CN108084477B - High-molecular oriented film and preparation method and application thereof - Google Patents

High-molecular oriented film and preparation method and application thereof Download PDF

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CN108084477B
CN108084477B CN201810102667.0A CN201810102667A CN108084477B CN 108084477 B CN108084477 B CN 108084477B CN 201810102667 A CN201810102667 A CN 201810102667A CN 108084477 B CN108084477 B CN 108084477B
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polycaprolactone
film
oriented film
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CN108084477A (en
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闫寿科
王俊杰
李慧慧
孙晓丽
任忠杰
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
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    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2427/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2465/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Abstract

The invention discloses a high-molecular oriented film and a preparation method and application thereof. The method comprises the following steps: (1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; (2) and attaching the second polymer blend solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain the high molecular oriented film with parallel platelets. The invention also provides a regulation and control method for the nano-scale phase separation of the high-molecular oriented film. The method of the invention has simple operation and can prepare the polymer oriented film with high orientation degree and uniform orientation in a large area.

Description

High-molecular oriented film and preparation method and application thereof
Technical Field
The invention relates to a high-molecular oriented film and a preparation method and application thereof.
Background
Electronic devices of polymer semiconductors have attracted much attention. However, semiconductor polymer thin films generally have a defect of poor ordering. It is very necessary to improve the order of the structure of the polymer film. In general, a small molecule monomer is polymerized by living polymerization, condensation polymerization, electrochemical polymerization, or the like to prepare a conductive polymer; the conductive polymer is then subjected to mechanical shearing, solution drawing, melt drawing, and the like to obtain a highly oriented film. The mechanical shearing method is difficult to prepare uniform oriented films, and the orientation degree of the films obtained by the solution pulling method is low; the melt-stretching method is not suitable for preparing a polymer film having a high melting point, poor solubility and high rigidity.
In one aspect, CN103407179A discloses a method for preparing a highly oriented film, in which a uniform film is formed on a hot stage, and the film is taken up from the hot stage by a rotating roller which is automatically lifted up and down, so as to form a continuous oriented film between the hot stage and the roller, and the thickness of the film is controlled by adjusting the rotating speed of the roller. CN103451698A discloses a method for preparing a highly oriented conductive polymer film, which comprises preparing a highly oriented polymer film by melt-stretching, modifying an electrode for electrochemical polymerization with the polymer film, and electrochemically polymerizing a conductive polymer monomer on the modified electrode to form the highly oriented conductive polymer film. The above method can obtain a nano-sized single-component polymer film, but further improvement is required for the preparation of a blended polymer oriented film.
On the other hand, common blend films can be classified into three types of amorphous/noncrystalline, crystalline/noncrystalline and crystalline/crystalline according to the crystalline properties of the constituent polymers. For the crystalline/amorphous type, during crystallization of the crystalline component, the amorphous component cannot be discharged into its crystal lattice and gradually rejected from the crystal region. This repulsion process is influenced by the interaction between the two component segments, the ability of the amorphous component to diffuse, and the rate of crystal growth of the crystalline component. When crystallization is complete, the final distribution of the amorphous component may be in the region between platelets, between bundles of platelet fibers, or between spherulites of the crystalline component. The distribution of the amorphous component from between platelets to between spherulites of the crystalline component illustrates the varying degree of diffusion of the amorphous component from nano-scale to micro-scale during the crystallization process. For the crystallization/crystallization type, crystallization of two components can produce two different crystal types. The polymer material blend can form an alternating arrangement of common platelet stacking regions, and can also form independent platelet stacking regions. The alignment position may be a series of single phase stacks connected to a series of other phase stacks. How to realize the nanometer-level phase separation of multi-component macromolecules is a problem which troubles the development of the industry.
Disclosure of Invention
An object of the present invention is to provide a method for producing a polymer oriented film, which can obtain a nano-scale phase-separated film.
Another object of the present invention is to provide a polymer oriented film on which platelets are regularly arranged.
It is still another object of the present invention to provide a use of the above-mentioned polymer oriented film.
The invention also aims to provide a regulation and control method for the nanometer-level phase separation of the known polymer oriented film, which has simple process and can realize the nanometer-level phase separation.
According to one aspect of the present invention, there is provided a method for producing a polymer oriented film, comprising the steps of:
(1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; wherein the first polymer in the first polymer oriented film is selected from crystalline polyolefins or crystalline polyhalogenated olefins;
(2) attaching the second polymer blending solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain a high molecular oriented film with parallel platelets; wherein the second polymer blend solution is formed by dissolving a second polymer in an organic solvent, the second polymer comprising at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer; the organic solvent is a solvent that is not capable of dissolving the first polymer but is capable of dissolving the second polymer.
According to the preparation method of the present invention, preferably, in the step (1), the crystalline polyolefin is selected from polyethylene or polypropylene, and the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride and polytetrafluoroethylene; the substrate is selected from a glass sheet or a silicon wafer.
