CN113861388B - Melt-processable polymer material, and preparation method and application thereof - Google Patents

Melt-processable polymer material, and preparation method and application thereof Download PDF

Info

Publication number
CN113861388B
CN113861388B CN202110948260.1A CN202110948260A CN113861388B CN 113861388 B CN113861388 B CN 113861388B CN 202110948260 A CN202110948260 A CN 202110948260A CN 113861388 B CN113861388 B CN 113861388B
Authority
CN
China
Prior art keywords
polymer material
melt
preparation
spin valve
valve device
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.)
Active
Application number
CN202110948260.1A
Other languages
Chinese (zh)
Other versions
CN113861388A (en
Inventor
孙向南
祝向伟
常艺琳
谷现荣
秦阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Center for Nanosccience and Technology China
Original Assignee
National Center for Nanosccience and Technology China
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by National Center for Nanosccience and Technology China filed Critical National Center for Nanosccience and Technology China
Priority to CN202110948260.1A priority Critical patent/CN113861388B/en
Publication of CN113861388A publication Critical patent/CN113861388A/en
Application granted granted Critical
Publication of CN113861388B publication Critical patent/CN113861388B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/124—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one nitrogen atom in the ring
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Magnetic active materials
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/124—Copolymers alternating
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/141—Side-chains having aliphatic units
    • C08G2261/1412—Saturated aliphatic units
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3221—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3225—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more Se atoms as the only heteroatom
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3241—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more nitrogen atoms as the only heteroatom, e.g. carbazole
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3243—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing one or more sulfur atoms as the only heteroatom, e.g. benzothiophene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention provides a melt-processable polymer material, a preparation method and application thereof. The structural general formula of the melt-processable polymer material is as follows:

