant pressure funnel in 1~2h
It drops evenly in three-necked flask, then proceedes to reaction 20h, 12ml acetic anhydride and 3ml triethylamine is then added, is warming up to 45 DEG C
The reaction was continued 14h, reaction terminate to discharge in methyl alcohol after being cooled to room temperature, filter, washing repeats 2~3 times, is finally placed in 80
In DEG C vacuum oven it is dry for 24 hours, obtain lurid super-branched polyimide polymer, structural formula is as follows:
。
Embodiment 6
The synthesis of 6,6'- (5-amino-1,3-phenylene) bis (naphthalen-2-amine):
By 5.018 (0.02mol) 3,5-dibromoaniline and 9.350g (0.05mol) (6-
Aminonaphthalen-2-yl) boronic acid is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF),
The solution of potassium carbonate 75mL of 2mol/L is added, and the aliquat336 of 0.5mL is added, magnetic agitation simultaneously leads to argon gas, and oil bath adds
0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in heat, and for 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of precipitating analysis
Out.It is filtered with funnel, decompression boils off solvent.Product is with methylene chloride: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is solid
It is fixed mutually to make column chromatography purification, it collects product and is spin-dried for, drying for 24 hours, obtains target product 5.632g, yield is in 90 DEG C of vacuum
75%.
The synthesis of polyimides:
6,6'- (5-amino-1,3-phenylene) bis (naphthalen-2-amine) 0.3755g (1mmol) and N,
Dinethylformamide 8ml is added in three-necked flask, is passed through argon gas, is warming up to 30 DEG C, by 3,3', 4,4'-- bibenzene tetracarboxylics two
Acid anhydride (BPDA) 0.2942g (1mmol), which is dissolved into 8ml N,N-dimethylformamide, uniformly to be dripped with constant pressure funnel in 1~2h
It is added in three-necked flask, then proceedes to reaction 18h.Gained super-branched polyimide acid glue is scratched into the glass in dried and clean
On plate, then glass plate is placed in vacuum drying oven, vacuumized, 80 lower dry 3h, constant temperature whole process after then raising temperature to 120 DEG C
2h, from 120 DEG C be warming up to 200 DEG C after constant temperature whole process 2h, be warming up to 350 DEG C of constant temperature whole process 1h from 200 DEG C, it is cooling,
Super-branched polyimide film is taken out, structural formula is as follows:
Embodiment 7
N,N'-(5'-amino-[1,1':3',1”-terphenyl]-4,4”-diyl)bis(4-aminobenzamide)
Synthesis:
By 5.018 (0.02mol) 3,5-dibromoaniline and 12.803g (0.05mol) (4- (4-
Aminobenzamido) phenyl) boronic acid is added in 500mL there-necked flask, it is added 400mL tetrahydrofuran (THF),
The solution of potassium carbonate 75mL of 2mol/L is added, and the aliquat336 of 0.5mL is added, magnetic agitation simultaneously leads to argon gas, and oil bath adds
0.020g tetra-triphenylphosphine palladium is added to after 75 DEG C in heat, and for 24 hours, reaction solution is poured into water for back flow reaction, there is a large amount of precipitating analysis
Out.It is filtered with funnel, decompression boils off solvent.Product is with methylene chloride: n-hexane=3: 1 (volume ratio) is that mobile phase silica gel is solid
It is fixed mutually to make column chromatography purification, it collects product and is spin-dried for, drying for 24 hours, obtains target product 7.190g, yield is in 90 DEG C of vacuum
70%.
