CN109438470A - One kind is containing two compound anhydride of thiophene and its synthetic method and application - Google Patents
One kind is containing two compound anhydride of thiophene and its synthetic method and application Download PDFInfo
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- CN109438470A CN109438470A CN201811579520.7A CN201811579520A CN109438470A CN 109438470 A CN109438470 A CN 109438470A CN 201811579520 A CN201811579520 A CN 201811579520A CN 109438470 A CN109438470 A CN 109438470A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
- C07D495/14—Ortho-condensed systems
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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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The dianhydride compound and preparation method thereof containing thiophene-structure that the invention discloses a kind of, the structure of the compound areBy dibenzo thiophene phenyl -1,1 ', 2,2 ',-tetrabasic carboxylic acid is dissolved in the organic solvents such as acetic acid, acetic anhydride, 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 two compound anhydride dibenzo thiophene phenol -1 of thiophene accordingly, 1 ', 2,2 '-dianhydrides, after having reacted, it filtered, recrystallized, 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
Dibenzo thiophene phenol -1,1 ', 2,2 '-dianhydrides are a kind of dianhydride compounds of novel thienyl-containing group, are had good
Electron donor, can be with a variety of aminated compounds polymerization polyimides.Polyimides have high-intensitive, low dielectric, high-modulus,
The excellent properties such as high temperature resistant and radiation hardness and be concerned, space flight, aviation, space, microelectronics, precision machinery, medical instrument,
Organic light emission sends a telegraph many high-technology fields such as material, optical storage and has broad application prospects and huge business valence
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.
Thiophene is a kind of good electron donor with armaticity, and D- π-A system easy to form is close with high electronics
Degree and good rigid structure.The present invention rolls into a ball building dianhydride compound with dibenzo thiophene phenyl, then prepared with diamines monomer
In polyimides, the electron donation of dianhydride structure can be strengthened, increase molecule delocalization, it is made to embody excellent storage performance
And photoelectric properties.
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 thiophene-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 thiophene-structure.
The object of the present invention is achieved like this, a kind of two compound anhydride containing thiophene, its main feature is that the compound structure
It is as follows:
The compound is used for the synthesis of polyimide material.
In order to achieve the object of the present invention, above-mentioned to use following synthetic route containing two compound anhydride of thiophene:
With dibenzo thiophene phenyl -1 shown in structure I, 1 ', 2,2 ',-tetrabasic carboxylic acid is raw material, organic molten with acetic acid, acid anhydrides etc.
Agent is reaction medium, under silicon substrate solid dehydrating agent SH-01 catalysis, under oxygen-free environment, is heated to reflux 5~10h of heat preservation, obtains
To corresponding two anhydride compound ii dibenzo thiophene phenol -1 containing thiophene, 1 ', 2,2 '-dianhydrides after having reacted, are filtered, are recrystallized,
Its purified II > 99% of ω, reaction yield are 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 thienyl-containing, utilizes this dianhydride system
The polyimides of the standby structure containing thiophene, has excellent storage performance and good photoelectric properties.
Beneficial effects of the present invention are as follows:
1. the thienyl group containing strong cyclic voltammetry method is introduced into two compound anhydrides by the present invention, synthesis of polyimides
Afterwards, electron transport ability is greatly improved.
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 528~574 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 dianhydride monomer BPDA correlation data:
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.
A kind of two compound anhydride containing thiophene, structure are as follows:
Preparation method is: to equipped with mechanical stirring, reflux condensing tube, nitrogen protection device, charging hopper 500mL tri-
Dibenzo thiophene phenyl -1,1 ', 2,2 ',-tetrabasic carboxylic acid 30g, silicon substrate solid dehydrating agent SH-01 are sequentially added in mouth reaction flask
0.15g, tetrahydrofuran 100mL, acetic acid 90mL, acetic anhydride 110mL start to be heated with stirring to reflux, react 6h, sampling analysis,
Result is analyzed according to GC and determines reaction terminating, and chloroform recrystallization is added in cooling, filtering, and purified, disposing mother liquor obtains
Product 20.21g.Purity ω: 99.3%, yield 74.85%.
Product structure confirmation: elemental analysis measured value is W (C)=59.48%, W (H)=1.28%, W (S)=9.67%,
W (O)=29.57%；Theoretical value is W (C)=59.26%, W (H)=1.24%, W (S)=9.89%, W (O)=29.61%；
Fusing point > 370；DEG C MS:m/s=324.26 (M+)；FT-IR (KBr) ν C=O:1786CM-1, 1720CM-1；1H NMR=
(400MHz,DCCl3)；δ 8.84 (d, J=8.0Hz, 2H, ArH), 8.96 (d, 2H, ArH).
Claims (5)
1. a kind of two compound anhydride containing thiophene, it is characterized in that the structure of the compound is as follows:
Such compound can be used for the synthesis of polyimide material.
2. a kind of synthetic method of two compound anhydride described in claim 1 containing thiophene, it is characterized in that using following synthesis road
Line:
With dibenzo thiophene phenyl -1 shown in structure I, 1 ', 2,2 ',-tetrabasic carboxylic acid is raw material, with acetic acid, acetic anhydride, trifluoroacetic acid
One or more of organic solvents are reaction medium in acid anhydride, toluene, ethylbenzene, dimethylbenzene or tetrahydrofuran, in silicon substrate solid dehydrating agent
Under SH-01 catalysis, under oxygen-free environment, it is heated to reflux 5~10h of heat preservation, obtains containing two anhydride compound ii of thiophene accordingly
Dibenzo thiophene phenol -1,1 ', 2,2 '-dianhydrides after having reacted, are filtered, are recrystallized, purified II > 99% of ω, reaction yield
Greater than 70%.
It is organic molten described in feature 3. a kind of synthetic method of two compound anhydride containing thiophene according to claim 2
Agent 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 thiophene 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778339A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Polythiophene dianhydride compound and synthesis method thereof |
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| US4046779A (en) * | 1975-05-30 | 1977-09-06 | Standard Oil Company (Indiana) | Dibenzofuran-2,3,6,7-tetracarboxylic acid dianhydride |
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| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
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2018
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| US4046779A (en) * | 1975-05-30 | 1977-09-06 | Standard Oil Company (Indiana) | Dibenzofuran-2,3,6,7-tetracarboxylic acid dianhydride |
| US4138392A (en) * | 1975-05-30 | 1979-02-06 | Standard Oil Company (Indiana) | Imide nitrogen dibenzofurans polymers |
| CN1605587A (en) * | 2003-10-08 | 2005-04-13 | 中国科学院化学研究所 | Fluoro-aromatic organic tetracarboxylic dianhydride and its preparation method and use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778339A (en) * | 2021-02-08 | 2021-05-11 | 山东盛华科技创业园有限公司 | Polythiophene dianhydride compound and synthesis method thereof |
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