Description

Melt-processable polymer material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of spinning, in particular to a melt-processable polymer material, a preparation method and application thereof.
Background
Since the birth of the last 80 th century spintronics, people gradually recognize that a new generation of microelectronic devices which are more convenient to operate, more powerful, faster in processing speed and lower in energy consumption can be obtained by utilizing the spin properties of electrons, thereby realizing the leap development of the information age. Traditional spintronics materials tend to have strong spin-orbit coupling effect, and the spin relaxation time of electrons is short (nanosecond order), which severely limits the application of the spintronics materials in spintronics devices. The organic semiconductor material is mainly composed of light elements (H, C, N, O and the like) with low atomic numbers, the spin-orbit coupling effect is weak, the spin relaxation time of electrons is long (in the order of seconds), and great potential is reserved in the aspects of realizing efficient spin transport and room temperature spin control. At present, development of efficient spin transport materials has become a key point of sustainable development of organic spin electronics, and is also a necessary premise for further realizing electron spin control and constructing spin information operation processing type electronic devices.
In the aspect of preparing an organic spin electronic device, a thermal evaporation film forming method which is commonly adopted at present is utilized, and although a purer active layer film can be prepared and an external spin scattering center is not easy to introduce, the method is not suitable for an organic semiconductor material processed by a mainstream solution method at present. While organic films prepared by spin-coating solutions typically have residual solvents and vacancies caused by solvent evaporation, these defects tend to form spin scattering centers that impair the spin transport ability of the material.
In view of this, the present invention is specifically proposed.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a melt processable polymeric material. The polymer material has low melting point, is applied to spintronics for the first time by a melt processing technology, can reduce defects caused by film formation by a solution method in the melt processing film formation process, and weakens spin scattering. Moreover, the polymer molecule movement is aggravated in the melt processing process, the aggregation state structure of the organic layer can be optimized, and the method has important scientific significance for realizing high-efficiency and long-distance spin transportation.
It is a further object of the present invention to provide a method for preparing said melt processable polymeric material.
It is a further object of the present invention to provide the use of said melt processable polymeric material.
The technical scheme for realizing the purposes of the invention is as follows:
a melt processable polymeric material having the structural formula:
wherein, D is any one of thiophene-alkyl-thiophene, selenophene-alkyl-selenophene or bithiophene-alkyl-bithiophene;
a is a bipyridylpyrrolopyrrole dione unit;
n represents the number of repeating units of the polymer.
Wherein D is selected from any one of the following units:
a is:
wherein n is 1 Represents the number of carbon atoms in the alkyl chain linking the two aromatic groups in the D unit, n 1 An integer selected from 2 to 15;
r is a substituted or unsubstituted straight or branched alkyl group having 30 or less carbon atoms.
Further, n 1 An integer selected from 3 to 6; r is a branched alkyl group having 8 to 20 carbon atoms.
The preparation method of the melt-processable polymer material comprises the following steps:
(1) Under the protection of inert gas, one of thiophene, selenophene or benzothiophene reacts with dibromoalkane in a first organic solvent under the action of n-butyllithium;
(2) Under the protection of inert gas, the product obtained in the step (1) reacts with trimethyltin chloride in a first organic solvent under the action of n-butyllithium;
(3) And (3) reacting the product obtained in the step (2) with a halogen substituted bipyridyl pyrrolopyrrole dione unit in a second organic solvent under the catalysis of a palladium complex under the protection of inert gas.
Wherein in the step (1), the dibromoalkane is selected from one of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane and dibromodecane; the mol ratio of one of thiophene, selenophene or benzothiophene to dibromoalkane is (2-3): 1. The reaction temperature of the step (1) is-5 ℃.
In the step (2), the molar ratio of the product obtained in the step (1) to trimethyltin chloride is 1 (2-3); the reaction temperature in the step (2) is-90 to-70 ℃.
In step (3), the palladium complex is selected from the group consisting of tetrakis triphenylphosphine palladium or a combination of tris (dibenzylideneacetone) dipalladium and tri-o-tolylphosphine; the addition amount of the palladium complex is 0.01-1% of the molar amount of the product obtained in the step (2); the reaction temperature of the step (3) is 75-120 ℃.
Wherein the first organic solvent is selected from one or more of tetrahydrofuran and dimethyl tetrahydrofuran; the second organic solvent is selected from one or more of toluene, xylene or chlorobenzene.
The melt-processable polymer material is applied to the preparation of an organic spin valve device, and is formed into a film by a melt processing method.
The invention has the beneficial effects that:
the invention provides a novel melt-processible polymer material, which has a low melting point PDBPyTPT, and can be used for constructing an organic spin valve device by adopting a melt processing method, wherein the device shows a spin valve effect of up to 13%, and has potential application prospects in the field of organic spin electronics;
the invention adopts the melt processing method to prepare the organic spin valve device, and has the advantages of strong operability and easy repetition.
Drawings
FIG. 1 is a DSC curve of the polymer PDBPyTPT.
Fig. 2 is a magnetic resistance curve (MR) at room temperature of a polymer PDBPyTPT-based organic spin valve device prepared using a melt processing method.
Detailed Description
The following preferred examples illustrate the invention but are not intended to limit the scope thereof.
The means or materials used in the examples are all technical means or materials known in the art unless specifically stated otherwise.
Example 1
A melt processable polymeric material having the structural formula:
the present example also provides a method of preparing the polymer:
(1) N-butyllithium (1.2 mol) is slowly dripped into tetrahydrofuran dissolved with thiophene (1 mol) under the protection of nitrogen and at a low temperature (0 ℃), and then 1, 3-dibromopropane (0.4 mol) is added to obtain a precursor of a compound TPT;
(2) N-butyllithium (2.4 mol) is slowly dripped into tetrahydrofuran dissolved with a compound TPT precursor (1 mol) under the protection of nitrogen and at a low temperature (-78 ℃), and then trimethyltin chloride (3 mol) is added to obtain the compound TPT;
(3) Under the protection of nitrogen and at the temperature of 110 ℃, the compound DBPyBr-20 (1 mmol) and the compound TPT (1 mol) are polymerized in toluene for 12 hours under the action of a tetraphenylphosphine palladium catalyst (0.01 mmol) to obtain the polymer material PDBPyTPT.
The DSC curve of the polymer PDBPyTPT is shown in FIG. 1, indicating that the polymer material PDBPyTPT has a lower melting point.
Example 2 organic spin valve device
In this example, a PDBPyTPT-based organic spin valve device was prepared and characterized using a melt processing method as follows:
the organic spin valve device structure based on the melt processing PDBPyTPT is Co/AlOx/PDBPyTPT/Ni 80 Fe 20 . First, in the cleaned SiO 2 Electricity utilization on a substrateBeamlet evaporationA 20nm ferromagnetic metal Co was evaporated as bottom electrode. Subsequently, the electron beam evaporation method is continued for +.>Metal Al of 2nm is evaporated at a rate of 2 nm. Then, PDBPyTPT was formed into a film by spin coating and heated above the melting point for 60min. Finally, evaporating 15nm Ni on the top electrode by using electron beam 80 Fe 20 . The electron beam evaporation process is carried out in a high vacuum chamber, and the organic layer film forming and melt processing processes are carried out in a dry and oxygen-free glove box.
Fig. 2 is a magnetic resistance curve (MR) at room temperature of an organic spin valve device based on polymer PDBPyTPT prepared using a melt processing method, and shows that the organic spin valve device constructed using the melt processing method can exhibit a spin valve effect as high as 13%.
Example 3
A melt processable polymeric material having the structural formula:
the selenophene was used as a starting material and produced in the same manner as in example 1.
Example 4
A melt processable polymeric material having the structural formula:
the same procedure as in example 1 was followed except that benzothiophene was used as the starting material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims (9)