According to the production method of the present invention, preferably, in the step (2), the at least two polymers are selected from the group consisting of polycaprolactone, polybutylene adipate, polybutylene (adipate-co-succinate), polylactic acid, polyalkylene oxide, polythiophene, polyacrylate, polymethacrylate, polyamide, polyolefin, and polyhalogenated olefin.
According to the preparation method of the invention, preferably, in the step (2), the at least two polymers are two polymers capable of generating surface-induced orientation with the first polymer, the weight ratio of the two polymers is 1-3: 3-1, and the total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%; the organic solvent is selected from one or more of dichloromethane, acetonitrile or trichloromethane.
According to the preparation method of the present invention, preferably, in the step (2), the heat treatment is: heat treatment is carried out at 60-150 ℃ for 3-1000 minutes, and then heat treatment is carried out at 10-50 ℃ for 5-30 hours.
According to the production method of the present invention, preferably, in the step (2), the thickness of the polymer oriented film is 60nm to 2 μm, and the thickness of the platelets is 1nm to 100 nm.
According to another aspect of the present invention, there is provided an oriented polymer film obtained by any one of the above-mentioned production methods, the oriented polymer film having a thickness of 60nm to 2 μm, comprising a first oriented polymer film and a second oriented polymer film attached to the first oriented polymer film, the second oriented polymer film having platelets aligned in parallel and having a thickness of 1nm to 100 nm.
According to a further aspect of the present invention, there is provided a use of the above-mentioned polymer-oriented film in a light emitting diode, a solar cell or a field effect transistor.
According to another aspect of the present invention, there is provided a method for controlling nanoscale phase separation of a polymer oriented film, comprising the following steps:
(1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; wherein the first polymer in the first polymer oriented film is selected from crystalline polyolefins or crystalline polyhalogenated olefins;
(2) attaching the second polymer blending solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain a high molecular oriented film with parallel platelets; wherein the second polymer blend solution is formed by dissolving a second polymer in an organic solvent, the second polymer comprising at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer; the organic solvent is a solvent that is not capable of dissolving the first polymer but is capable of dissolving the second polymer.
According to the regulation method of the present invention, preferably, in the step (1), the crystalline polyolefin is selected from polyethylene or polypropylene, and the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride and polytetrafluoroethylene; the substrate is selected from a glass sheet or a silicon wafer; in the step (2), the at least two polymers are two polymers capable of generating surface-induced orientation with the first polymer, the weight ratio of the two polymers is 1-3: 3-1, and the total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%; the organic solvent is selected from one or more of dichloromethane, acetonitrile or trichloromethane; the heat treatment comprises the following steps: heat treatment is carried out at 60-150 ℃ for 3-1000 minutes and then at 10-50 ℃ for 5-30 hours.
The method of the invention has simple operation and can prepare the polymer film with high orientation degree and uniform orientation in a large area. In addition, the method of the invention is suitable for preparing most of high molecular orientation films. According to the preferred technical scheme of the invention, the process from random state macromolecules to macromolecule oriented films can be completed by only one step, and the phase separation of the polymer blend at a nanometer level can be achieved.
Drawings
FIGS. 1 and 2 are respectively a polarization microscope photograph (0 ℃ C., (45 ℃ C.)) of the oriented polymer film of example 1. And observing a corresponding extinction phenomenon through contrast of light and shade change, and proving that the obtained film obtains an oriented structure.
Fig. 3 and 4 are a height view and a phase diagram of atomic force microscope images of the oriented polymer film of example 1, respectively. The film has a parallel platelet structure, and the thickness of the platelets is 20 nm.
Fig. 5 and 6 are atomic force microscope images of the temperature changing process of the oriented polymer thin film of example 1. FIG. 5 shows the crystallization of poly (1, 4-butylene adipate) and polycaprolactone, and FIG. 6 shows the crystallization of polycaprolactone after temperature increase, thus demonstrating phase separation at the nanoscale level.
FIG. 7 is a transmission electron micrograph of an oriented polymer film of example 1. The diffraction points (003) and (004) show that the polycaprolactone and the poly adipic acid-1, 4-butanediol ester have the same orientation structure, and the poly adipic acid-1, 4-butanediol ester is in a beta crystal form.
Detailed Description
The present invention will be further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
In the present invention, "parallel" means that the directions of the two are substantially the same, and the directions are not limited to be absolutely the same.
< Polymer oriented film and Process for producing the same >
The preparation method of the polymer oriented film comprises the following steps: (1) a first polymer oriented film forming step; (2) and forming a polymer oriented film.
In step (1) of the present invention, a first polymer-oriented film is prepared by a melt-stretching method, and the first polymer-oriented film is attached to a substrate. The melt-drawing process may be carried out using apparatus and processes known in the art, for example as disclosed in CN103407179A or CN103451698A, the entire contents of which are incorporated herein by reference. The melt-stretching method can conveniently obtain a polymer oriented film with the thickness of nanometer level.