The synthesis of polyimides:
N,N'-(5'-amino-[1,1':3',1”-terphenyl]-4,4”-diyl)bis(4-aminobenzamide)
1.0272g (2mmol) and n,N-Dimethylformamide 8ml are added in three-necked flask, are passed through argon gas, are warming up to 30 DEG C, by 3,3',
4,4'- benzophenone tetracid dianhydride (BTDA) 0.6444g (2mmol), which is dissolved into 8ml N,N-dimethylformamide, uses constant pressure addition
Funnel drops evenly in three-necked flask in 1~2h, then proceedes to reaction 10h, 6ml acetic anhydride and 2ml triethylamine is then added,
45 DEG C being warming up to the reaction was continued 12h, reaction terminates to discharge in ethanol after being cooled to room temperature, filter, and washing repeats 2~3 times,
It is finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtains the super-branched polyimide polymer of brown, structural formula is as follows:
。
Embodiment 8
N,N'-(5'-amino-[1,1':3',1”-terphenyl]-4,4”-diyl)bis(4-aminobenzamide)
Synthesis:
S1. synthetic intermediate N, N'- (5'-amino- [1,1':3', 1 "-terphenyl] -4,4 "-diyl) bis (4-
Nitrobenzamide):
By 5.018 (0.02mol) 3,5-dibromoaniline and 14.3025g (0.05mol) (4- (4-
Nitrobenzamido) phenyl) boronic acid is added in 500mL there-necked flask, and tetrahydrofuran (THF) is solvent, then
The aliquat336 of the solution of potassium carbonate 75mL and 0.5mL of 2mol/L, magnetic agitation and logical argon gas is added, oil bath heating is to 75 DEG C
Afterwards, be added 0.020g tetra-triphenylphosphine palladium, back flow reaction for 24 hours after, reaction solution is poured into water, there is a large amount of Precipitations.With leakage
Bucket filters, and decompression boils off solvent.Product is using methylene chloride: n-hexane=3: 1 (volume ratio) is mobile phase silica gel as stationary phase work
Column chromatography purification is collected product and is spin-dried for, and drying for 24 hours, obtains yellow solid, yield 70% in 90 DEG C of vacuum.Among this
Body structure is as follows:
S2. N is synthesized, and N'- (5'-amino- [1,1':3', 1 "-terphenyl] -4,4 "-diyl) bis (4-
aminobenzamide)
By 5.7355g (0.01mol) N, N'- (5'-amino- [1,1':3', 1 "-terphenyl] -4,4 "-diyl) bis
(4-nitrobenzamide) is added in 500mL there-necked flask, and 450mL dehydrated alcohol, magnetic agitation and logical argon gas, oil bath is added
After being heated to 80 DEG C, the palladium carbon 0.1g of 10%wt is added, and 10mL hydrazine hydrate is added, after back flow reaction 30h, reaction solution is taken out
Filtrate cold crystallization is filtered 80 DEG C of filter cake vacuum drying of gained for 24 hours, obtains product 4.6223g, yield 90% by filter.
The synthesis of polyimides:
N,N'-(5'-amino-[1,1':3',1”-terphenyl]-4,4”-diyl)bis(4-aminobenzamide)
1.0272g (2mmol) and n,N-Dimethylformamide 8ml are added in three-necked flask, are passed through argon gas, are warming up to 30 DEG C, by 3,3',
4,4'- benzophenone tetracid dianhydride (BTDA) 0.6444g (2mmol), which is dissolved into 8ml N,N-dimethylformamide, uses constant pressure addition
Funnel drops evenly in three-necked flask in 1~2h, then proceedes to reaction 10h, 6ml acetic anhydride and 2ml triethylamine is then added,
45 DEG C being warming up to the reaction was continued 12h, reaction terminates to discharge in ethanol after being cooled to room temperature, filter, and washing repeats 2~3 times,
It is finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtains the super-branched polyimide polymer of brown, structural formula is as follows:
。
Embodiment 9
The synthesis of 7,7'- (5-amino-1,3-phenylene) bis (2-amino-9H-fluoren-9-one):
S1. synthetic intermediate 7,7', 7 "-(benzene-1,3,5-triyl) tris (2-nitro-9H-fluoren-9-
One):
By 5.018 (0.02mol) 3,5-dibromoaniline and 13.451g (0.05mol) (7-nitro-9-oxo-
9H-fluoren-2-yl) boronic acid is added in 500mL there-necked flask, and tetrahydrofuran (THF) is solvent, is added
The aliquat336 of the solution of potassium carbonate 37.5mL and 0.5mL of 2mol/L, magnetic agitation and logical argon gas, oil bath heating is to 75 DEG C
Afterwards, be added 0.020g tetra-triphenylphosphine palladium, back flow reaction for 24 hours after, reaction solution is poured into water, there is a large amount of Precipitations.With leakage
Bucket filters, and decompression boils off solvent.Product is using methylene chloride: n-hexane=3: 1 (volume ratio) is mobile phase silica gel as stationary phase work
Column chromatography purification is collected product and is spin-dried for, and drying for 24 hours, obtains yellow solid, yield 70% in 90 DEG C of vacuum.Among this
Body structure is as follows:
S2. synthesis 7,7'- (5-amino-1,3-phenylene) bis (2-amino-9H-fluoren-9-one) will
5.3949g (0.01mol) 7,7', 7 "-(benzene-1,3,5-triyl) tris (2-nitro-9H-fluoren-9-one) add
Enter into 500mL there-necked flask, be added 450mL dehydrated alcohol, magnetic agitation simultaneously logical argon gas, oil bath heating is added to after 80 DEG C
The palladium carbon 0.1g of 10%wt, and 12mL hydrazine hydrate is added, after back flow reaction 30h, reaction solution is filtered, filtrate cold crystallization is taken out
