CN108911992A - 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 PDFInfo
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- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a kind of Triamine monomers and its preparation method and application.The present invention or from the phenyl ring monomer replaced containing a halogen atom and an amino, through the preparation of the series of chemical such as Ullmann coupling reaction, Suzuki reaction, reduction reaction using phenyl ring as the function Triamine monomer of core.Simple using phenyl ring as the synthetic method craft of the function Triamine monomer of core involved in the present invention, purifying is easy, thus is suitable for industrial production.The structure that Triamine monomer prepared by the present invention is included is all heterocycle or benzene ring structure, these rigid structures introduce the thermal stability that Triamine monomer is remarkably improved monomer.Triamine monomer prepared by the present invention can be used for the polymer such as synthesis of super branched and functional poly amide, polyimides, polyamidoimide and polyesterimide, the thermal stability and mechanical performance that polymer prepared therefrom can be effectively improved, improve the processing performance of polymer.
Description
Technical field
The present invention relates to material science and technology fields, more particularly, to a kind of Triamine monomer and preparation method thereof and use
On the way.
Background technique
Polyimides is had been widely used at present due to its performance characteristics outstanding in Aeronautics and Astronautics, microelectronics, nanometer, liquid
The fields such as crystalline substance, seperation film, laser.Recently, each state all by the research of polyimides, exploitation and using being included in 21 century most and having it is uncommon
One of engineering plastics of prestige.Either as structural material or as functional material, huge application prospect has been obtained
To sufficient understanding.But thermal stability and solvent resistance that polyimides is excellent, so that its machine-shaping is more difficult.
Dissaving polymer has the branched structure of height due to itself, shows spies much different from line polymer
Different performance, if dissolubility is good, no chain entanglement, it is difficult to or do not crystallize, low solution and melting viscosity, splendid heat-resisting, solvent resistant
With the performances such as high dielectric, the in recent years concern by vast researcher.Branched structure is introduced into polyimide structures, is made
Standby super-branched polyimide, it shows properties much different from line polymer, such as melt viscosity and solution viscosity
Low, dissolubility is good.Relative to linear polyimide, the dissolubility of super-branched polyimide is good, but its heat resistance relative drop, this
It is limited in the extensive use in the fields such as space flight, aviation aircraft structure or function component.The type phase of Triamine monomer at present
To less, and the hot property of existing triamine is unstable, and synthetic ratio is low, and industrialized monomeric species are just more limited, less
Monomeric species largely hinder the application of super-branched polyimide, it has also become its develop bottleneck problem.
Present invention design synthesizes a kind of Triamine monomer containing the rigid structures such as heterocycle or phenyl ring, and thermal stability is high, uses
Such Triamine monomer prepares super-branched polyimide, the heat resistance of polymer not only can be improved, and by triamine multiple
Rigid aromatic structure is introduced into super-branched polyimide main chain, can expand the distance between polymer chain, increase polymer
Free volume further improves its dissolubility and processing performance, improves its gas permeability.It is prepared by Triamine monomer of the present invention
Super-branched polyimide there is high thermal stability and excellent solubility property simultaneously, permeated in high temperature resistant field and gas
The Material Fields such as seperation film are with good application prospect.
Summary of the invention
The technical problem to be solved by the present invention is to unstable for Triamine monomer hot property in the prior art, synthetic method is multiple
Miscellaneous, synthetic ratio is low, unstable quality, the polyimides of preparation cannot get both excellent hot property and dissolubility the deficiencies of, provide
A kind of Triamine monomer, polyamide, polyimides, polyamidoimide and the polyester acyl that can be used for synthesis of super branched and functionalization are sub-
The polymer such as amine.
Another technical problem to be solved by the present invention is that providing the synthetic method of above-mentioned Triamine monomer.
The present invention also one will solve the problems, such as the application for being to provide above-mentioned Triamine monomer.
A kind of Triamine monomer structure provided by the invention is as shown in logical formula (I)：
Wherein Ar1Selected from any one of following structural：
Preferably, the Ar1It is selected from
Wherein Ar2And Ar3Selected from any one of following structural：
Preferably, the Ar2It is selected from
One of.
Preferably, the Ar3It is selected from
One of.
