阅读说明：本技术 可熔融加工型聚合物材料及其制备方法和应用 (Melt-processable polymer material, and preparation method and application thereof ) 是由 孙向南 祝向伟 常艺琳 谷现荣 秦阳 于 2021-08-18 设计创作，主要内容包括：本发明提供一种可熔融加工型聚合物材料及其制备方法和应用。所述可熔融加工型聚合物材料的结构通式如下：其中,D为噻吩-烷基-噻吩、硒吩-烷基-硒吩或并噻吩-烷基-并噻吩中的任意一种；A为二吡啶基吡咯并吡咯二酮单元；n代表聚合物的重复单元个数。本发明提供了一类新型可熔融加工型聚合物材料,聚合物材料PDBPyTPT具有较低的熔点,采用熔融加工法可构建有机自旋阀器件,该器件表现出高达13％的自旋阀效应,在有机自旋电子学领域展现潜在的应用前景。(The invention provides a melt-processable polymer material and a preparation method and application thereof. The structural general formula of the melt-processable polymer material is as follows:)

1. A melt processable polymeric material having the general structural formula:

wherein D is any one of thiophene-alkyl-thiophene, selenophene-alkyl-selenophene or bithiophene-alkyl-bithiophene;

a is a dipyridyl pyrrolopyrroledione unit;

n represents the number of repeating units of the polymer.

2. A melt processable polymeric material according to claim 1 wherein D is selected from any one of the following units:

a is as follows:

wherein n is₁Represents the number of carbon atoms in the alkyl chain connecting the two aromatic groups in the D unit, n₁An integer selected from 2 to 15;

r is a substituted or unsubstituted linear or branched alkyl group having 30 or less carbon atoms.

3. A melt processable polymeric material according to claim 1 or 2 wherein n is n₁An integer selected from 3 to 6; r is a branched alkyl group of 8 to 20 carbon atoms in number.

4. A method of producing a melt processable polymeric material according to any one of claims 1 to 3, comprising the steps of:

(1) under the protection of inert gas, one of thiophene, selenophene or bithiophene reacts with dibromoalkane in a first organic solvent under the action of n-butyl lithium;

(2) under the protection of inert gas, reacting the product obtained in the step (1) with trimethyl tin chloride in a first organic solvent under the action of n-butyl lithium;

(3) and (3) under the protection of inert gas, reacting the product obtained in the step (2) with a halogen substituted dipyridyl pyrrolo-pyrrole-dione unit in a second organic solvent under the catalysis of a palladium complex.

5. A method of producing a melt-processable polymer material according to claim 4, wherein in the step (1), the dibromoalkane is selected from one of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane and dibromodecane; the molar ratio of one of thiophene, selenophene or bithiophene to dibromoalkane is (2-3) to 1.

6. A method of producing a melt processable polymeric material according to claim 5, wherein the reaction temperature in step (1) is from-5 ℃ to 5 ℃.

7. A method for preparing a melt-processable polymer material according to claim 4, wherein in the step (2), the molar ratio of the product obtained in the step (1) to the trimethyl tin chloride is 1 (2-3); the reaction temperature of the step (2) is-90 to-70 ℃.

8. A method of preparing a melt processable polymeric material according to claim 4, wherein in step (3), the palladium complex compound is selected from tetrakistriphenylphosphine 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 weight of the product obtained in the step (2); the reaction temperature in the step (3) is 75-120 ℃.

9. A method of preparing a melt processable polymeric material according to any one of claims 4 to 8, 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.

10. Use of a melt processable polymeric material according to any one of claims 1 to 3 in the manufacture of an organic spin valve device wherein the polymeric material is formed into a film by a melt processing method.

Technical Field

The invention relates to the technical field of spinning, in particular to a melt-processable polymer material and a preparation method and application thereof.

Background

Since the birth of spintronics at the end of the last 80 th century, people gradually realize that by utilizing the spin property of electrons, a new-generation microelectronic device with more convenient operation and control, stronger function, faster processing speed and lower energy consumption can be obtained, thereby realizing the leap development of the information age. The traditional spintronics material has stronger spin-orbit coupling effect, the spin relaxation time of electrons is short (nanosecond level), and the application of the traditional spintronics material in the aspect of spintronics is severely limited. The organic semiconductor material is mainly composed of light elements (H, C, N, O and the like) with lower atomic number, the spin-orbit coupling effect of the organic semiconductor material is weak, the spin relaxation time of electrons is very long (in the order of seconds), and the organic semiconductor material has great potential in the aspects of realizing high-efficiency spin transport and room-temperature spin control. At present, the development of high-efficiency spin transport materials has become the key point of the continuous development of organic spintronics, and is also the necessary premise for further realizing the electronic spin control and constructing a spin information operation processing type electronic device.

In the preparation of organic spin electronic devices, a thermal evaporation film forming method which is commonly adopted at present is utilized, and although a relatively pure active layer film can be prepared and a foreign spin scattering center is not easy to introduce, the method is not suitable for the organic semiconductor material which is processed by the mainstream solution method at present. The organic thin film prepared by the solution spin coating method generally has residual solvent and vacancies caused by solvent volatilization, and the defects tend to form spin scattering centers to weaken the spin transport capability of the material.

In view of this, the present invention is specifically set forth.

Disclosure of Invention

In view of the deficiencies 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 the spinning electronics by a melt processing process for the first time, can reduce the defects caused by film formation by a solution method in the melt processing film formation process, and weakens the spin scattering. In addition, the polymer molecules are accelerated 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 transport.

It is another 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 above purpose of the invention is as follows:

a melt processable polymeric material having the general structural formula:

wherein D is any one of thiophene-alkyl-thiophene, selenophene-alkyl-selenophene or bithiophene-alkyl-bithiophene;

a is a dipyridyl pyrrolopyrroledione unit;

n represents the number of repeating units of the polymer.

Wherein D is selected from any one of the following units:

a is as follows:

wherein n is₁Represents the number of carbon atoms in the alkyl chain connecting the two aromatic groups in the D unit, n₁An integer selected from 2 to 15;

r is a substituted or unsubstituted linear or branched alkyl group having 30 or less carbon atoms.

Further, n₁An integer selected from 3 to 6; r is a branched alkyl group of 8 to 20 carbon atoms in number.

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 bithiophene reacts with dibromoalkane in a first organic solvent under the action of n-butyl lithium;

(2) under the protection of inert gas, reacting the product obtained in the step (1) with trimethyl tin chloride in a first organic solvent under the action of n-butyl lithium;

(3) and (3) under the protection of inert gas, reacting the product obtained in the step (2) with a halogen substituted dipyridyl pyrrolo-pyrrole-dione unit in a second organic solvent under the catalysis of a palladium complex.

In the step (1), the dibromo alkane is selected from one of dibromoethane, dibromopropane, dibromobutane, dibromopentane, dibromohexane, dibromoheptane, dibromooctane, dibromononane and dibromodecane; the molar ratio of one of thiophene, selenophene or bithiophene to dibromoalkane is (2-3) to 1. The reaction temperature in the step (1) is-5 ℃.

In the step (2), the molar ratio of the product obtained in the step (1) to trimethyl tin chloride is 1 (2-3); the reaction temperature of the step (2) is-90 to-70 ℃.

In the step (3), the palladium complex is selected from tetratriphenylphosphine 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 weight 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 dimethyltetrahydrofuran; the second organic solvent is selected from one or more of toluene, xylene or chlorobenzene.

The invention discloses application of a melt-processable polymer material in preparation of an organic spin valve device, wherein the polymer material is formed into a film by a melt processing method.

The invention has the beneficial effects that:

the invention provides a novel melt-processable polymer material, wherein the polymer material PDBPyTPT has a lower melting point, an organic spin valve device can be constructed by adopting a melt processing method, the device shows a spin valve effect as high as 13 percent, and the potential application prospect is shown in the field of organic spin electronics;

the method for preparing the organic spin valve device by adopting the melt processing method has the advantages of strong operability and easy repetition.

Drawings

FIG. 1 is a DSC curve of polymer PDBPyTPT.

FIG. 2 is a graph of the Magnetoresistance (MR) at room temperature for an organic spin valve device based on the polymer PDBPyTPT prepared by melt processing.

Detailed Description

The present invention will now be illustrated by the following preferred examples, which should not be construed as limiting the scope of the invention.

Unless otherwise indicated, all means or materials used in the examples are technical means or materials known in the art.

Example 1

A melt processable polymeric material having the formula:

this example also provides a method for preparing the polymer:

(1) under the conditions of nitrogen protection and low temperature (0 ℃), slowly dropwise adding n-butyllithium (1.2mol) into tetrahydrofuran dissolved with thiophene (1mol), and then adding 1, 3-dibromopropane (0.4mol) to obtain a precursor of a compound TPT;

(2) under the conditions of nitrogen protection and low temperature (-78 ℃), slowly dropwise adding n-butyllithium (2.4mol) into tetrahydrofuran in which a compound TPT precursor (1mol) is dissolved, and then adding trimethyl tin chloride (3mol) to obtain a compound TPT;

(3) under the protection of nitrogen and at the temperature of 110 ℃, a compound DBPyBr-20(1mmol) and a compound TPT (1mol) are subjected to a polymerization reaction in toluene for 12 hours under the action of a tetratriphenylphosphine palladium catalyst (0.01mmol), so as to obtain a polymer material PDBPyTPT.

The DSC curve of the polymer PDBPyTPT is shown in figure 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 based on the melt processing PDBPyTPT has the structure of Co/AlOx/PDBPyTPT/Ni₈₀Fe₂₀. First, in the cleaned SiO₂The substrate is coated by electron beam evaporation20nm of ferromagnetic metal Co was evaporated as bottom electrode. Then, the electron beam evaporation method is continuously adopted to2nm of metallic Al is evaporated. Then, pdbpyttp was film-formed by spin coating and heated to above the melting point for 60 min. Finally, a top electrode 15nm Ni was evaporated by electron beam₈₀Fe₂₀. The electron beam evaporation process is carried out in a high vacuum chamber, and the organic layer film forming and melting process are carried out in an anhydrous and oxygen-free glove box.

FIG. 2 is the magnetoresistive curve (MR) at room temperature of an organic spin valve device based on the polymer PDBPyTPT prepared by a melt processing method, and the result shows that the organic spin valve device constructed by the melt processing method can show the spin valve effect of up to 13%.

Example 3

A melt processable polymeric material having the formula:

prepared by using selenophene as a starting material by the same method as in example 1.

Example 4

A melt processable polymeric material having the formula:

was prepared in the same manner as in example 1, using bithiophene as a starting material.

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present 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 solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.