The first polymer is dissolved in an organic solvent to obtain a solution having a first polymer concentration of 0.1 to 5 wt%, for example 1 to 3 wt%. Preheating a hot table to 110-235 ℃, preferably 130-200 ℃, and more preferably 135-165 ℃, then pouring the solution onto a substrate (such as a glass plate or a silicon wafer) placed on the preheated hot table, and uniformly coating to form a thin film. After the organic solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 60-200 rpm, for example 100-120 rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a preset height, and at the moment, a first polymer oriented film in melt stretching orientation is formed between the rotating roller and the substrate. And taking down the first polymer orientation film by a substrate attaching mode.
According to one embodiment of the invention, the polyethylene is dissolved in xylene to give a solution with a polyethylene concentration of 1% by weight. Preheating a heating table to 135 ℃, pouring the solution onto a glass plate placed on the preheated heating table, and uniformly coating to form a film. After the solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 120rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a certain height, and at the moment, a melt-stretched oriented polyethylene film is formed between the rotating roller and the glass plate. And taking down the polyethylene film in a substrate attaching mode. Thus, a nano-scale oriented film can be easily obtained.
In step (1) of the present invention, the first polymer in the first polymer-oriented film may be selected from a crystalline polyolefin or a crystalline polyhalogenated olefin. Examples of crystalline polyolefins include, but are not limited to, polyethylene, polypropylene, polybutylene, and mixtures thereof. For example, the crystalline polyolefin is selected from polyethylene or polypropylene. Crystalline polyhalogenated olefins include polyfluorinated olefins or polychloro olefins and the like, and specific examples include, but are not limited to, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride and the like. For example, the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride and polytetrafluoroethylene. The invention finds that the oriented film formed by the polymer is used as a substrate, and is very beneficial to the phase separation of a subsequent polymer blend at a nanometer level. According to one embodiment of the invention, the first polymer is selected from polyethylene, polypropylene or polyvinylidene fluoride, preferably polyethylene. The first polymer oriented film formed by polyethylene can effectively promote the phase separation of subsequent polymer blends to a nanometer level.
In the step (1) of the present invention, the substrate is not particularly limited. Preferably, the substrate is selected from a glass sheet or a silicon wafer, which facilitates subsequent heat treatment operations.
In step (2) of the present invention, a second polymer blend solution is attached to the first polymer oriented film by spin coating to form a second polymer film, and then heat treatment is performed to obtain a polymer oriented film having parallel platelets. The second polymer blend solution may be formed from a second polymer dissolved in an organic solvent.
In the second polymer blend solution, the organic solvent is a solvent that is incapable of dissolving the first polymer, but capable of dissolving the second polymer; specific examples include, but are not limited to, halogenated hydrocarbons, nitrile solvents, and the like. In certain embodiments, the organic solvent is selected from one or more of dichloromethane, acetonitrile, or chloroform; preferably chloroform. With the above solvents, the second polymer is very advantageous for nano-scale phase separation on the first polymer oriented film.
In the second polymer blend solution, the second polymer comprises at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer. The crystalline polymer is a polymer capable of forming a polymer crystal under a certain condition. The second polymer is a blend of at least two polymers. In a preferred embodiment of the invention, the at least two polymers are both capable of producing surface-induced orientation with the first polymer. Examples of the second polymer include, but are not limited to, polycaprolactone, polybutylene adipate, poly (butylene adipate-co-succinate), polylactic acid, polyalkylene oxide, polythiophene, polyacrylate, polymethacrylate, polyamide, polyolefin, and polyhalogenated olefin. Poly (adipic acid-co-succinic acid) butylene glycol represents a copolyester of adipic acid, succinic acid and butylene glycol. According to an embodiment of the present invention, the at least two polymers may be selected from the group consisting of polycaprolactone, polybutylene adipate, polybutylene (adipate-co-succinate), polylactic acid, polyalkylene oxide, polythiophene, polyacrylate, polymethacrylate, polyamide, polyolefin, and polyhalogenated olefin. Examples of polylactic acid include, but are not limited to, poly-l-lactic acid and the like. An example of a polybutylene adipate is 1, 4-butanediol adipate. Examples of polyalkylene oxides include, but are not limited to, polyethylene oxide, polypropylene oxide, and the like. Examples of polyacrylates include polymethyl acrylate, polyethyl acrylate, and the like. Examples of polymethacrylates include polymethyl methacrylate, polyethyl methacrylate, and the like. Examples of polyolefins include polypropylene, polyethylene, and the like. Examples of the polyhalogenated olefin include polyvinyl chloride, polyvinylidene fluoride and the like. Preferably, the polyolefin, polyhalogenated olefin, in the second polymer is different from the first polymer. The polymer of the above type is adopted to facilitate the epitaxial crystallization on the first polymer oriented film, thereby achieving the phase separation at the nanometer level.