It is of the present invention using phenyl ring as the function Triamine monomer of core.Specifically include following preparation step：
S1. the Ar that will replace containing a halogen atom and an amino1Monomer with contain a halogen atom and a nitro
Substituted Ar2Monomer is added in solvent, obtains monomer 1 by Ullmann coupling reaction；
S2. replaced using monomer 1 in step S1 with containing a boric acid and an amino or a boric acid and a nitro
Ar3Monomer is added in solvent, reacts to obtain monomer 2 or monomer 3 by Suzuki；
S3. monomer 2 in step S2 or monomer 3 are added in solvent, by reduction reaction up to shown in general structure (I)
Triamine monomer；
Further, monomer 1 in step S1, monomer 2 and monomer 3 are respectively provided with following structure feature in step S2：
Wherein X is F, Cl, Br or I.
Further, the Ullmann coupling reaction is to be passed through protective gas during the reaction, heating, and alkali is added and returns
It is purified after stream reaction, it is dry in vacuum.
Further, the Suzuki reaction is that alkali is added during the reaction, stirs and is passed through protective gas, heat,
Catalyst is added, is purified after back flow reaction, it is dry.
Further, the reduction reaction is to be passed through protective gas during the reaction, heating, and reducing agent, reflux is added
It is purified after reaction, it is dry.
Further, the Ar in the Ullmann coupling reaction1Monomer and Ar2The ratio of the amount of the substance that feeds intake of monomer is 1 ︰
1.6~1 ︰ 6, the dosage of alkali are Ar11~3 times of the amount of monomeric substance.
Further, the monomer 1 and Ar in the Suzuki reaction3The ratio of the amount of the substance that feeds intake of monomer is 1 ︰, 1~1 ︰
2, the amount of the substance of alkali is Ar31~6 times of the amount of monomeric substance.
Further, the ratio of the amount of the substance that feeds intake of the monomer 2 in the reduction reaction or monomer 3 and reducing agent is 1 ︰ 2
~1 ︰ 32.
Preferably, Ar in the Ullmann coupling reaction1Monomer and Ar2The mass ratio of the material that feeds intake of monomer is 1 ︰ 5, alkali
Dosage is Ar12 times of the amount of monomeric substance；Monomer 1 and Ar in the Suzuki reaction3The mass ratio of the material that feeds intake of monomer is 1 ︰
1.5, the dosage of alkali is Ar33 times of the amount of monomeric substance；The object that feeds intake of monomer 2 or monomer 3 and reducing agent in the reduction reaction
The amount ratio of matter is 1 ︰, 15~1 ︰ 25.
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 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 solvent in step S1 is dimethyl sulfoxide, n,N-Dimethylformamide, tetrahydrofuran, Isosorbide-5-Nitrae
One or more of dioxane, toluene, dimethylbenzene, acetone, acetonitrile, diphenyl ether；Solvent described in step S2 is dimethyl
One of sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4 dioxane, toluene, dimethylbenzene, acetone, acetonitrile, water or
It is several；Solvent described in step S3 is ethyl alcohol, methanol, normal propyl alcohol, the tert-butyl alcohol, tert-pentyl alcohol, ethyl alcohol, hexanol, tetrahydrofuran, 1,4
One or more of dioxane, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, toluene.
Further, the heating temperature is 50 DEG C~170 DEG C, and the reflux time is 10~48h；The drying
40 DEG C~120 DEG C of temperature, the drying time is 6~30h.
Preferably, 100 DEG C~170 DEG C of heating temperature in the step S1,50 DEG C~100 DEG C of heating temperature in step S2,
70 DEG C~100 DEG C of heating temperature in step S3, reflux time are 20~28h, and drying temperature is 70 DEG C~90 DEG C, when dry
Between be 6~30h.
Further, the protective gas is one of nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas or several
Kind.
Compared with prior art, the invention has the advantages that：
The present invention prepares Triamine monomer, Ar by core of common phenyl ring2And Ar3The structure for being included is all heterocycle or benzene
Ring structure, these rigid structures introduce the thermal stability that Triamine monomer is remarkably improved monomer, also can be improved prepared therefrom poly-
Close the thermal stability and mechanical performance of object.In addition, it is good with super-branched polyimide dissolubility prepared by Triamine monomer of the present invention, it is difficult
With or do not crystallize, solution and melting viscosity are low, with excellent processing performance and high dielectric property, while also have it is excellent
Good electricity and magnetic performance.
