CN112778338A - Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof - Google Patents
Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof Download PDFInfo
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- CN112778338A CN112778338A CN202110170614.4A CN202110170614A CN112778338A CN 112778338 A CN112778338 A CN 112778338A CN 202110170614 A CN202110170614 A CN 202110170614A CN 112778338 A CN112778338 A CN 112778338A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
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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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
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Abstract
The invention discloses a fluorine-containing polycarbazole dianhydride-containing compound and a synthesis method thereof, wherein the structure of the compound is as follows:
Description
Technical Field
The invention belongs to the technical field of polyimide materials, and particularly relates to a fluorine-containing polycarbazole-containing dianhydride compound.
Background
3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenylcarbazole dianhydride ] } carbazole is a novel fluorine-containing dianhydride compound containing polycarbazole groups, has a good electron donor, and can be polymerized with various amine compounds to produce polyimide. Polyimide has excellent properties such as high strength, low dielectric, high modulus, high temperature resistance, radiation resistance and the like, is concerned, and has wide application prospect and great commercial value in a plurality of high and new technical fields such as aerospace, aviation, space, microelectronics, precise machinery, medical appliances, organic light-emitting and electricity-generating materials, optical storage and the like.
Polyimide is generally prepared from dianhydride and diamine through binary copolymerization, and different monomer structures determine various properties of polyimide materials, so the research and development of polyimide monomer raw materials are a prerequisite condition for developing novel polyimide materials. At present, polyimides with single performance are very common, and how to develop a polyimide with multiple functional properties at the same time is an important subject of polyimide research at present.
The fluorine-containing polycarbazolyl is a group which has good electron transfer capacity, high electron density and good rigid structure, and has good light transmittance in a visible light region. In the polyimide prepared by using the dianhydride compound constructed by the fluorine-containing polycarbazole group and the diamine monomer, the ultraviolet absorption range of the dianhydride structure can be strengthened, and the molecular delocalization is increased, so that the polyimide has excellent storage performance and photoelectric performance.
Disclosure of Invention
The invention aims to improve the performance of a polyimide material, and provides a dianhydride compound containing a fluorine-containing polycarbazolyl structure and having high planarity and a synthesis method thereof.
The invention aims to realize the following that the fluorine-containing polycarbazole dianhydride-containing compound is characterized by having the following structure:
the compound is used for synthesizing polyimide materials.
In order to achieve the object of the present invention, the fluorine-containing polycarbozole-containing compound is prepared by the following synthetic route:
the 3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenylcarbazole dicarboxylic acid ] } carbazole shown in the structure I is used asThe method comprises the steps of taking organic solvents such as acetic acid and acid anhydride as reaction media, heating to reflux and preserving heat for 5-10 hours in an oxygen-free environment under the catalysis of a silicon-based solid dehydrating agent SH-01 to obtain a corresponding fluorine-containing polycarbozole compound II 3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenyl carbazole dianhydride ] } carbazole, filtering and recrystallizing after the reaction is finished, purifying omega II to be more than 99%, and obtaining the reaction yield to be more than 50%.
In order to further achieve the purpose of the invention, the organic solvent may be one or more of acetic acid, acetic anhydride, trifluoroacetic anhydride, xylene, tetrahydrofuran, and the like.
In order to further realize the purpose of the invention, the reaction temperature can be 30-150 ℃, and the reaction time can be 5-10 h.
When the structure of the compound is designed, the fluorine-containing polycarbazole-containing dianhydride compound is designed and synthesized, and the dianhydride is used for preparing the fluorine-containing polycarbazole-containing polyimide, so that the fluorine-containing polycarbazole-containing polyimide has excellent storage performance and good photoelectric performance. The invention has the following beneficial effects:
1. the invention introduces the fluorine-containing polycarbazole group containing strong intramolecular electron transfer into the dianhydride compound, and after the polyimide is synthesized, the electron transfer capability is greatly improved.
2. The dianhydride compound synthesized by the invention and the diamine monomer are polymerized to generate polyimide, and the polyimide has good random static storage behavior and good tensile property.
3. The dianhydride compound synthesized by the invention and the diamine monomer are polymerized to generate polyimide, the polyimide has better ultraviolet absorption capacity and good light transmission in a visible light region, and the monomer is transparent in the visible light region.
4. The data for the compounds of the invention compared to BPDA are shown in the following table:
| name of Compound | Molecular weight | Boiling point/. degree.C | Melting Point/. degree.C |
| BPDA | 294.22 | 609 | 199 |
| Ⅱ | 1061.78 | 905 | 420 |
Detailed Description
The present invention is further illustrated by the following examples, which are included merely for the purpose of clarity and are not intended to limit the invention.
A fluorine-containing polycarbazole-containing dianhydride compound has the following structure:
the synthetic route is as follows:
adding 30g of 3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenylcarbazole dicarboxylic acid ] } carbazole, 100mL of tetrahydrofuran, 90mL of acetic acid and 1000mL of acetic anhydride into a 500mL three-neck reaction flask provided with a mechanical stirring device, a reflux condenser, a nitrogen protection device and an addition funnel in sequence, starting stirring and heating until the mixture flows back, reacting for 6 hours, sampling and analyzing, determining the reaction termination according to the LC analysis result, cooling, filtering, adding dichloromethane for recrystallization, purifying, and recovering mother liquor to obtain 14.5g of a product. Purity ω: 99.3 percent of the total weight of the mixture,the yield was 50.01%.
The dianhydride monomer and the 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl monomer are synthesized into a copolymerization type fluorine-containing Polyimide (PI) film according to a certain proportion, the film has good tensile property, the tensile strength is 100MPa-120MPa, and the tensile property of the copolymerization type fluorine-containing Polyimide (PI) film synthesized by the biphenyl dianhydride and the 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl monomer is only about 80 MPa; the PI material formed by the dianhydride monomer and the diamine monomer can be used for engineering plastics, such as thermosetting plastics and thermoplastic plastics, can be molded and molded by injection molding or transfer molding (RTM), and is mainly used for self-lubricating, sealing, insulating and structural materials;
and (3) product structure confirmation: the elemental analysis measured values were w (c) = 63.37%, w (h) =2.16%, w (f) = 21.40%, w (n) =3.99%, w (o) = 9.08%; theoretical values of w (c) = 63.35%, w (h) = 2.18%, w (f) = 21.47%, w (n) =3.96%, w (o) = 9.04%; melting Point>470℃；MS：m/s= 1061.78（M+)。
Claims (5)
1. A fluorine-containing polycarbazole-containing dianhydride compound is characterized in that the structure of the compound is as follows:
the compound can be used for synthesizing polyimide materials.
2. The synthesis method of the fluorine-containing polycarbazole dianhydride based compound of claim 1, which is characterized by adopting the following synthesis route:
the method comprises the steps of taking 3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenylcarbazole dicarboxylic acid ] } carbazole shown in a structure I as a raw material, taking an organic solvent as a reaction medium, heating to reflux and preserving heat for 5-10 h under the catalysis of a silicon-based solid dehydrating agent SH-01 and in an oxygen-free environment to obtain a corresponding fluorine-containing polycarbazole dianhydride compound II 3, 6-bis { N- [ 3, 5-bis (trifluoromethyl) phenylcarbazole dianhydride ] } carbazoleAfter the reaction is finished, the purified omega II is more than 99 percent through filtration and recrystallization, and the reaction yield is more than 50 percent.
3. The method for synthesizing fluorine-containing polycarbazole dianhydride based compound according to claim 2, wherein the organic solvent is one or more of acetic acid, acetic anhydride, trifluoroacetic anhydride, xylene and tetrahydrofuran.
4. The synthesis method of the fluorine-containing polycarbozole dianhydride compound according to claim 2, wherein the reaction temperature is 30-150 ℃ and the reaction time is 5-10 h.
5. The application of the fluorine-containing polycarbazole-containing dianhydride compound of claim 1 in the field of polyimide.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110170614.4A CN112778338A (en) | 2021-02-08 | 2021-02-08 | Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof |
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| CN202110170614.4A CN112778338A (en) | 2021-02-08 | 2021-02-08 | Fluorine-containing polycarbazole-containing dianhydride compound and synthesis method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980493A (en) * | 2014-05-30 | 2014-08-13 | 北京化工大学常州先进材料研究院 | Isomerized polyimide capable of being used for flexible high-density information storage material, and preparation of isomerized polyimide |
| CN109535139A (en) * | 2018-12-24 | 2019-03-29 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of carbazole and its synthetic method and application |
| CN110655649A (en) * | 2019-08-28 | 2020-01-07 | 武汉华星光电半导体显示技术有限公司 | Polyimide and preparation method thereof |
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2021
- 2021-02-08 CN CN202110170614.4A patent/CN112778338A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980493A (en) * | 2014-05-30 | 2014-08-13 | 北京化工大学常州先进材料研究院 | Isomerized polyimide capable of being used for flexible high-density information storage material, and preparation of isomerized polyimide |
| CN109535139A (en) * | 2018-12-24 | 2019-03-29 | 山东盛华新材料科技股份有限公司 | One kind is containing two compound anhydride of carbazole and its synthetic method and application |
| CN110655649A (en) * | 2019-08-28 | 2020-01-07 | 武汉华星光电半导体显示技术有限公司 | Polyimide and preparation method thereof |
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Application publication date: 20210511 |