In the present invention, the second polymer is preferably one of the following combinations: (1) poly (1, 4-butylene adipate) and polycaprolactone; (2) poly (butylene adipate-co-succinate) and polycaprolactone; (3) polymethyl methacrylate and polycaprolactone; (4) polyvinyl chloride and polycaprolactone; (5) polyoxyethylene and polycaprolactone; (6) polypropylene and polycaprolactone; (7) poly-1, 4-butylene adipate and polythiophene.
The second polymer of the present invention may comprise two polymers, and the weight ratio of the two polymers may be 1 to 3:3 to 1, preferably 1 to 1.5:1.5 to 1, for example 1: 1. In the present invention, the polymer blend with the weight ratio can obtain random distribution of the same parallel platelets, and macroscopically, the nano-phase structure of the two is understood to be parallel platelets arranged alternately. The total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%, and more preferably 0.1-3 wt%; more preferably 0.5 to 2 wt%. The total concentration means the concentration of the entire polymer in the solution.
And attaching the second polymer blend solution to the first polymer oriented film by using a spin coating method to form a second polymer film. The spin coating method may be performed using a homogenizer. The rotation speed is determined by the concentration of the particular polymer blend and the desired thickness of the second polymer film. The rotation speed may be 800 to 3500rpm, preferably 1000 to 3000 rpm. And uniformly throwing the second polymer blend solution on the surface of the first polymer oriented film by using a liquid-transferring gun.
The first polymer oriented film to which the second polymer film is attached is subjected to heat treatment to obtain a polymer oriented film. The heat treatment can be carried out in two stages. The first stage is heat-treated at 60 to 150 ℃, preferably 80 to 120 ℃ for 3 to 1000 minutes, preferably 5 to 100 minutes. The second stage is heat-treated at 10 to 50 ℃ and preferably 30 to 35 ℃ for 5 to 30 hours and preferably 10 to 25 hours. By controlling the heat treatment conditions, the two polymers can be made to form oriented nanocrystals and the distribution can be made more uniform.
In the step (2) of the present invention, the thickness of the polymer oriented film obtained may be 60nm to 2 μm, preferably 70nm to 1 μm, and more preferably 180nm to 500 nm. The thickness of the platelets may be from 1nm to 100nm, preferably from 5nm to 30 nm.
The polymer oriented film can be obtained by the preparation method. The oriented polymer film includes a first oriented polymer film and a second oriented polymer film attached to the first oriented polymer film. The second polymer film has platelets arranged in parallel and having a thickness of 1nm to 100nm, preferably 5nm to 30 nm. The thickness of the polymer oriented film is 60nm to 2 μm, preferably 70nm to 1 μm, and more preferably 180nm to 500 nm. The high molecular orientation film can be used for a light-emitting diode, a solar cell or a field effect transistor.
< method for regulating Nano-scale phase separation >
The invention also provides a regulation and control method for the nanometer-level phase separation of the high-molecular oriented film, which comprises the following steps: (1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; wherein the first polymer in the first polymer oriented film is selected from crystalline polyolefins or crystalline polyhalogenated olefins; (2) attaching the second polymer blending solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain a high molecular oriented film with parallel platelets; wherein the second polymer blend solution is formed by dissolving a second polymer in an organic solvent, the second polymer comprising at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer; the organic solvent is a solvent that is not capable of dissolving the first polymer but is capable of dissolving the second polymer. According to one embodiment of the present invention, in step (1), the crystalline polyolefin is selected from polyethylene or polypropylene, and the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride, polytetrafluoroethylene; the substrate is selected from a glass sheet or a silicon wafer; in the step (2), the at least two polymers are two polymers capable of generating surface-induced orientation with the first polymer, the weight ratio of the two polymers is 1-3: 3-1, and the total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%; the organic solvent is selected from one or more of dichloromethane, acetonitrile or trichloromethane; the heat treatment comprises the following steps: heat treatment is carried out at 60-150 ℃ for 3-1000 minutes, and then heat treatment is carried out at 10-50 ℃ for 5-30 hours.
In step (1), the first polymer in the first polymer oriented film may be selected from a crystalline polyolefin or a crystalline polyhalogenated olefin. Examples of crystalline polyolefins include, but are not limited to, polyethylene, polypropylene, polybutylene, and copolymers thereof. For example, the crystalline polyolefin is selected from polyethylene or polypropylene. Crystalline polyhalogenated olefins include polyfluorinated olefins or polychloro olefins and the like, and specific examples include, but are not limited to, polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl chloride and the like. For example, the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride and polytetrafluoroethylene. The invention finds that the oriented film formed by the polymer is used as a substrate, and is very beneficial to the phase separation of a subsequent polymer blend at a nanometer level. According to one embodiment of the invention, the first polymer is selected from polyethylene, polypropylene or polyvinylidene fluoride, preferably polyethylene. The first polymer oriented film formed by polyethylene can effectively promote the phase separation of subsequent polymer blends to a nanometer level. The substrate may be selected from a glass sheet or a silicon wafer, which may facilitate subsequent thermal processing operations.