The present invention effectively increases the synthetic ratio of Triamine monomer by reasonable material proportion, the compatible technique of selection,
And the synthesis technology of Triamine monomer proposed by the invention is simple, and purifying is easy, and yield is high, thus is suitable for industrial production.This
The Triamine monomer of invention can be used for polyamide, polyimides, polyamidoimide and the polyester acyl of synthesis of super branched and functionalization
The polymer such as imines.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of monomer obtained by Examples 1 to 5, wherein：
A corresponds to N4,N4-bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-diamine；
B corresponds to N3,N3-bis(4-aminophenyl)-[1,1'-biphenyl]-3,4'-diamine；
C corresponds to N2,N2-bis(4-aminophenyl)-[1,1'-biphenyl]-2,4'-diamine；
D corresponds to N2-(6-aminonaphthalen-2-yl)-N2-(4-(5-aminothiophen-2-yl)phenyl)
naph-thalene-2,6-diamine；
E corresponds to N2-(4-(6-aminonaphthalen-2-yl)phenyl)-N2-(5-aminothiophen-2-yl)
thiop-hene-2,5-diamine。
It can see from infrared spectrogram, in 3502-3348cm-1In the range of there is-NH2Characteristic absorption peak,
1625cm-1For the bending vibration absorption peak of N-H key；1245cm-1There is the characteristic absorption peak of C-N stretching vibration in place；1536cm-1
And 1500cm-1There is the phenyl ring skeleton stretching vibration absworption peak of feature, 1108~750cm in place-1For the spy of Ar-H stretching vibration
Absorption peak is levied, these, which all illustrate product synthesized by Examples 1 to 5 all, has the feature structure of fragrant triamine.
Specific embodiment
Example is given below so that the present invention will be described in more detail, it is necessary to be pointed out that following embodiment cannot be explained
For the limitation to invention protection scope, the person skilled in the art in the field makes the present invention according to foregoing invention content some
Nonessential modifications and adaptations should belong to the scope of protection of the present invention.
Embodiment 1
N4,N4- bis (4-aminophenyl)-[1,1'-biphenyl] -4,4'-diamine synthesis：
S1. synthetic intermediate 4-bromo-N, N-bis (4-nitrophenyl) aniline：
1.720g (0.01mol) 4- bromaniline and 7.055mL (0.05mol) p-fluoronitrobenzene are added to tri- mouthfuls of 250mL
In bottle, DMSO is solvent, magnetic agitation and logical argon gas, is heated to 150 DEG C of oil bath, adds 3.038g (0.02mol) cesium fluoride
(CsF), back flow reaction is for 24 hours.Reaction solution is poured into ice water, is extracted with dichloromethane, be decompressed to -101.325kPa boil off it is molten
Agent, product is with methylene chloride:N-hexane=1:2 (volume ratios) are mobile phase, silica gel is that stationary phase makees column chromatography purification, collect and produce
Object is simultaneously spin-dried for, and drying for 24 hours, obtains product 2.485g, yield 60% in 80 DEG C of vacuum.The intermediate structure is as follows：
S2. synthetic intermediate N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine：
By 8.284 (0.02mol) 4-bromo-N, N-bis (4-nitrophenyl) aniline and 5.202g
(0.03mol) p-aminophenyl boric acid hydrochloride is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), is added
The solution of potassium carbonate 45mL of 2mol/L, and the aliquat336 of 5mL is added, magnetic agitation and logical argon gas, oil bath heating is to 75 DEG C
Afterwards, 0.020g tetra-triphenylphosphine palladium is added, back flow reaction is for 24 hours.Reaction solution is decompressed to -101.325kPa and boils off solvent, product
With methylene chloride:N-hexane=1:1 (volume ratio) is mobile phase, silica gel is that stationary phase makees column chromatography purification, collects product and revolves
Dry, drying for 24 hours, obtains product 6.396g, yield 75% in 80 DEG C of vacuum.The intermediate structure is as follows：
S3. N is synthesized4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine：
4.264g (0.01mol) 3,6-dinitro-9- (4-nitrophenyl) -9H-carbazole is added to
In 500mL there-necked flask, it is added 450mL dehydrated alcohol, 10%wt is added to after 80 DEG C in magnetic agitation simultaneously logical argon gas, oil bath heating
Palladium carbon 0.1g, and 10mL hydrazine hydrate is added, back flow reaction for 24 hours after, reaction solution is filtered, filtrate crystallisation by cooling is taken out again
80 DEG C of the filter cake vacuum drying of filter gained for 24 hours, obtain product 3.481g, yield 95%.The infrared spectrogram of compound such as Fig. 1 institute
Show.
