CN105885017A - Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond - Google Patents
Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond Download PDFInfo
- Publication number
- CN105885017A CN105885017A CN201510010629.9A CN201510010629A CN105885017A CN 105885017 A CN105885017 A CN 105885017A CN 201510010629 A CN201510010629 A CN 201510010629A CN 105885017 A CN105885017 A CN 105885017A
- Authority
- CN
- China
- Prior art keywords
- molecular polymer
- novel high
- keys
- high molecular
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a naphthalene tetracarboxylic diimide novel high-molecular polymer with a triple bond. The polymer is mainly applied to photoelectric materials, light emitting materials, organic semiconductors and solar cell materials. The general structural formula is shown in the description, wherein n1 is any one natural number from 1-3, n2 is an any natural number, and R1 and R2 are the same substituent group or different substituent groups such as hydrogen, alkyl group, alkoxy, phenyl or alkoxyl benzene. The high-molecular polymer contains thiophene, triple bond and naphthalene tetracarboxylic diimide units, the performance advantages of the thiophene, triple bond and naphthalene tetracarboxylic diimide units are combined, the absorption range of the organic semiconductor material for sun light is enlarged, and therefore the high-molecular polymer is widely applied in organic optoelectronic materials.
Description
[technical field]
The invention belongs to organic photoelectrical material field, a kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys, mainly apply
In photoelectric material, luminescent material, organic semiconductor and solar cell material.
[background technology]
Studying in recent years relatively active has polythiophene, polyaniline, polypyrrole, poly quinoline, a polypyridine etc., wherein polythiophene class material due to
There is good stability and machinability, in sides such as conduction, luminescence, solaode, electromagnetic shielding, memory, microwave absorption and artificial organs
Face has a good application prospect and extremely gazes at.Polythiophene class polymer is its good luminescence property as photoelectric display material, its advantage,
Glow color can be regulated and controled by the regularity of the regulation conjugation length of chain link, the kind of substituent group and polymer, and synthesis difficulty is low.
Owing to naphthalenetetracarbacidic acidic diimide contains big planar conjugate system and good molecule coplanarity, enhance organic semiconducting materials and divide
Interaction between son and electronics, hole transport character, electrochemical reduction character；In addition, naphthalenetetracarbacidic acidic diimide also have stronger can
Modified, it is possible to use easy method introduces alkyl chain and improves dissolubility.
Containing thiophene, acetylene and naphthalenetetracarbacidic acidic diimide unit, take into account the performance advantage of three, and extended this organic semiconductor material
The material absorption region to sunlight, thus effectively extend this photoelectric material solaode, organic electroluminescence optical device, organic field effect tube,
Application in organic optical memory part and organic laser apparatus.
[summary of the invention]
It is an object of the invention to provide a kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys
Another object of the present invention is to provide the preparation method of a kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys
It is a kind of containing the naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys that the present invention provides, and its structural formula is shown below:
Wherein n1For arbitrary natural number of 1-3, n2For arbitrary natural number, R1、R2For identical or different substituent group, can be hydrogen, alkyl,
Alkoxyl, phenyl or alkoxy benzene.
The present invention implements to further provide for the preparation method of a kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys, its step
As follows:
The novel high molecular polymer of structure formula (I), the novel high molecular polymer of structure formula (II), structure formula (III) are provided respectively
Novel high molecular polymer:
The preparation method of example one structure formula (I) compound:
(1) synthetic route of monomer A:
The first step: synthesis reference literature Chaignon, F.；M.；Karlsson, S.；Blart, E.；Odobel, F.；
L.Chem.Commun.2007,64.
Second step: raw material 2-octyldodecyl synthesized reference document Letizia, J.A.；Salata, M.R.；Tribout, C.M.；Facchetti, A.；
Ratner, M.A.；Marks, T.J.J.Am.Chem.Soc.2008,130,9679.
In the there-necked flask that 250mL is dried, addition dibromine naphthalene acid anhydride (1.13g, 2.65mmol), compound 2-octyldodecyl amine (2.0g,
6.7mmol), evacuation changes nitrogen three times, adds 60mL propanoic acid, 130 DEG C of heated and stirred 2h, stops heating.After cooling, add 150ml water,
Extracting three times with dichloromethane, merge organic facies, the potassium hydroxide aqueous solution of organic facies 0.2M washes twice, and washes with water three times, and salt is washed
Washing once, magnesium sulfate is dried.Silica gel column chromatography separating-purifying, eluent dichloromethane/petroleum ether is 1: 4.Screw out solvent and obtain yellow solid 1.9g,
Productivity 35%.1H NMR (300MHz, CDCl3) δ 8.95 (s, 2H), 4.12 (d, 4H), 1.97 (m, 2H), 1.20-1.40 (m, 64H), 0.84-0.89
(m, 12H).