In step (1), the melt-drawing process may be carried out using apparatuses and processes known in the art, for example, apparatuses and processes disclosed in CN103407179A or CN 103451698A. For example, the first polymer is dissolved in an organic solvent to obtain a solution having a first polymer concentration of 0.1 to 5 wt%, for example 1 to 3 wt%. Preheating a hot table to 110-235 ℃, preferably 130-200 ℃, and more preferably 135-165 ℃, then pouring the solution onto a substrate (such as a glass plate or a silicon wafer) placed on the preheated hot table, and uniformly coating to form a thin film. After the organic solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 60-200 rpm, for example 100-120 rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a preset height, and at the moment, a first polymer oriented film in melt stretching orientation is formed between the rotating roller and the substrate. And taking down the first polymer orientation film by a substrate attaching mode. According to one embodiment of the invention, the polyethylene is dissolved in xylene to give a solution with a polyethylene concentration of 1% by weight. Preheating a heating table to 135 ℃, pouring the solution onto a glass plate placed on the preheated heating table, and uniformly coating to form a film. After the solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 120rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a certain height, and at the moment, a melt-stretched oriented polyethylene film is formed between the rotating roller and the glass plate. And taking down the polyethylene film in a substrate attaching mode. Thus, a nano-scale oriented film can be easily obtained.
In the step (2), the second polymer blend solution is attached to the first polymer oriented film by spin coating to form a second polymer film. The spin coating method may be performed using a homogenizer. The rotation speed is determined by the concentration of the particular polymer blend and the desired thickness of the second polymer film. The rotation speed may be 800 to 3500rpm, preferably 1000 to 3000 rpm. And uniformly throwing the second polymer blend solution on the surface of the first polymer oriented film by using a liquid-transferring gun.
In step (2), specific examples of the organic solvent include, but are not limited to, halogenated hydrocarbons, nitrile solvents, and the like. In certain embodiments, the organic solvent is selected from one or more of dichloromethane, acetonitrile, or chloroform; preferably chloroform. With the above solvents, the second polymer is very advantageous for nano-scale phase separation on the first polymer oriented film.
In step (2), the second polymer is a blend of at least two polymers. In a preferred embodiment of the invention, the at least two polymers are both capable of producing surface-induced orientation with the first polymer. Examples of the second polymer include, but are not limited to, polycaprolactone, polybutylene adipate, poly (butylene adipate-co-succinate), polylactic acid, polyalkylene oxide, polythiophene, polyacrylate, polymethacrylate, polyamide, polyolefin, and polyhalogenated olefin. According to an embodiment of the present invention, the at least two polymers may be selected from the group consisting of polycaprolactone, polybutylene adipate, polybutylene (adipate-co-succinate), polylactic acid, polyalkylene oxide, polythiophene, polyacrylate, polymethacrylate, polyamide, polyolefin, and polyhalogenated olefin. An example of a polybutylene adipate is 1, 4-butanediol adipate. Examples of polylactic acid include, but are not limited to, poly-l-lactic acid and the like. Examples of polyalkylene oxides include, but are not limited to, polyethylene oxide, polypropylene oxide, and the like. Examples of polyacrylates include polymethyl acrylate, polyethyl acrylate, and the like. Examples of polymethacrylates include polymethyl methacrylate, polyethyl methacrylate, and the like. Examples of polyolefins include polypropylene, polyethylene, and the like. Examples of the polyhalogenated olefin include polyvinyl chloride, polyvinylidene fluoride and the like. Preferably, the polyolefin, polyhalogenated olefin, in the second polymer is different from the first polymer. The polymer of the above type is adopted to facilitate the epitaxial crystallization on the first polymer oriented film, thereby achieving the phase separation at the nanometer level. In the present invention, the second polymer is preferably one of the following combinations: (1) poly (1, 4-butylene adipate) and polycaprolactone; (2) poly (butylene adipate-co-succinate) and polycaprolactone; (3) polymethyl methacrylate and polycaprolactone; (4) polyvinyl chloride and polycaprolactone; (5) polyoxyethylene and polycaprolactone; (6) polypropylene and polycaprolactone; (7) poly-1, 4-butylene adipate and polythiophene.
In step (2), the second polymer may comprise two polymers, and the weight ratio of the two polymers may be 1 to 3:3 to 1, preferably 1 to 1.5:1.5 to 1, for example 1: 1. In the present invention, the polymer blend with the weight ratio can obtain random distribution of the same parallel platelets, and macroscopically, the nano-phase structure of the two is understood to be parallel platelets arranged alternately. The total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%, and more preferably 0.1-3 wt%; more preferably 0.5 to 2 wt%. The total concentration means the concentration of the entire polymer in the solution.
In step (2), the heat treatment may be performed in two stages. The first stage is heat-treated at 60 to 150 ℃, preferably 80 to 120 ℃ for 3 to 1000 minutes, preferably 5 to 100 minutes. The second stage is heat-treated at 10 to 50 ℃ and preferably 30 to 35 ℃ for 5 to 30 hours and preferably 10 to 25 hours. By controlling the heat treatment conditions, the two polymers can be made to form oriented nanocrystals and the distribution can be made more uniform.