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 N4,N4-bis(4-aminophenyl)-[1,1'-biphenyl]-4,
4'-diamine0.3665g (1mmol) is dissolved into 40mlN, and dinethylformamide is uniformly dripped with constant pressure funnel in 1~2h
It is added in three-necked flask, then proceedes to reaction 12h, 6ml acetic anhydride and 2ml triethylamine is then added, be warming up to 45 DEG C and continue instead
10h is answered, reaction terminates to discharge in methyl alcohol after being cooled to room temperature, filter, washing repeats 2~3 times, is finally placed in 80 DEG C of vacuum
Drying for 24 hours, obtains the super-branched polyimide polymer of yellow, structural formula is as follows in drying box：
Embodiment 2
N3,N3- bis (4-aminophenyl)-[1,1'-biphenyl] -3,4'-diamine synthesis：
S1. synthetic intermediate 3-bromo-N, N-bis (4-nitrophenyl) aniline：
1.720g (0.01mol) 3- bromaniline and 7.055mL (0.05mol) p-fluoronitrobenzene are added to tri- mouthfuls of 250mL
In bottle, DMSO is solvent, magnetic agitation and logical argon gas, is heated to 150 DEG C of oil bath, adds 3.038g (0.02mol) cesium fluoride
(CsF), back flow reaction is for 24 hours.Reaction solution is poured into ice water, is extracted with dichloromethane, be decompressed to -101.325kPa boil off it is molten
Agent, product is with methylene chloride:N-hexane=1:3 (volume ratios) are mobile phase, silica gel is that stationary phase makees column chromatography purification, collect and produce
Object is simultaneously spin-dried for, and drying for 24 hours, obtains product 2.692g, yield 65% in 80 DEG C of vacuum.The intermediate structure is as follows：
S2. synthetic intermediate N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine：
By 8.284 (0.02mol) 4-bromo-N, N-bis (4-nitrophenyl) aniline and 5.202g
(0.03mol) p-aminophenyl boric acid hydrochloride is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), is added
The solution of potassium carbonate 45mL of 2mol/L, and the aliquat336 of 5mL is added, magnetic agitation and logical argon gas, oil bath heating is to 75 DEG C
Afterwards, 0.020g tetra-triphenylphosphine palladium is added, back flow reaction is for 24 hours.Reaction solution is decompressed to -101.325kPa and boils off solvent, product
With methylene chloride:N-hexane=1:1 (volume ratio) is mobile phase, silica gel is that stationary phase makees column chromatography purification, collects product and revolves
Dry, drying for 24 hours, obtains product 6.396g, yield 75% in 80 DEG C of vacuum.The intermediate structure is as follows：
S3. N is synthesized4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine：
By 4.264g (0.01mol) N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine
It is added in 500mL there-necked flask, is 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 10mL hydrazine hydrate is added, back flow reaction for 24 hours after, reaction solution is filtered, by filtrate crystallisation by cooling,
80 DEG C of filter cake vacuum drying of gained are filtered again for 24 hours, obtain product 3.298g, yield 90%.The infrared spectrogram of compound
As shown in Figure 1.
The synthesis of polyimides：
Three mouthfuls of burnings are added in pyromellitic acid anhydride (PMDA) 0.903g (4.14mmol) and DMAC N,N' dimethyl acetamide 3ml
In bottle, it is passed through argon gas, is warming up to 30 DEG C, by Triamine monomer N3,N3-bis(4-aminophenyl)-[1,1'-biphenyl]-3,
4'-diamine0.733g (2mmol) is dissolved into 2mlN, and N- dimethyl acetamide is dropped evenly with constant pressure funnel in 1~2h
Enter in three-necked flask, then proceedes to reaction 15h, 12.4ml acetic anhydride and 4.2ml triethylamine is then added, is warming up to 45 DEG C of continuation
12h is reacted, reacts and discharges after terminating to be cooled to room temperature in ethanol, filter, washing repeats 2~3 times, is finally placed in 80 DEG C very
Drying for 24 hours, obtains the super-branched polyimide polymer of brown, structural formula is as follows in empty drying box：
Embodiment 3
N2,N2- bis (4-aminophenyl)-[1,1'-biphenyl] -2,4'-diamine synthesis：
S1. synthetic intermediate 2-bromo-N, N-bis (4-nitrophenyl) aniline：
1.720g (0.01mol) 2- bromaniline and 7.055mL (0.05mol) p-fluoronitrobenzene are added to tri- mouthfuls of 250mL
In bottle, DMSO is solvent, magnetic agitation and logical argon gas, is heated to 150 DEG C of oil bath, adds 3.038g (0.02mol) cesium fluoride
(CsF), back flow reaction is for 24 hours.Reaction solution is poured into ice water, is extracted with dichloromethane, be decompressed to -101.325kPa boil off it is molten
Agent, product is with methylene chloride:N-hexane=1:3 (volume ratios) are mobile phase, silica gel is that stationary phase makees column chromatography purification, collect and produce
Object is simultaneously spin-dried for, and drying for 24 hours, obtains product 2.692g, yield 65% in 80 DEG C of vacuum.The intermediate structure is as follows：
S2. synthetic intermediate N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine：
By 8.284 (0.02mol) 2-bromo-N, N-bis (4-nitrophenyl) aniline and 5.202g
(0.03mol) p-aminophenyl boric acid hydrochloride is added in 500mL there-necked flask, is added 400mL tetrahydrofuran (THF), is added
The solution of potassium carbonate 45mL of 2mol/L, and the aliquat336 of 5mL is added, magnetic agitation and logical argon gas, oil bath heating is to 75 DEG C
Afterwards, 0.020g tetra-triphenylphosphine palladium is added, back flow reaction is for 24 hours.Reaction solution is decompressed to -101.325kPa and boils off solvent, product
With methylene chloride:N-hexane=1:1 (volume ratio) is mobile phase, silica gel is that stationary phase makees column chromatography purification, collects product and revolves
Dry, drying for 24 hours, obtains product 6.396g, yield 75% in 80 DEG C of vacuum.The intermediate structure is as follows：
S3. N is synthesized2,N2-bis(4-nitrophenyl)-[1,1'-biphenyl]-2,4'-diamine：
By 4.264g (0.01mol) N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine
It is added in 500mL there-necked flask, is 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 11mL hydrazine hydrate is added, back flow reaction for 24 hours after, reaction solution is filtered, by filtrate crystallisation by cooling,
80 DEG C of filter cake vacuum drying of gained are filtered again for 24 hours, obtain product 3.371g, yield 92%.The infrared spectrogram of compound
As shown in Figure 1.