1. The application of a melt-processable polymer material in the preparation of an organic spin valve device is characterized in that the polymer material is formed into a film by adopting a melt processing method, and the polymer material has the following structural general formula:
wherein D is any one of thiophene-alkyl-thiophene, selenophene-alkyl-selenophene or benzothiophene-alkyl-benzothiophene;
a is a bipyridylpyrrolopyrrole dione unit;
n represents the number of repeating units of the polymer.
2. Use of a melt processable polymer material according to claim 1 in the preparation of an organic spin valve device, wherein D is selected from any one of the following units:
a is:
wherein n is 1 Represents the number of carbon atoms in the alkyl chain linking the two aromatic groups in the D unit, n 1 An integer selected from 2 to 15;
r is a substituted or unsubstituted straight or branched alkyl group having 30 or less carbon atoms.
3. Use of a melt processable polymer material according to claim 2 in the preparation of an organic spin valve device, characterized in that n 1 An integer selected from 3 to 6; r is a branched alkyl group having 8 to 20 carbon atoms.
4. Use of the melt-processable polymeric material of claim 1 in the preparation of an organic spin valve device, wherein the method of preparing the melt-processable polymeric material comprises the steps of:
(1) Under the protection of inert gas, one of thiophene, selenophene or benzothiophene reacts with dibromoalkane in a first organic solvent under the action of n-butyllithium;
(2) Under the protection of inert gas, the product obtained in the step (1) reacts with trimethyltin chloride in a first organic solvent under the action of n-butyllithium;
(3) And (3) reacting the product obtained in the step (2) with a halogen substituted bipyridyl pyrrolopyrrole dione unit in a second organic solvent under the catalysis of a palladium complex under the protection of inert gas.
5. The use of a melt processable polymer material according to claim 4 in the preparation of an organic spin valve device, wherein in step (1) the dibromoalkane is selected from one of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane, dibromodecane; the molar ratio of one of thiophene, selenophene or benzothiophene to dibromoalkane is (2-3): 1.
6. Use of a melt processable polymer material according to claim 5 in the preparation of an organic spin valve device, wherein the reaction temperature of step (1) is between-5 and 5 ℃.
7. The use of a melt processable polymer material according to claim 4 in the preparation of an organic spin valve device, wherein in step (2), the molar ratio of the product obtained in step (1) to trimethyltin chloride is 1 (2-3); the reaction temperature in the step (2) is-90 to-70 ℃.
8. The use of a melt processable polymer material according to claim 4 in the preparation of an organic spin valve device, wherein in step (3) the palladium complex is selected from the group consisting of tetrakis triphenylphosphine palladium or a combination of tris (dibenzylideneacetone) dipalladium and tri-o-tolylphosphine; the addition amount of the palladium complex is 0.01-1% of the molar amount of the product obtained in the step (2); the reaction temperature of the step (3) is 75-120 ℃.
9. Use of a melt processable polymer material according to any one of claims 4-8 in the preparation of an organic spin valve device, wherein the first organic solvent is selected from one or more of tetrahydrofuran, dimethyltetrahydrofuran; the second organic solvent is selected from one or more of toluene, xylene or chlorobenzene.
CN202110948260.1A 2021-08-18 2021-08-18 Melt-processable polymer material, and preparation method and application thereof Active CN113861388B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110948260.1A CN113861388B (en) 2021-08-18 2021-08-18 Melt-processable polymer material, and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110948260.1A CN113861388B (en) 2021-08-18 2021-08-18 Melt-processable polymer material, and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113861388A CN113861388A (en) 2021-12-31
CN113861388B true CN113861388B (en) 2024-02-13