By adopting the steps, the thickness of the polymer oriented film can reach 60 nm-2 μm, preferably 70 nm-1 μm, and more preferably 180 nm-500 nm; the thickness of the lamella is 1nm to 100nm, preferably 5nm to 30 nm.
The following further illustrates embodiments of the invention by way of specific examples.
The apparatus of the following example is illustrated as follows:
the polyethylene film was prepared using the apparatus disclosed in CN103407179A or CN103451698A, and the polyethylene film can also be prepared using apparatuses known in the art.
The test methods of the following examples are illustrated below:
(1) the test was performed with an Axioskop 40A polarizing microscope from zeiss, using a polarizer, and the sample was photographed at 0 ° and then rotated at 45 °.
(2) The test was carried out with an Agilent Technologies 5500 afm, Agilent Technologies, scanning mode, probe type ppp-nch, with the help of a heat distribution table, and with a temperature control procedure that was accurate, by setting the ramp rate sufficiently slow (0.1 ℃/min) until the scan time of the afm scanning a map itself was negligible. First, the height and phase diagrams at room temperature were scanned, and the scans were performed at elevated temperatures under the same conditions, followed by another scan at the melting temperature of one of the low melting polymers of the blend.
(3) The test was carried out with a transmission electron microscope of JEM-2100, and the accelerating voltage was 200 kV. The sample film was attached to a copper mesh and the resulting diffraction pattern was scanned.
Example 1
High density polyethylene HDPE was dissolved in xylene to give a 1 wt% polyethylene solution. Preheating a heating table to 135 ℃, pouring the solution onto a glass plate placed on the preheated heating table, and uniformly coating to form a film. After the solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 120rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a certain height, and at the moment, a melt-stretched oriented polyethylene film A is formed between the rotating roller and the glass plate. And taking down the polyethylene film A in a substrate attaching mode.
The polyethylene film is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Poly (1, 4-butylene adipate) and polycaprolactone (weight ratio 1:1) were dissolved in chloroform to obtain a blend solution with a polymer concentration of 1 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film was observed by a polarizing microscope, see FIGS. 1 and 2. The corresponding extinction phenomenon is observed through the contrast of light and shade change, and the obtained polymer oriented film is proved to have an oriented structure.
The polymer oriented film was tested using atomic force microscopy, see fig. 3 and 4. The thickness of the obtained polymer oriented film is 200 nm; the thickness of the platelets formed on the polyethylene film was 20nm and were arranged in parallel. In view of the difference of melting points of poly-1, 4-butanediol adipate and polycaprolactone, it can be easily observed that the poly-1, 4-butanediol adipate and polycaprolactone achieve phase separation at nanometer level by atomic force microscope during temperature variation process, see fig. 5 and 6.
The polymer oriented film was tested using transmission electron microscopy, see fig. 7. The diffraction points (003) and (004) show that the polycaprolactone and the poly adipic acid-1, 4-butanediol ester have the same orientation structure, and the poly adipic acid-1, 4-butanediol ester is in a beta crystal form.
Example 2
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Poly (butylene adipate-co-succinate) and polycaprolactone (weight ratio of 1:1) were dissolved in chloroform to obtain a blend solution with a polymer concentration of 1 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 200 nm; the thickness of the platelets formed on the polyethylene film was 20nm and were arranged in parallel. The phase separation of poly (butylene adipate-co-succinate) and polycaprolactone at a nanometer level can be easily observed by an atomic force microscope in a temperature changing process. The polymer orientation film is tested by adopting a transmission electron microscope, and polycaprolactone and poly (adipic acid-co-succinic acid) butanediol ester have the same orientation structure.
Example 3
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Polymethyl methacrylate and polycaprolactone (weight ratio 1:1) were dissolved in chloroform to give a blend solution with a polymer concentration of 2 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 120 ℃ for heat treatment for 12 hours and then transferred onto a hot stage at 35 ℃ for heat treatment for 12 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 500 nm; the thickness of the platelets formed on the polyethylene film was 40nm and were arranged in parallel. The phase separation of the polymethyl methacrylate and the polycaprolactone at the nanometer level can be easily observed through an atomic force microscope in the temperature changing process. The polymer oriented film is tested by adopting a transmission electron microscope, and polycaprolactone and polymethyl methacrylate have the same oriented structure.
Example 4
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Polyvinyl chloride and polycaprolactone (weight ratio 1:1) were dissolved in chloroform to give a blend solution with a polymer concentration of 2 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Polyvinyl chloride which can not generate epiphytic crystallization with polyethylene film can also be induced by polycaprolactone to ensure that the blend obtains an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 300 nm; the thickness of the platelets formed on the polyethylene film was 30nm and were arranged in parallel. The phase separation of the polyvinyl chloride and the polycaprolactone at a nanometer level can be easily observed through an atomic force microscope in the temperature changing process. The polymer oriented film is tested by adopting a transmission electron microscope, and polycaprolactone and polyvinyl chloride have the same oriented structure.
