CN109535139A - One kind is containing two compound anhydride of carbazole and its synthetic method and application - Google Patents
One kind is containing two compound anhydride of carbazole and its synthetic method and application Download PDFInfo
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- CN109535139A CN109535139A CN201811579518.XA CN201811579518A CN109535139A CN 109535139 A CN109535139 A CN 109535139A CN 201811579518 A CN201811579518 A CN 201811579518A CN 109535139 A CN109535139 A CN 109535139A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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Abstract
The dianhydride compound and preparation method thereof containing carbazole structure that the invention discloses a kind of, the structure of the compound areR1 is fluorine in formula, chlorine, H, the straight chained alkyl of C1-C5, the unbranched alkoxy of C1-C5, one of cyano, R2 is fluorine, chlorine, H, the straight chained alkyl of C1-C5, the unbranched alkoxy of C1-C5, one of cyano, R3 is fluorine, chlorine, H, the straight chained alkyl of C1-C5, the unbranched alkoxy of C1-C5, one of cyano, R1, R2, R3 is identical or different, by 4, 4 ', (N- (n- fluorine) phenyl carbazole) -1, 1 ', 2, 2 ', tetraphenyl carboxylic acid is dissolved in acetic acid, in the organic solvents such as acetic anhydride, under silicon substrate solid dehydrating agent SH-01 catalysis, under oxygen-free environment, it is heated to 5~10h of reflux heat preservation, after having reacted, through filtering, recrystallization, its purified ω(Ⅱ)> 99%, reaction yield are greater than 70%；Such compound can be used for the synthesis of polyimide material.
Description
Technical field
The invention belongs to polyimide material technical fields, and in particular to a kind of two anhydride monomers and its synthetic method and answer
With.
Background technique
4,4 ',-(N- (n- fluorine) phenyl carbazole) -1,1 ', 2,2 ',-phenyl dianhydride is the two of a kind of novel carbazolyl-containing group
Acid anhydride compound has big non-planar big conjugated structure, can be with a variety of aminated compounds polymerization polyimides.Polyimides
Be concerned with excellent properties such as high-intensitive, low dielectric, high-modulus, high temperature resistant and radiation hardness, space flight, aviation, space,
Microelectronics, precision machinery, medical instrument, organic light emission send a telegraph many high-technology fields such as material, optical storage with wide
Application prospect and huge commercial value.
Polyimides is generally made by dianhydride and diamines by binary copolymerization, and different monomer structures decides polyimides
The properties of material, so being to develop the prerequisite of new type polyimide material to the research and development of polyimide monomers raw material.
The polyimides for having single performance at present is very common, and the poly- of multiple functions property can be had simultaneously by how developing one kind
Acid imide is the important topic of current polyimides research.
Carbazole compound intramolecular has biggish conjugated system and strong cyclic voltammetry method, with special rigid
Property condensed cyclic structure, general thermal stability and photochemical stability with higher, and be easy to carry out structural modification on carbazole ring to draw
Enter a variety of functional groups.Polyimides containing carbazole structure has good thermal stability, photoelectric properties and excellent storage performance.
Summary of the invention
It is an object of the invention to improve the performance of polyimide material, provide it is a kind of containing carbazole structure have high plane
Property dianhydride compound, the compound be applied to polyimides synthesis.
The synthetic method of another object of the present invention is to provide above-mentioned two compound anhydrides containing carbazole structure.
The object of the present invention is achieved like this, a kind of two compound anhydride containing carbazole, its main feature is that the compound structure
It is as follows:
R1 is one of fluorine, chlorine, the straight chained alkyl of H, C1-C5, the unbranched alkoxy of C1-C5, cyano in formula, and R2 is
One of fluorine, chlorine, the straight chained alkyl of H, C1-C5, the unbranched alkoxy of C1-C5, cyano, R3 be fluorine, chlorine, H, C1-C5 it is straight
One of alkyl group, the unbranched alkoxy of C1-C5, cyano, R1, R2, R3 are identical or different, such compound is sub- for polyamides
The synthesis of amine material.
In order to achieve the object of the present invention, above-mentioned to use following synthetic route containing two compound anhydride of carbazole:
With 4,4 '-shown in structure I (N- (n- fluorine) phenyl carbazole) -1,1 ', 2,2 ',-tetraphenyl carboxylic acid is raw material, with second
Acid, acid anhydrides organic solvent are reaction medium, under silicon substrate solid dehydrating agent SH-01 catalysis, under oxygen-free environment, are heated to flowing back
5~10h is kept the temperature, obtains containing two anhydride compound ii 4,4 ' of carbazole accordingly,-(N- (n- fluorine) phenyl carbazole) -1,1 ', 2,2 ', -
Phenyl dianhydride after having reacted, is filtered, is recrystallized, purified II > 99% of ω, and reaction yield is greater than 70%.
In order to further realize the purpose of the present invention, can be the organic solvent is acetic acid, acetic anhydride, trifluoroacetic acid
One or more of acid anhydride, toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran.
In order to further realize the purpose of the present invention, it can be 30~150 DEG C of reaction temperature, 5~10h of reaction time.
For the present invention when designing compound structure, design has synthesized the dianhydride compound of carbazolyl-containing, utilizes this dianhydride system
The standby polyimides containing carbazole structure, has good thermal stability, photoelectric properties and excellent storage performance.
Beneficial effects of the present invention are as follows:
1. the carbazole group containing strong cyclic voltammetry method is introduced into two compound anhydrides by the present invention, synthesis of polyimides
Afterwards, carbazole group is greatly improved as electron-donating group, electron transport ability.
2. two compound anhydrides and the diamine monomer polymerization that the present invention synthesizes generate polyimides, polyimides has good
Thermal stability, 10% decomposition temperature scope of polyimides reaches 546~596 DEG C.Polyimides can be used for manufacturing resin
With the high molecular materials such as PI new membrane.
3. the compound in the present invention see the table below with BPDA correlation data:
| Compound name | Molecular weight | Boiling point/DEG C | Fusing point/DEG C |
| BPDA | 294.22 | 609 | 199 |
| Ⅱ(1) | 589.47 | 834 | 564 |
| Ⅱ(2) | 553.49 | 786 | 482 |
| Ⅱ(3) | 535.50 | 705 | 397 |
The stability of dianhydride monomer of the present invention is more preferable in terms of molten boiling point.
Specific embodiment
The present invention is further described with reference to embodiments, it should be noted that embodiment below is only for clear
Understand the present invention, the present invention is not limited to this embodiment.
Embodiment 1, a kind of two compound anhydride containing carbazole, structure are as follows:
Preparation method is: to equipped with mechanical stirring, reflux condensing tube, nitrogen protection device, charging hopper 500mL tri-
4,4 '-(N- (3,4,5- trifluoro) phenyl carbazole) -1,1 ', 2,2 ',-tetraphenyl carboxylic acid 30g, silicon are sequentially added in mouth reaction flask
Base solid dehydrating agent SH-01 0.15g, tetrahydrofuran 100mL, acetic acid 90mL, acetic anhydride 110mL, start to be heated with stirring to back
Stream reacts 6h, and sampling analysis analyzes result according to GC and determines reaction terminating, and chloroform recrystallization, warp is added in cooling, filtering
Purifying, disposing mother liquor obtain product 21.68g.Purity ω: 99.4%, yield 76.69%.
Product structure confirmation: elemental analysis measured value is W (C)=68.96%, W (H)=2.45%, W (N)=2.16%,
W (O)=16.71%, W (F)=9.78%；Theoretical value is W (C)=69.27%, W (H)=2.39%, W (N)=2.38%, W
(O)=16.29%, W (F)=9.67%；Fusing point > 560 DEG C；MS:m/s=589.08 (M+)；FT-IR (KBr) ν C=O:
1786CM-1, 1738CM-1；1H NMR=(400MHz, DCCl3)；δ 6.70 (d, J=8.0Hz, 2H, ArH), 7.46 (d, 2H,
ArH), 7.30 (d, 2H, ArH), 7.46 (d, 2H, ArH), 7.77 (m, 2H, ArH), 8.03 (d, 2H, ArH), 8.40 (d, 2H,
ArH), 8.56 (d, 2H, ArH).
Embodiment 2, a kind of two compound anhydride containing carbazole, structure are as follows:
Preparation method is: to equipped with mechanical stirring, reflux condensing tube, nitrogen protection device, charging hopper 500mL tri-
4,4 '-(N-4- fluorophenyl carbazole) -1,1 ', 2,2 ',-tetraphenyl carboxylic acid 30g are sequentially added in mouth reaction flask, silicon substrate solid takes off
Aqua SH-01 0.15g, tetrahydrofuran 100mL, acetic acid 90mL, acetic anhydride 110mL start to be heated with stirring to reflux, react 6h,
Sampling analysis analyzes result according to GC and determines reaction terminating, and chloroform recrystallization, purified, mother liquor is added in cooling, filtering
Recycling, obtains product 21.08g.Purity ω: 99.6%, yield 74.84%.
Product structure confirmation: elemental analysis measured value is W (C)=73.12%, W (H)=2.96%, W (N)=2.74%,
W (O)=17.97%, W (F)=3.21%；Theoretical value is W (C)=73.78%, W (H)=2.91%, W (N)=2.53%, W
(O)=17.35%, W (F)=3.43%；Fusing point > 480 DEG C；MS:m/s=553.10 (M+)；FT-IR (KBr) ν C=O:
1786CM-1, 1738CM-1；1H NMR=(400MHz, DCCl3)；δ 7.0 (d, J=8.0Hz, 2H, ArH), 7.20 (d, 2H,
ArH), 7.30 (d, 2H, ArH), 7.46 (d, 2H, ArH), 7.77 (m, 2H, ArH), 8.03 (d, 2H, ArH), 8.40 (d, 2H,
ArH), 8.56 (d, 2H, ArH).
Embodiment 3, a kind of two compound anhydride containing carbazole, structure are as follows:
Preparation method is: to equipped with mechanical stirring, reflux condensing tube, nitrogen protection device, charging hopper 500mL tri-
4,4 '-(N- phenyl carbazole) -1,1 ', 2,2 ',-tetraphenyl carboxylic acid 30g, silicon substrate solid dehydrating agent are sequentially added in mouth reaction flask
SH-01 0.15g, tetrahydrofuran 100mL, acetic acid 90mL, acetic anhydride 115mL start to be heated with stirring to reflux, react 6h, sampling
Analysis analyzes result according to GC and determines reaction terminating, and cooling is filtered, addition chloroform recrystallization, purified, disposing mother liquor,
Obtain product 21.24g.Purity ω: 99.5%, yield 75.56%.
Product structure confirmation: elemental analysis measured value is W (C)=76.92%, W (H)=3.08%, W (N)=2.48%,
W (O)=17.52%；Theoretical value is W (C)=76.25%, W (H)=3.20%, W (N)=2.62%, W (O)=17.93%；
Fusing point > 385 DEG C；MS:m/s=535.11 (M+)；FT-IR (KBr) ν C=O:1786CM-1, 1738CM-1；1H NMR=
(400MHz,DCCl3)；δ 7.3 (m, J=8.0Hz, 7H, ArH), 7.46 (d, 2H, ArH), 7.77 (m, 2H, ArH), 8.03 (d,
2H, ArH), 8.40 (d, 2H, ArH), 8.56 (d, 2H, ArH).
Claims (5)
1. a kind of two compound anhydride containing carbazole, it is characterized in that the structure of the compound is as follows:
In formula R1 be one of fluorine, chlorine, the straight chained alkyl of H, C1-C5, the unbranched alkoxy of C1-C5, cyano, R2 be fluorine, chlorine,
H, one of the straight chained alkyl of C1-C5, the unbranched alkoxy of C1-C5, cyano, R3 be fluorine, chlorine, H, C1-C5 straight chained alkyl,
One of the unbranched alkoxy of C1-C5, cyano, R1, R2, R3 are identical or different, such compound can be used for polyimides material
The synthesis of material.
2. a kind of synthetic method of two compound anhydride described in claim 1 containing carbazole, it is characterized in that using following synthesis road
Line:
In formula R1 be one of fluorine, chlorine, the straight chained alkyl of H, C1-C5, the unbranched alkoxy of C1-C5, cyano, R2 be fluorine, chlorine,
H, one of the straight chained alkyl of C1-C5, the unbranched alkoxy of C1-C5, cyano, R3 be fluorine, chlorine, H, C1-C5 straight chained alkyl,
One of the unbranched alkoxy of C1-C5, cyano, R1, R2, R3 are identical or different；
With 4,4 '-shown in structure I (N- (n- fluorine) phenyl carbazole) -1,1 ', 2,2 ',-tetraphenyl carboxylic acid is raw material, with acetic acid,
One or more of organic solvents are reaction medium in acetic anhydride, trifluoroacetic anhydride, toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran,
Under silicon substrate solid dehydrating agent SH-01 catalysis, under oxygen-free environment, it is heated to reflux 5~10h of heat preservation, obtains containing carbazole accordingly
Two anhydride compound iis 4,4 ',-(N- (n- fluorine) phenyl carbazole) -1,1 ', 2,2 ',-phenyl dianhydride after having reacted, is filtered, again
Crystallization, purified II > 99% of ω, reaction yield are greater than 70%.
3. the synthetic method of a kind of two compound anhydride containing carbazole according to claim 2, it is characterized in that described is organic
Solvent is one or more of acetic acid, acetic anhydride, trifluoroacetic anhydride, toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran.
4. the synthetic method of a kind of two compound anhydride containing carbazole according to claim 2, it is characterized in that reaction temperature 30
~150 DEG C, 5~10h of reaction time.
5. a kind of application of compound described in claim 1 in polyimides field.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778322A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | N-phenyl carbazole dianhydride-containing compound and synthesis method thereof |
| CN112778338A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof |
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| CN101787129A (en) * | 2010-03-04 | 2010-07-28 | 南京航空航天大学 | Soluble and high-temperature resistant aromatic polyimide and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101787129A (en) * | 2010-03-04 | 2010-07-28 | 南京航空航天大学 | Soluble and high-temperature resistant aromatic polyimide and preparation method thereof |
| CN102086181A (en) * | 2011-01-21 | 2011-06-08 | 南京航空航天大学 | Synthesis method of 2,2'-diaryl-4,4',5,5'-biphenyl tetraacid dianhydride monomer |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778322A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | N-phenyl carbazole dianhydride-containing compound and synthesis method thereof |
| CN112778338A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof |
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