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 N2,N2-bis(4-aminophenyl)-[1,1'-
Biphenyl] -2,4'-diamine0.3665g (1mmol) is dissolved into 8mlN- methyl pyrrolidone constant pressure funnel 1
~2h is dropped evenly in three-necked flask, then proceedes to reaction for 24 hours, and 12ml acetic anhydride and 3ml triethylamine is then added, is warming up to
45 DEG C of the reaction was continued 10h, reaction terminate to discharge in methyl alcohol after being cooled to room temperature, filter, washing repeats 2~3 times, most postposition
Drying for 24 hours, obtains the super-branched polyimide polymer of brown, structural formula is as follows in 80 DEG C of vacuum ovens：
Embodiment 4
N2-(6-aminonaphthalen-2-yl)-N2-(4-(5-aminothiophen-2-yl)phenyl)
The synthesis of naphthalene-2,6-diamine：
S1. synthetic intermediate N- (4-bromophenyl) -6-nitro-N- (6-nitronaphthalen-2-yl)
naphthalen-2-amine：
By 1.720g (0.01mol) 4- bromaniline and 14.953mL (0.05mol) 2-iodo-6-nitronaphthalene
It is added in 250mL there-necked flask, DMSO is solvent, magnetic agitation and logical argon gas, is heated to 150 DEG C of oil bath, adds 3.038g
(0.02mol) cesium fluoride (CsF), back flow reaction is for 24 hours.Reaction solution is poured into ice water, is extracted with dichloromethane, be decompressed to-
101.325kPa boils off solvent, and product is with methylene chloride:N-hexane=1:1 (volume ratio) is mobile phase, silica gel is that stationary phase is made
Column chromatography purification is collected product and is spin-dried for, and drying for 24 hours, obtains product 2.692g, yield 65% in 80 DEG C of vacuum.In this
Mesosome structure is as follows：
S2. synthetic intermediate 5- (4- (bis (6-nitronaphthalen-2-yl) amino) phenyl) thiophen-
2-amine：
By 10.287 (0.02mol) N- (4-bromophenyl) -6-nitro-N- (6-nitronaphthalen-2-yl)
Naphthalen-2-amine and 4.289g (0.03mol) (5-aminothiophen-2-yl) boronicacid are added to
In 500mL there-necked flask, it is added 400mL tetrahydrofuran (THF), adds the solution of potassium carbonate 45mL of 2mol/L, and be added 5mL's
0.020g tetra-triphenylphosphine palladium, back flow reaction is added to after 75 DEG C in aliquat336, magnetic agitation simultaneously logical argon gas, oil bath heating
24h.Reaction solution is decompressed to -101.325kPa and boils off solvent, product is with methylene chloride:N-hexane=1:1 (volume ratio) is stream
Dynamic phase, silica gel are that stationary phase makees column chromatography purification, collect product and are spin-dried for, drying for 24 hours, obtains product in 80 DEG C of vacuum
6.396g, yield 75%.The intermediate structure is as follows：
S3. N is synthesized2,N2-bis(4-nitrophenyl)-[1,1'-biphenyl]-2,4'-diamine：
By 5.326g (0.01mol) N4,N4-bis(4-nitrophenyl)-[1,1'-biphenyl]-4,4'-diamine
It is added in 500mL there-necked flask, is 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 10mL hydrazine hydrate is added, back flow reaction for 24 hours after, reaction solution is filtered, by filtrate crystallisation by cooling,
80 DEG C of filter cake vacuum drying of gained are filtered again for 24 hours, obtain product 4.253g, yield 90%.The infrared spectrogram of compound
As shown in Figure 1.
The synthesis of polyimides：
N2-(6-aminonaphthalen-2-yl)-N2-(4-(5-aminothiophen-2-yl)phenyl)
Naphthalene-2,6-diamine0.9452g (2mmol) and n,N-Dimethylformamide 8ml are added in three-necked flask, are passed through
Argon gas is warming up to 30 DEG C, and 3,3', 4,4'- benzophenone tetracid dianhydride (BTDA) 0.6444g (2mmol) are dissolved into 8mlN, N- bis-
Dropped evenly in three-necked flask with constant pressure funnel in 1~2h in methylformamide, then proceed to reaction 14h, then plus
Enter 6ml acetic anhydride and 2ml triethylamine, be warming up to 45 DEG C the reaction was continued 10h, reaction terminates after being cooled to room temperature discharging in ethyl alcohol
In, it filters, washing repeats 2~3 times, is finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtains filemot hyperbranched poly
Imide polymer, structural formula are as follows：
Embodiment 5
N2-(4-(6-aminonaphthalen-2-yl)phenyl)-N2-(5-aminothiophen-2-yl)
The synthesis of thiophene-2,5-diamine：