80 DEG C of the filter cake vacuum drying of filter gained for 24 hours, obtain product 4.4117g, yield 92%.
The synthesis of polyimides:
7,7'-(5-amino-1,3-phenylene)bis(2-amino-9H-fluoren-9-one)0.9591g
(2mmol) and n,N-dimethylacetamide 5ml are added in three-necked flask, are passed through argon gas, are warming up to 30 DEG C, by hexafluorodianhydride (6FDA)
(6FDA) 0.8618g (1.94mmol) is dissolved into 5.5ml DMAC N,N' dimethyl acetamide equal in 1~2h with constant pressure funnel
It is even to be added dropwise in three-necked flask, reaction 15h is then proceeded to, 6ml acetic anhydride then is added and 2ml triethylamine is warming up to 45 DEG C of continuation
14h is reacted, reacts and discharges after terminating to be cooled to room temperature in methyl alcohol, filter, washing repeats 2~3 times, is finally placed in 80 DEG C very
Drying for 24 hours, obtains super-branched polyimide polymer russet, structural formula is as follows in empty drying box:
Using the differential scanning calorimeter (DSC204) of Nai Chi company and the thermogravimetric analyzer (Q50) of TA company respectively to reality
It applies super-branched polyimide prepared by example 1~9 and carries out glass transition temperature (Tg) and the survey of 5% thermal weight loss temperature (T5%)
Examination, test result is as shown in table 1, and the solubility property data of super-branched polyimide are as shown in table 2.
The hot property of 1 super-branched polyimide of table
The dissolubility of 2 super-branched polyimide of table
Note: ++ representing room temperature can be completely dissolved
As can be seen from Table 1 and Table 2, turned by super-branched polyimide prepared by Triamine monomer of the present invention with high-vitrification
Temperature and thermal stability, excellent dissolubility.
Detailed process equipment and process flow of the invention that the present invention is explained by the above embodiments, but the present invention is not
It is confined to above-mentioned detailed process equipment and process flow, that is, does not mean that the present invention must rely on above-mentioned detailed process equipment and work
Skill process could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to product of the present invention
The equivalence replacement of each raw material and addition, the selection of concrete mode of auxiliary element etc., all fall within protection scope of the present invention and public affairs
Within the scope of opening.
Claims (10)
1. a kind of function Triamine monomer centered on aniline structure, which is characterized in that the monomer structure is as shown in (I) general formula:
Wherein, Ar1Selected from one of following structural:
Preferably, the Ar1It is selected from
2. the function Triamine monomer according to claim 1 centered on aniline structure, which is characterized in that the Ar2It is selected from
Any one in following structural:
；
Preferably, the Ar2It is selected from
One of.
3. the preparation method of the function Triamine monomer of any of claims 1 or 2 centered on aniline structure, which is characterized in that
The following steps are included:
The Ar that will replace containing two halogen atoms1Monomer and the Ar replaced containing a boric acid and an amino2Solvent is added in monomer
In, it is reacted by Suzuki up to the function Triamine monomer as shown in general structure (I) centered on aniline structure；
Or the Ar that S1. replaces two halogen atoms1Monomer and the Ar replaced containing a boric acid and a nitro2Monomer is added molten
Agent reacts to obtain monomer 1 by Suzuki；
S2. monomer 1 in step S1 is added in solvent, through reduction reaction to obtain the final product as shown in general structure I with aniline knot
Function Triamine monomer centered on structure；
Monomer 1 has the following structure feature in step S1:
4. the preparation method of the function Triamine monomer according to claim 3 centered on aniline structure, which is characterized in that
It needs to be added alkali in the Suzuki reaction process, stirs simultaneously logical protective gas, after heating, be added catalyst, after back flow reaction
Purification, drying；Need to stir and lead to protective gas during the reduction reaction, heating is added reducing agent, passes through after back flow reaction
Purification, drying.
5. the preparation method of the function Triamine monomer according to claim 4 centered on aniline structure, which is characterized in that
Ar in the Suzuki reaction1Monomer and Ar2The feed ratio of monomer is 1 ︰, 1.5~1 ︰ 6；The amount that alkali feeds intake is Ar2Monomer dosage
1~6 times；The mass ratio of the material that feeds intake of monomer 1 and reducing agent is 1 ︰, 2~1 ︰ 32 in the reduction reaction.
6. the preparation method of the function Triamine monomer according to claim 4 centered on aniline structure, which is characterized in that
The protective gas is nitrogen, one or more of helium, neon, argon gas, Krypton, xenon, radon gas；The alkali is hydrogenation
Sodium, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-BuLi, potassium tert-butoxide, the tert-butyl alcohol receive, hexamethyl two
One or more of silicon substrate amido lithium.
7. the preparation method of the function Triamine monomer according to claim 3 centered on aniline structure, which is characterized in that
Solvent described in step S1 is dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4 dioxane, toluene, diformazan
One or more of benzene, acetone, acetonitrile, water；Solvent described in step S2 is ethyl alcohol, methanol, normal propyl alcohol, the tert-butyl alcohol, uncle penta
Alcohol, ethyl alcohol, hexanol, tetrahydrofuran, 1,4 dioxane, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, in toluene
One or more.
8. the preparation method of the function Triamine monomer according to claim 4 centered on aniline structure, which is characterized in that
The catalyst is Pd [PPh3]4、Pd(DPPF)Cl2、PdCl2(CH3CN)2、PdCl2、Pd(OAc)2、Pd(PPh3)2Cl2In one
Kind is several；The reducing agent is hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, one in zinc powder
Kind is several.
9. the preparation method of the function Triamine monomer according to claim 4 centered on aniline structure, which is characterized in that
The heating temperature is 50 DEG C~170 DEG C, and the reflux time is 10~48h, the vacuum drying temperature 40 DEG C~120
DEG C, the drying time is 6~32h.
10. the function Triamine monomer according to any one of claims 1 to 9 centered on aniline structure is applied to synthesis of super branched
With functionalized polyimides, polyamide, polyamidoimide or polyesterimide polymer.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342845A (en) * | 1964-11-05 | 1967-09-19 | Upjohn Co | Terphenyl triisocyanates |
| US4110294A (en) * | 1974-04-08 | 1978-08-29 | Ciba-Geigy Corporation | Processing aids for high temperature polymers |
| US4251417A (en) * | 1979-04-25 | 1981-02-17 | Gulf Oil Corporation | Novel acetylene end-capped polyimide oligomers |
-
2018
- 2018-07-31 CN CN201810858582.5A patent/CN109053466A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342845A (en) * | 1964-11-05 | 1967-09-19 | Upjohn Co | Terphenyl triisocyanates |
| US4110294A (en) * | 1974-04-08 | 1978-08-29 | Ciba-Geigy Corporation | Processing aids for high temperature polymers |
| US4251417A (en) * | 1979-04-25 | 1981-02-17 | Gulf Oil Corporation | Novel acetylene end-capped polyimide oligomers |
Non-Patent Citations (4)
| Title |
|---|
| MATTHIAS GEORG SCHWAB等: "Photocatalytic hydrogen evolution through fully conjugated poly(azomethine) networks", 《CHEM.COMMUN.》 * |
| P.N.PRESTON等: "Studies on Bismaleimides and Related Materials. 4.Synthesis and Characterization of New Bismaleimides Based on Terphenyl, Tetraphenylketazine, and Bisphenol A: "Reactive Building Blocks" for Bismaleimides", 《MACROMOLECULES》 * |
| PIOTR MILART等: "Synthesis of Di- and Triamino-l,l":3",l"-terphenyls from Arylethylidene- and Arylidenemalonodinitriles", 《TETRAHEDRON》 * |
| 胡敏: "新型含萘结构二胺单体的设计合成及其在聚酰亚胺中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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