(2) monomer B synthetic route:
The first step: be dried in three mouthfuls to 250mL, addition 2,5-dibromo thiophene (4.0g, 16.53mmol), 13mg PdCl2(PPh3)2(0.69g, 0.98
Mmol), CuI (0.38g, 1.98mmol), evacuation changes nitrogen three times, adds the oxolane that 80ml heavily steams, 40ml triethylamine, is subsequently adding
Trimethylsilyl acetylene (6.49g, 66.12mmol), is heated to 45 DEG C of stirrings.18h is reacted under nitrogen protection.Stop heating, screw out solvent, silica gel
Column chromatography for separation purifies, and eluent is normal hexane.Obtaining product 2, double [(TMS) acetenyl] thiophene of 5-is yellow solid (2.54g, 55.5%).1H NMR (300MHz, CDCl3): δ 7.04 (s, 2H), 0.24 (s, 18H).
Second step: 250ml there-necked flask evacuation is changed nitrogen three times, by 2, double [(TMS) acetenyl] thiophene of 5-(0.40g, 1.45
Mmol) it is dissolved in 20ml dichloromethane solution, adds the methanol saturated solution of 50ml potassium carbonate, be stirred overnight under room temperature.Screw out solvent, silicon
Plastic column chromatography separating-purifying, eluent is petroleum ether, and vacuum is spin-dried for, and obtaining monomer B (2,5-double thiophene acetylenes) is stickiness oily liquids 0.14g, produces
Rate 73%.1H NMR (300MHz, CDCl3): δ 7.09 (s, 2H), 3.32 (s, 2H).
(3) the novel high molecular polymer synthetic route of structure formula (I):
In the there-necked flask that 50ml is dried, add monomer A (0.197g, 0.20mmol), 10mg PdCl2(PPh3)2, 5mg CuI, Yi Jidan
Body B (0.205mmol, 1.025eq), evacuation changes nitrogen three times, adds 10ml and heavily steams oxolane and 10ml diisopropylamine, is heated to 80 DEG C
It is stirred at reflux, under nitrogen protection, reacts 48h.Cooling, instills in 200ml methanol solution and is co-precipitated, and extracts with apparatus,Soxhlet's under nitrogen protection,
Solvent is respectively methanol, acetone, petroleum ether, oxolane, instills in methanol and is co-precipitated, and filters, and the rope that the solid obtained is carried out again carries,
Finally it is co-precipitated with acetone, filters, 50 DEG C of dry 48h of vacuum.Obtain product 0.176g, productivity: 92%.GPC (THF): Mw=62,300 PDI=2.86
The preparation method of example two structure formula (II) compound:
(1) monomer A synthetic route: with in example one about the synthesis of monomer A
(2) monomer C synthetic route:
The first step: adding compound 2,2-di-thiophene (1.66g, 0.01mol) in the there-necked flask that 250m is dried, evacuation changes nitrogen three times,
It is subsequently adding 50ml chloroform, 50ml acetic acid, adds NBS (2.05eq) the most in three batches.The lower room temperature reaction 24h of nitrogen protection.Cooling, adds 200ml
Water, with petroleum ether extraction three times, merges organic facies, and organic phase washed with water three times, once, magnesium sulfate is dried brine.Silica gel column chromatography divides
From purification, eluent is petroleum ether.Obtaining product 5, the double bromine di-thiophene of 5-is white plates crystal (3.0g, 92%).1H NMR(CDCl3, 300
MHz) δ 7.18 (d, 2H), 6.80 (d, 2H).
Second step: be dried in there-necked flask to 250mL, adds 5,5-double bromo-2,2-di-thiophene (1.0g, 2.4mmol), PdCl2(PPh3)2(0.09
G, 0.12mmol), CuI (46mg, 0.24mmol), evacuation changes nitrogen three times, the oxolane that addition 30ml heavily steams, 15ml triethylamine, then
Add trimethylsilyl acetylene (0.56g, 5.8mmol), be heated to 45 DEG C of stirrings.18h is reacted under nitrogen protection.Stop heating, screw out solvent, silica gel
Column chromatography for separation purifies, and eluent is dichloromethane/petroleum ether (1: 4).Vacuum screws out solvent, obtains product 5, double [(TMS) acetylene of 5-
Base] di-thiophene is yellow solid (0.80g, 95%).1H NMR(CDCl3) δ 7.11 (d, 2H), 7.00 (d, 2H), 0.25 (s, 18H).
3rd step: 250ml there-necked flask evacuation is changed nitrogen three times, by raw material 5, double [(TMS) acetenyl] the di-thiophene of 5-(0.70g,
2.0mmol) it is dissolved in 30ml dichloromethane solution, adds the methanol saturated solution of 70ml potassium carbonate, be stirred overnight under room temperature.Screw out solvent, silicon
Plastic column chromatography separating-purifying, eluent is petroleum ether, and vacuum is spin-dried for, and obtaining monomer C (5,5-double acetenyl di-thiophene) is yellow-brown solid 0.43
G, productivity 99%.1H NMR (300MHz, CDCl3): δ 7.18 (d, 2H), 7.04 (d, 2H), 3.41 (s, 2H).
(3) the novel high molecular polymer synthetic route of structure formula (II):
In the there-necked flask that 50mL is dried, add monomer A (0.197g, 0.20mmol), 10mg PdCl2(PPh3)2, 5mg CuI, Yi Jidan
Body C (0.205mmol, 1.025eq), evacuation changes nitrogen three times, adds 10ml and heavily steams oxolane and 10ml diisopropylamine, is heated to 80 DEG C
It is stirred at reflux, under nitrogen protection, reacts 48h.Cooling, instills in 200ml methanol solution and is co-precipitated, and extracts with apparatus,Soxhlet's under nitrogen protection,
Solvent is respectively methanol, acetone, petroleum ether, oxolane, instills in methanol and is co-precipitated, and filters, and the rope that the solid obtained is carried out again carries,
Finally it is co-precipitated with acetone, filters, 50 DEG C of dry 48h of vacuum.Obtain product 0.180g, productivity: 86%.GPC (THF): Mw=75,400
PDI=2.97.
The preparation method of example three structure formula (III) compound:
(1) monomer A synthetic route: with in example one about the synthesis of monomer A
(2) monomer D synthetic route:
The first step: adding compound [2,2 '-5 ', 2 "]-ter thiophene (0.62g, 2.5mol) in the there-necked flask that 250ml is dried, evacuation changes nitrogen
Three times, it is subsequently adding 25mL chloroform and 25mL acetic acid, adds NBS (0.92g, 5.13mmol, 2.05eq) the most in three batches.The lower room temperature of nitrogen protection
Reaction 24h.Cooling, add 200ml water, with chloroform extract three times, merge organic facies, organic phase washed with water three times, brine once, sulfur
Acid magnesium is dried.Screw out solvent, the solid dehydrated alcohol recrystallization obtained, obtain product 5, the double bromine ter thiophene of 5-be light yellow flat crystal (0.90g,
88%).1H NMR(CDCl3, 300MHz) and δ 6.88 (d, 2H), 6.65 (s, 2H), 6.39 (d, 2H).
Second step: be dried in three mouthfuls to 250ml, adds raw material 5, double bromine ter thiophene (0.244g, 0.6mmol) of 5-, PdCl2(PPh3)2(0.030
G, 0.03mmol), CuI (12mg, 0.08mmol), evacuation changes nitrogen three times, the oxolane that addition 20ml heavily steams, 10ml triethylamine, so
Rear addition trimethylsilyl acetylene (0.14g, 1.45mmol), is heated to 45 DEG C of stirrings, reacts 18h under nitrogen protection.Stop heating, add shrend and go out
Reaction, extracts three times with chloroform, and once, salt is washed once in washing.Vacuum screws out solvent, and the solid normal hexane recrystallization obtained repeatedly, obtains
Product 5, double [(TMS) acetenyl] the ter thiophene of 5-is shallow orange crystal (0.21g, 77%).1H NMR(CDCl3) δ 7.14 (d, 2H),
7.07 (s, 2H), 7.01 (d, 2H), 0.26 (s, 18H).
3rd step: 250mL there-necked flask evacuation is changed nitrogen three times, by raw material 5, double [(TMS) acetenyl] the ter thiophene of 5-(0.16g,
0.36mmo]) it is dissolved in 20ml dichloromethane solution, add the methanol saturated solution of 50ml potassium carbonate, under room temperature, stir 48h.Screw out solvent,
Adding dichloromethane to dissolve, wash twice, salt is washed once.Vacuum is spin-dried for, and with normal hexane as eluent, silica gel column chromatography separating-purifying, obtains
It is yellow crystals 0.096g to product monomer D (5,5-double acetenyl ter thiophene), productivity 89%.1H NMR (300MHz, CDCl3): δ 7.19 (d,
2H), 7.09 (s, 2H), 7.03 (d, 2H), 3.48 (s, 2H).
(3) the novel high molecular polymer synthetic route of structure formula (II):
In the there-necked flask that 50mL is dried, add monomer A (0.197g, 0.20mmol), 10mg PdCl2(PPh3)2, 5mg CuI, Yi Jidan
Body D (0.205mmol, 1.025eq), evacuation changes nitrogen three times, adds 10ml and heavily steams oxolane and 10ml diisopropylamine, is heated to 80 DEG C
It is stirred at reflux, under nitrogen protection, reacts 48h.Cooling, instills in 200ml methanol solution and is co-precipitated, and extracts with apparatus,Soxhlet's under nitrogen protection,
Solvent is respectively methanol, acetone, petroleum ether, oxolane, instills in methanol and is co-precipitated, and filters, and the rope that the solid obtained is carried out again carries,
Finally it is co-precipitated with acetone, filters, 50 DEG C of dry 48h of vacuum.Obtain product 0.200g, productivity: 89%.GPC (THF): Mw=79,800
PDI=3.34.
The above is the representative embodiment of the present invention, and not in order to limit the present invention, protection scope of the present invention is with appended right
Claim limits.
Claims (8)
1. the naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys, it is characterised in that there is general structure:
Wherein, n1For arbitrary natural number of 1-3, n2For arbitrary natural number, R1、R2For identical or different substituent group, can be hydrogen, alkyl, alkane
Epoxide, phenyl or alkoxy benzene.
2. the naphthalenetetracarbacidic acidic diimide class novel high molecular polymer preparation method containing three keys, it is characterised in that by monomer A, monomer B with urge
Agent joins in organic solvent, and under nitrogen gas is protected, temperature 70～110 DEG C, insulation reaction 48～72h, cooling, nitrogen protection is lower to be utilized
Apparatus,Soxhlet's carries out rope and carries, and then filtration, 50 DEG C of vacuum are dried 24～72h, obtain the naphthalenetetracarbacidic acidic diimide class novel high polymer containing three keys
Polymer.
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer preparation method containing three keys, it is characterised in that single
Body A general structure isIn formula, n is arbitrary natural number of 1-3；Described monomer B structure formula isIn formula
R1、R2For identical or different substituent group, can be hydrogen, alkyl, alkoxyl, phenyl or alkoxy benzene.
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer preparation method containing three keys, it is characterised in that institute
The mol ratio stating monomer A and monomer B is 1～1.25: 1.
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer preparation method containing three keys, it is characterised in that institute
State that catalyst amount is monomer A and monomer B consumption sum 0.01～10%.
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys prepares catalyst amount, and its feature exists
In, described catalyst is Hydro-Giene (Water Science). and the mixture of organophosphor ligand, Pd (PPh3)4Or PdCl2(PPh3)2。
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer preparation method containing three keys, it is characterised in that institute
Stating organic solvent is at least one in DMF, oxolane, normal hexane, diisopropylamine, methanol, acetone, petroleum ether.
A kind of naphthalenetetracarbacidic acidic diimide class novel high molecular polymer containing three keys the most according to claims 1 to 7, be mainly used in photoelectric material,
Luminescent material, organic semiconductor and solar cell material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510010629.9A CN105885017A (en) | 2015-01-07 | 2015-01-07 | Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510010629.9A CN105885017A (en) | 2015-01-07 | 2015-01-07 | Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105885017A true CN105885017A (en) | 2016-08-24 |
Family
ID=56998923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510010629.9A Pending CN105885017A (en) | 2015-01-07 | 2015-01-07 | Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105885017A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161002A (en) * | 2018-06-30 | 2019-01-08 | 华南理工大学 | N-shaped conjugated polymer based on alcoxyl thiophene alkynes unit and its application in organic photovoltaic |
| CN109553757A (en) * | 2018-12-21 | 2019-04-02 | 福州大学 | A kind of benzene-naphthalene diimide receptoroid polymer of two-dimensional structure and the preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295754A (en) * | 2010-06-28 | 2011-12-28 | 海洋王照明科技股份有限公司 | Naphthalene tetracarboxylic diimide-naphtho dithiophene-containing copolymer and preparation method as well as application thereof |
-
2015
- 2015-01-07 CN CN201510010629.9A patent/CN105885017A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102295754A (en) * | 2010-06-28 | 2011-12-28 | 海洋王照明科技股份有限公司 | Naphthalene tetracarboxylic diimide-naphtho dithiophene-containing copolymer and preparation method as well as application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ARNOŠT SEIDLER ET AL.: ""The synthesis of p-electron molecular rods with athiophene or thieno[3,2- b]thiophene core unit and sulfur alligator clips"", 《TETRAHEDRON LETTERS》 * |
| MATTHEW M. DURBAN，ET AL.: ""Synthesis and Characterization of Thiophene-Containing Naphthalene Diimide n-Type Copolymers for OFET Applications"", 《MACROMOLECULES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161002A (en) * | 2018-06-30 | 2019-01-08 | 华南理工大学 | N-shaped conjugated polymer based on alcoxyl thiophene alkynes unit and its application in organic photovoltaic |
| CN109553757A (en) * | 2018-12-21 | 2019-04-02 | 福州大学 | A kind of benzene-naphthalene diimide receptoroid polymer of two-dimensional structure and the preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112778327B (en) | Organic non-fullerene electron acceptor material and preparation method and application thereof | |
| CN106905306B (en) | Hexafluoro quinoxaline compounds and hexafluoro quinoxaline copolymer and application | |
| CN104428303A (en) | Photoelectric material preparation | |
| CN103193696B (en) | Norbornene imide system Mesogen-jacketed polymer monomer and polymkeric substance thereof | |
| CN107778319B (en) | A-D-A type micromolecule compound containing hepta-fused ring structure indacene and preparation method thereof | |
| CN108129447A (en) | A kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application | |
| CN105175691B (en) | Conjugated polymer semi-conducting material, preparation and its high-efficiency polymer solar cell application of the one kind based on thieno (hetero) aryl indole unit | |
| CN103435782B (en) | Organic semiconducting materials containing 9,9 '-difluorenylene and derivant thereof and preparation method thereof and application | |
| CN104892629B (en) | Yi Zhong perylene diimide class midbody compounds and preparation method thereof | |
| WO2012109747A1 (en) | Organic semiconducting compounds and devices generated therefrom | |
| CN105885017A (en) | Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond | |
| CN108148184A (en) | One kind contains acenaphthene simultaneously conjugated polymer of [1,2-b] quinoxaline imidodicarbonic diamide and its preparation method and application | |
| CN110575795A (en) | High-thermal-stability supermolecule organogel and preparation thereof | |
| CN102070771A (en) | Perylene diimide photoelectric functional materials and preparation method thereof | |
| KR101059783B1 (en) | Organic Thin Film Transistors Containing Fullerene Derivatives | |
| CN106832227B (en) | Dendritic conjugated compound, ink, film, preparation method and application | |
| CN109956955A (en) | Star-like D-A structure conjugated molecule and its preparation method and application based on benzo three (the double five yuan of heteroaromatics of cyclopenta) | |
| CN103880849A (en) | Narrow-band gap conjugated molecule as well as preparation method and application thereof | |
| CN108218870B (en) | Tetraaza nano graphene functional material and preparation method thereof | |
| CN100410292C (en) | Polyphenylene ethylene and its derivant, preparation process and application | |
| Barros et al. | Synthesis and photophysical properties of tetraphenylethylene derivatives as luminescent downshifting materials for organic photovoltaic applications | |
| CN109879854A (en) | A kind of cyclobutane ketone compounds and preparation method thereof with antioxidation | |
| CN109553757A (en) | A kind of benzene-naphthalene diimide receptoroid polymer of two-dimensional structure and the preparation method and application thereof | |
| CN109354674B (en) | Semi-fluoroalkyl dovetail side chain substituted naphthalene diimide-based copolymer, preparation method and application thereof | |
| CN108690046A (en) | Asymmetric aromatic fused ring compound and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160824 |
|
| WD01 | Invention patent application deemed withdrawn after publication |