S1. synthetic intermediate N- (4-bromophenyl) -5-nitro-N- (5-nitrothiophen-2-yl)
thiophen-2-amine：
1.720g (0.01mol) 4- bromaniline and 12.752mL (0.05mol) 2-iodo-5-nitrothiophene are added
Enter into 250mL there-necked flask, DMSO is solvent, magnetic agitation and logical argon gas, is heated to 150 DEG C of oil bath, adds 3.038g
(0.02mol) cesium fluoride (CsF), back flow reaction is for 24 hours.Reaction solution is poured into ice water, is extracted with dichloromethane, be decompressed to-
101.325kPa boils off solvent, and product is with methylene chloride:N-hexane=1:1 (volume ratio) is mobile phase, silica gel is that stationary phase is made
Column chromatography purification is collected product and is spin-dried for, and drying for 24 hours, obtains product 2.131g, yield 50% in 80 DEG C of vacuum.In this
Mesosome structure is as follows：
S2. synthetic intermediate N- (4- (6-aminonaphthalen-2-yl) phenyl) -5-nitro-N- (5-
nitrothiophen-2-yl)-thiophen-2-amine：
By 8.525 (0.02mol) N- (4-bromophenyl) -5-nitro-N- (5-nitrothiophen-2-yl)
Thiophen-2-amine and 5.61g (0.03mol) (6-aminonaphthalen-2-yl) boronicacid are added to
In 500mL there-necked flask, it is added 400mL tetrahydrofuran (THF), adds the solution of potassium carbonate 45mL of 2mol/L, and be added 5mL's
0.020g tetra-triphenylphosphine palladium, back flow reaction is added to after 75 DEG C in aliquat336, magnetic agitation simultaneously logical argon gas, oil bath heating
24h.Reaction solution is decompressed to -101.325kPa and boils off solvent, product is with methylene chloride:N-hexane=1:1 (volume ratio) is stream
Dynamic phase, silica gel are that stationary phase makees column chromatography purification, collect product and are spin-dried for, drying for 24 hours, obtains product in 80 DEG C of vacuum
6.351g, yield 65%.The intermediate structure is as follows：
S3.
N2-(4-(6-aminonaphthalen-2-yl)phenyl)-N2-(5-aminothiophen-2-yl)
The synthesis of thiophene-2,5-diamine intermediate：
By 4.885g (0.01mol) N- (4- (6-aminonaphthalen-2-yl) phenyl) -5-nitro-N- (5-
Nitrothiophen-2-yl)-thiophen-2-amine is added in 500mL there-necked flask, and 450mL dehydrated alcohol, magnetic is added
Power stirs and leads to argon gas, and to after 80 DEG C the palladium carbon 0.1g of 10%wt is added, and 10mL hydrazine hydrate is added, reflux is anti-in oil bath heating
After answering for 24 hours, reaction solution is filtered, by filtrate crystallisation by cooling, 80 DEG C of filter cake vacuum drying of gained is filtered again for 24 hours, obtains product
3.857g, yield 90%.The infrared spectrogram of compound is as shown in Figure 1.
The synthesis of polyimides：
N2-(4-(6-aminonaphthalen-2-yl)phenyl)-N2-(5-aminothiophen-2-yl)
Thiophene-2,5-diamine0.8571g (2mmol) and n,N-dimethylacetamide 5ml are added in three-necked flask, are passed through argon
Gas is warming up to 30 DEG C, hexafluorodianhydride (6FDA) (6FDA) 0.8618g (1.94mmol) is dissolved into 5.5mlN, in N- dimethyl acetamide
Dropped evenly in three-necked flask with constant pressure funnel in 1~2h, then proceed to reaction 14h, then be added 6ml acetic anhydride and
2ml triethylamine is warming up to 50 DEG C the reaction was continued 12h, and reaction terminates to discharge in methyl alcohol after being cooled to room temperature, filters, wash, weight
It is 2~3 times multiple, it is finally placed in drying in 80 DEG C of vacuum ovens and for 24 hours, obtains super-branched polyimide polymer russet,
Structural formula is as follows：
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 1~5 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, there is high glass transition temperature by super-branched polyimide prepared by triamine of the present invention
Degree 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 Triamine monomer, which is characterized in that the monomer structure is as shown in logical formula (I)：
Wherein, Ar1Any one in following structural：
Preferably, the Ar1It is selected from
2. Triamine monomer according to claim 1, which is characterized in that the Ar2And Ar3Appointing in following structural
It anticipates one kind：
Preferably, the Ar2It is selected from
One of；
Preferably, the Ar3It is selected from
One of.
3. the preparation method of Triamine monomer according to claim 1 or 2, which is characterized in that include the following steps：
S1. the Ar that will replace containing a halogen atom and an amino1Monomer with replace containing a halogen atom and nitro
Ar2Monomer is added in solvent, obtains monomer 1 by Ullmann coupling reaction；
S2. monomer 1 in step S1 and the Ar containing a boric acid and the substitution of an amino or a boric acid and a nitro are utilized3
Monomer is added in solvent, reacts to obtain monomer 2 or monomer 3 by Suzuki；
S3. monomer 2 in step S2 or monomer 3 are added in solvent, by reduction reaction up to three shown in general structure (I)
Amine monomers；
Monomer 1 in step S1, monomer 2 and monomer 3 are respectively provided with following structure feature in step S2：
Wherein X is F, Cl, Br or I.
4. the preparation method of Triamine monomer according to claim 3, which is characterized in that the Ullmann coupling reaction is
It is passed through protective gas during the reaction, heats, is purified after alkali back flow reaction is added, it is dry in vacuum；The Suzuki reaction
It is that alkali is added during the reaction, stirs and be passed through protective gas, heat, catalyst is added, is purified after back flow reaction, it is dry；
The reduction reaction is to be passed through protective gas during the reaction, heating, and reducing agent is added, purifies after back flow reaction, dry.
5. the preparation method of Triamine monomer according to claim 4, which is characterized in that in the Ullmann coupling reaction
Ar1Monomer and Ar2The mass ratio of the material of monomer to feed intake is 1 ︰, 1.6~1 ︰ 6, and the dosage of alkali is Ar1The amount of the substance of monomeric charge
1~3 times, monomer 1 and Ar in Suzuki reaction3The mass ratio of the material of monomer to feed intake is 1 ︰, 1~1 ︰ 2, the dosage of alkali
It is Ar31~6 times of monomer dosage, monomer 2 or monomer 3 and the mass ratio of the material of reducing agent to feed intake are in the reduction reaction
1 ︰, 2~1 ︰ 32.
6. the preparation method of Triamine monomer according to claim 4, which is characterized in that the alkali is sodium hydride, hydroxide
Sodium, potassium hydroxide, sodium carbonate, potassium carbonate, cesium fluoride, n-BuLi, potassium tert-butoxide, the tert-butyl alcohol receive, two silicon substrate amido of hexamethyl
One or more of lithium.
7. the preparation method of Triamine monomer according to claim 4, which is characterized in that the catalyst is Pd [PPh3]4、
Pd(DPPF)Cl2、PdCl2(CH3CN)2、PdCl2、Pd(OAc)2、Pd(PPh3)2Cl2One or more of；The reducing agent is
One or more of hydrazine hydrate, ammonium formate, sodium borohydride, vitamin C, sodium citrate, iron powder, zinc powder.
8. the preparation method of Triamine monomer according to claim 4, which is characterized in that solvent described in step S1 is diformazan
Base sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4 dioxane, toluene, dimethylbenzene, acetone, acetonitrile, in diphenyl ether
It is one or more of；Solvent described in step S2 is dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, 1,4 dioxies six
One or more of ring, toluene, dimethylbenzene, acetone, acetonitrile, water；Solvent described in step S3 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-dimethylformamide, acetic acid
One or more of ethyl ester, toluene.
9. the preparation method of Triamine monomer according to claim 4, which is characterized in that the heating temperature be 50 DEG C~
170 DEG C, the reflux time is 10~48h；40 DEG C~120 DEG C of the drying temperature, the drying time is 6~30h；
The protective gas is one or more of nitrogen, helium, neon, argon gas, Krypton, xenon, radon gas.
10. Triamine monomer according to any one of claims 1 to 9 is applied to synthesis of super branched and functionalized polyimides, polyamides
Amine, polyamidoimide or polyesterimide polymer.
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| CN115286517A (en) * | 2022-06-01 | 2022-11-04 | 慧迈材料科技(广东)有限公司 | Diamine monomer and thermoplastic polyimide synthesized from same |
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