Example 5
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Polyoxyethylene and polycaprolactone (1: 1 by weight) were dissolved in chloroform to give a blend solution with a polymer concentration of 1 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 200 nm; the thickness of the platelets formed on the polyethylene film was 20nm and were arranged in parallel. The phase separation of the polyoxyethylene and the polycaprolactone at a nanometer level can be easily observed through an atomic force microscope in the temperature changing process. The polymer oriented film is tested by adopting a transmission electron microscope, and polycaprolactone and polyoxyethylene have the same oriented structure.
Example 6
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Polypropylene and polycaprolactone (weight ratio 1:1) were dissolved in chloroform to give a blend solution with a polymer concentration of 2 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 120 ℃ for heat treatment for 12 hours and then transferred onto a hot stage at 35 ℃ for heat treatment for 12 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 300 nm; the thickness of the platelets formed on the polyethylene film was 40nm and were arranged in parallel. The phase separation of the polypropylene and the polycaprolactone at the nanometer level can be easily observed through an atomic force microscope in the temperature changing process. The polymer oriented film is tested by adopting a transmission electron microscope, and polycaprolactone and polypropylene have the same oriented structure.
Example 7
The polyethylene film A is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Polyadipate 1, 4-butanediol ester and polythiophene (weight ratio of 1:1) were dissolved in chloroform to obtain a blend solution having a polymer concentration of 5 wt%. The rotation speed of the homogenizer was set to 1000rpm, the blend solution was uniformly thrown onto the surface of the polyethylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polyethylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure. Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 350 nm; the thickness of the platelets formed on the polyethylene film was 40nm and were arranged in parallel. The phase separation of the poly-1, 4-butanediol adipate and the polythiophene at the nanometer level can be easily observed by an atomic force microscope in the temperature change process. The polymer orientation film is tested by adopting a transmission electron microscope, and the poly adipic acid-1, 4-butanediol ester and the polythiophene have the same orientation structure.
Example 8
The polypropylene was dissolved in xylene to give a solution of polypropylene concentration of 1 wt%. Preheating a heating table to 165 ℃, then pouring the solution onto a glass plate placed on the preheated heating table, and uniformly coating to form a film. After the solvent is completely heated and volatilized, the rotating speed of the rotating roller is adjusted to be 120rpm, the rotating roller is controlled to be in rapid contact with the surface of the film and separated and lifted to a certain height, and at the moment, a melt-stretched and oriented polypropylene film B is formed between the rotating roller and the glass plate. And taking down the polypropylene film B in a substrate attaching mode.
The polypropylene film is used as a substrate of the overgrowth crystal and is attached to a silicon wafer. Poly (1, 4-butylene adipate) and polycaprolactone (weight ratio 1:1) were dissolved in chloroform to obtain a blend solution with a polymer concentration of 1 wt%. The rotation speed of the homogenizer was set to 3000rpm, the blend solution was uniformly thrown onto the surface of the polypropylene film with a pipette to form a blend film, which was placed on a hot stage at 80 ℃ for heat treatment for 5 minutes and then transferred onto a hot stage at 35 ℃ for heat treatment for 24 hours, thereby obtaining a polymer oriented film (polypropylene film + blend film).
The polymer oriented film is observed by a polarizing microscope, and a corresponding extinction phenomenon is observed by contrast of light and shade change, so that the obtained polymer oriented film is proved to have an oriented structure.
Testing the polymer oriented film by adopting an atomic force microscope, wherein the thickness of the obtained polymer oriented film is 350 nm; the thickness of the platelets formed on the polypropylene film was 20nm and were arranged in parallel. In view of the difference of the melting points of the poly-1, 4-butanediol adipate and the polycaprolactone, the nano-scale phase separation of the poly-1, 4-butanediol adipate and the polycaprolactone can be easily observed through an atomic force microscope in the temperature change process.
The polymer oriented film was tested using a transmission electron microscope. The diffraction points (003) and (004) show that the polycaprolactone and the poly adipic acid-1, 4-butanediol ester have the same orientation structure, and the poly adipic acid-1, 4-butanediol ester is in a beta crystal form.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.

Claims (19)

1. A method for preparing a polymer oriented film is characterized by comprising the following steps:
(1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; wherein the first polymer in the first polymer oriented film is selected from crystalline polyolefins or crystalline polyhalogenated olefins;
(2) attaching the second polymer blending solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain a high molecular oriented film with parallel platelets; wherein the second polymer blend solution is formed by dissolving a second polymer in an organic solvent, the second polymer comprising at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer; the organic solvent is a solvent that is incapable of dissolving the first polymer, but capable of dissolving the second polymer; wherein the second polymer is one of the following combinations:
(1) poly (1, 4-butylene adipate) and polycaprolactone;
(2) poly (butylene adipate-co-succinate) and polycaprolactone;
(3) polymethyl methacrylate and polycaprolactone;
(4) polyoxyethylene and polycaprolactone;
(5) polypropylene and polycaprolactone;
(6) poly-1, 4-butylene adipate and polythiophene.
2. The method according to claim 1, wherein in the step (1), the crystalline polyolefin is selected from polyethylene or polypropylene, and the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride or polytetrafluoroethylene; the substrate is selected from a glass sheet or a silicon wafer.
3. The method according to claim 2, wherein in the step (2), the second polymer is poly (1, 4-butylene adipate) and polycaprolactone in a weight ratio of 1: 1.
4. The method according to claim 2, wherein in the step (2), the second polymer is poly (butylene adipate-co-succinate) and polycaprolactone at a weight ratio of 1: 1.
5. The method according to claim 2, wherein in the step (2), the second polymer is polymethyl methacrylate and polycaprolactone at a weight ratio of 1: 1.
6. The method according to claim 2, wherein in the step (2), the second polymer is polyoxyethylene and polycaprolactone in a weight ratio of 1: 1.
7. The method according to claim 2, wherein in the step (2), the second polymer is polypropylene and polycaprolactone in a weight ratio of 1: 1.
8. The method according to claim 2, wherein in the step (2), the second polymer is poly (1, 4-butylene adipate) and polythiophene in a weight ratio of 1: 1.
9. The method according to claim 1, wherein in the step (2), the at least two polymers are two polymers capable of generating surface-induced orientation with the first polymer, and the weight ratio of the two polymers is 1-3: 3-1, and the total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%; the organic solvent is selected from one or more of dichloromethane, acetonitrile or trichloromethane.
10. The production method according to claim 9, wherein in the step (2), the heat treatment is: heat treatment is carried out at 60-150 ℃ for 3-1000 minutes, and then heat treatment is carried out at 10-50 ℃ for 5-30 hours.
11. The method according to claim 10, wherein in the step (2), the thickness of the polymer oriented film is 60nm to 2 μm, and the thickness of the platelets is 1nm to 100 nm.
12. A regulation and control method for nanometer-level phase separation of a high-molecular orientation film is characterized by comprising the following steps:
(1) preparing a first polymer oriented film by adopting a melt-stretching method, and attaching the first polymer oriented film on a substrate; wherein the first polymer in the first polymer oriented film is selected from crystalline polyolefins or crystalline polyhalogenated olefins;
(2) attaching the second polymer blending solution to the first polymer oriented film by adopting a spin coating method to form a second polymer film, and then carrying out heat treatment to obtain a high molecular oriented film with parallel platelets; wherein the second polymer blend solution is formed by dissolving a second polymer in an organic solvent, the second polymer comprising at least two polymers, wherein at least one polymer is a crystalline polymer capable of producing surface-induced orientation with the first polymer; the organic solvent is a solvent that is incapable of dissolving the first polymer, but capable of dissolving the second polymer; wherein the second polymer is one of the following combinations:
(1) poly (1, 4-butylene adipate) and polycaprolactone;
(2) poly (butylene adipate-co-succinate) and polycaprolactone;
(3) polymethyl methacrylate and polycaprolactone;
(4) polyoxyethylene and polycaprolactone;
(5) polypropylene and polycaprolactone;
(6) poly-1, 4-butylene adipate and polythiophene.
13. The method of regulating as claimed in claim 12, wherein:
in the step (1), the crystalline polyolefin is selected from polyethylene or polypropylene, and the crystalline polyhalogenated olefin is selected from polyvinylidene fluoride and polytetrafluoroethylene; the substrate is selected from a glass sheet or a silicon wafer;
in the step (2), the at least two polymers are two polymers capable of generating surface-induced orientation with the first polymer, the weight ratio of the two polymers is 1-3: 3-1, and the total concentration of the two polymers in the second polymer blending solution is 0.01-5 wt%; the organic solvent is selected from one or more of dichloromethane, acetonitrile or trichloromethane; the heat treatment comprises the following steps: heat treatment is carried out at 60-150 ℃ for 3-1000 minutes, and then heat treatment is carried out at 10-50 ℃ for 5-30 hours.
14. The method for controlling of claim 12, wherein in the step (2), the second polymer is poly (1, 4-butylene adipate) and polycaprolactone in a weight ratio of 1: 1.
15. The method according to claim 12, wherein in the step (2), the second polymer is poly (butylene adipate-co-succinate) and polycaprolactone in a weight ratio of 1: 1.
16. The method according to claim 12, wherein in the step (2), the second polymer is polymethyl methacrylate and polycaprolactone at a weight ratio of 1: 1.
17. The method for controlling according to claim 12, wherein in the step (2), the second polymer is polyoxyethylene and polycaprolactone in a weight ratio of 1: 1.
18. The method for controlling of claim 12, wherein in the step (2), the second polymer is polypropylene and polycaprolactone in a weight ratio of 1: 1.
19. The method for controlling according to claim 12, wherein in the step (2), the second polymer is poly (1, 4-butylene adipate) and polythiophene in a weight ratio of 1: 1.
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