Family

ID=78990565

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110948260.1A Active CN113861388B (en) 2021-08-18 2021-08-18 Melt-processable polymer material, and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113861388B (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10026898B2 (en) * 2015-02-18 2018-07-17 Purdue Research Foundation Methods and compositions for enhancing processability and charge transport of polymer semiconductors and devices made therefrom
US10109798B2 (en) * 2015-05-26 2018-10-23 Purdue Research Foundation Methods and compositions for enhancing processability and charge transport of polymer semiconductors
US11380845B2 (en) * 2017-11-01 2022-07-05 Purdue Research Foundation Semiconducting microfibers and methods of making the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Conjugation-Break Spacers in Semiconducting Polymers：Impact on Polymer Processability and Charge Transport Properties";Yan Zhao et al.;《Macromolecules》;第48卷;2048-2053 *

Also Published As

Publication number Publication date
CN113861388A (en) 2021-12-31

Similar Documents

Publication Publication Date Title
Lai et al. Isomer-free: precise positioning of chlorine-induced interpenetrating charge transfer for elevated solar conversion
Zhang et al. Recent advance in solution‐processed organic interlayers for high‐performance planar perovskite solar cells
Li et al. Additive‐Free Organic Solar Cells with Power Conversion Efficiency over 10%
Li et al. Alternating Copolymers of Cyclopenta [2, 1‐b; 3, 4‐b′] dithiophene and Thieno [3, 4‐c] pyrrole‐4, 6‐dione for High‐Performance Polymer Solar Cells
Chen et al. Recent research progress of organic small‐molecule semiconductors with high electron mobilities
Zuo et al. Influence of the backbone conformation of conjugated polymers on morphology and photovoltaic properties
Chen et al. Improving the performance of photonic transistor memory devices using conjugated block copolymers as a floating gate
Yin et al. A structurally simple linear conjugated polymer toward practical application of organic solar cells
KR101288128B1 (en) Dendritic polymer containing metal phthalocyanine, preparation method thereof and the organic light emitting diodes using the same
Han et al. Cyclic alkyl chains promote the polymer self-assembly and packing orders for solar cells
Zhu et al. A benzobis (thiadiazole)-based small molecule as a solution-processing electron extraction material in planar perovskite solar cells
Yan et al. Naphthalene-diimide selenophene copolymers as efficient solution-processable electron-transporting material for perovskite solar cells
KR101743241B1 (en) Naphthalene diimide based copolymers with high electron mobility and synthesizing method of the same
Gu et al. Non‐Conjugated Polymer Based on Polyethylene Backbone as Dopant‐Free Hole‐Transporting Material for Efficient and Stable Inverted Quasi‐2D Perovskite Solar Cells
CN113861388B (en) Melt-processable polymer material, and preparation method and application thereof
Zhao et al. Novel hyperbranched polymers as host materials for green thermally activated delayed fluorescence OLEDs
WO2012031403A1 (en) Perylenetetracarboxylic acid diimide organic semiconductive material, preparation method and use thereof
Xia et al. Synthesis of dithieno [2, 3-d: 2’, 3’-d’] benzo [1, 2-b: 4, 5-b’] dithiophene-alt-isoindigo conjugated polymer and enhancement of photovoltaic property with diphenyl sulfide additives
JP2014192291A (en) Polymerizable coating liquid, resin and organic electroluminescent element formed using the same, and method for producing polymerizable coating liquid and organic electroluminescent element
Liu et al. Ether chain functionalized fullerene derivatives as cathode interface materials for efficient organic solar cells
KR101550844B1 (en) Conjugated polymer for organic solar cells and Organic solar cells comprising the same
CN112745351B (en) Preparation and application of novel hole transport material based on N-P = X resonance structure
CN110283098B (en) Star-shaped aromatized inorganic acid radical semiconductor material and preparation and application thereof
KR102228274B1 (en) conjucated polymer for Low temperature process and organic solar cell using the same
Mikie et al. Ester-functionalized quinoxaline-based polymers for application in organic photovoltaics

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant