阅读说明：本技术 一种柔性超拉伸超疏水电子器件基底及其制备方法和应用 (Flexible super-stretching super-hydrophobic electronic device substrate and preparation method and application thereof ) 是由 李祎 肖淞 唐炬 张晓星 潘成 曾福平 于 2021-09-27 设计创作，主要内容包括：本发明公开了一种柔性超拉伸超疏水电子器件基底及其制备方法和应用。制备方法如下：(1)将苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)溶于溶剂中形成溶液A；(2)将氟化二氧化硅纳米颗粒(F-SiO-(2)NPs)在乙醇溶液中超声分散,形成分散液B；(3)将溶液A和分散液B基于共轭静电纺丝并经收集器收集后制备得到超拉伸超疏水电子器件基底。本发明提供的柔性电子器件基底具有拉伸率高、疏水性良好,可应用于制作电子器件基底薄膜,具有较大的应用前景和应用价值。本发明的原材料成本低廉,共轭静电纺丝加工方法具备大规模工业化应用的潜力。(The invention discloses a flexible super-stretching super-hydrophobic electronic device substrate and a preparation method and application thereof. The preparation method comprises the following steps: (1) dissolving a styrene-isoprene-styrene block copolymer (SIS) in a solvent to form a solution A; (2) fluorinated silica nanoparticles (F-SiO) 2 NPs) are ultrasonically dispersed in an ethanol solution to form a dispersion liquid B; (3) and (3) preparing the solution A and the dispersion liquid B based on conjugated electrostatic spinning and collecting by a collector to obtain the substrate of the super-stretching super-hydrophobic electronic device. The flexible electronic device substrate provided by the invention has high tensile rate and good hydrophobicityThe method can be applied to manufacturing the substrate film of the electronic device, and has a great application prospect and application value. The raw material cost of the invention is low, and the conjugate electrostatic spinning processing method has the potential of large-scale industrial application.)

1. The preparation method of the flexible super-stretched super-hydrophobic electronic device substrate is characterized by comprising the following steps

(1) Dissolving a styrene-isoprene-styrene block copolymer (SIS) in a solvent to form a solution A;

(2) fluorinated silica nanoparticles (F-SiO)₂NPs) are ultrasonically dispersed in an ethanol solution to form a dispersion liquid B;

(3) and (3) filling the solution A and the dispersion liquid B into an injector, processing by adopting a conjugated electrostatic spinning method, and collecting the micron fibers by a collector to prepare the super-stretched super-hydrophobic electronic device substrate.

2. The preparation method according to claim 1, wherein the solvent in the step (1) is a mixed solvent formed by mixing toluene and dimethylformamide, and the volume ratio of toluene to dimethylformamide is 85: 15.

3. The method as claimed in claim 1, wherein the styrene-isoprene-styrene block copolymer has a molecular weight of 70000-90000, wherein the mass fraction of styrene is 22%; the mass fraction of the styrene-isoprene-styrene block copolymer in the solution A is 20-25%.

4. The method according to claim 1, wherein the content of the fluorinated silica nanoparticles in the dispersion liquid B in the step (2) is 2mg/ml to 10mg/ml, and the particle size of the fluorinated silica nanoparticles is 20 nm to 30 nm.

5. The method of claim 1, wherein the pumping rate of the conjugate spinning of solution A and dispersion B is kept consistent and is 1.5ml/h to 2 ml/h.

6. The preparation method according to claim 1, wherein the pump outlets of the solution A and the dispersion B are opposite, the solution A is subjected to electrostatic spinning to generate the ultra-drawn micro-fibers, and the dispersion B is subjected to electrostatic spraying to generate the nano-particles.

7. The production method according to claim 1, wherein the conjugated electrospinning applied voltage is negative polarity-2 kV and positive polarity 20 kV.

8. A flexible, super stretched, super hydrophobic electronic device substrate prepared by the method of any one of claims 1 to 7.

9. Use of the flexible, super stretched, super hydrophobic electronic device substrate of claim 8 as a flexible electronic device substrate.

Technical Field

The invention belongs to the technical field of flexible electronic devices, and particularly relates to a flexible super-stretching super-hydrophobic electronic device substrate and a preparation method and application thereof.

Background

The flexible electronic device has good mechanical compliance and robustness, and has wide application prospect in the fields of wearable electronics and the like. For flexible electronic devices, the adaptability of the working environment of the flexible electronic devices can be further expanded due to the characteristics of super-stretching, super-hydrophobicity, air permeability and the like. The super-stretching capacity endows the device with the capacity of keeping normal working conditions under extreme deformation; the super-hydrophobicity is beneficial to improving the waterproof performance of the device, and the performance and service life attenuation of the device in humid and other environments are avoided; the gas permeability then helps promoting wearable electronic device's travelling comfort, has more important meaning to relying on gas release, sweat etc. to have more important as the sensor that detects the marker simultaneously, can guarantee that device work is not influenced when maintaining comfortable wearing nature.

At present, the super-stretching capability, the air permeability and the hydrophobicity of the electronic device are difficult to be compatible. The existing ultra-stretching electronic device is mostly based on a compact elastomer film substrate, such as PDMS, EVA, TPU and the like, although the substrate can meet the stretching requirement, the air permeability of the substrate is extremely poor due to the compact characteristic, and red swelling, allergy and the like are easily caused when the substrate is attached to the skin for a long time; meanwhile, the roughness of the compact flexible substrate is crossed, and the surface is lack of a micro-nano structure, so that the hydrophobicity of the film is poor.

Therefore, a substrate with good flexibility, super-stretch, super-hydrophobicity and air permeability is needed to improve the wearing comfort and environmental compatibility of the flexible electronic device.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides a flexible super-stretching super-hydrophobic electronic device substrate and a preparation method and application thereof.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

the invention provides a preparation method of a flexible super-stretched super-hydrophobic electronic device substrate in a first aspect, which comprises the following steps

(1) Dissolving a styrene-isoprene-styrene block copolymer (SIS) in a solvent to form a solution A;

(2) fluorinated silica nanoparticles (F-SiO)₂NPs) are ultrasonically dispersed in an ethanol solution to form a dispersion liquid B;

(3) and (3) filling the solution A and the dispersion liquid B into an injector, processing by adopting a conjugated electrostatic spinning method, and collecting the micron fibers by a collector to prepare the super-stretched super-hydrophobic electronic device substrate.

Further, the solvent in the step (1) is a mixed solvent formed by mixing toluene and dimethylformamide, and the volume ratio of the toluene to the dimethylformamide is 85: 15.

Further, the molecular weight of the styrene-isoprene-styrene block copolymer is 70000-90000, wherein the mass fraction of styrene is 22%; the mass fraction of the styrene-isoprene-styrene block copolymer in the solution A is 20-25%.

Further, in the step (2), the content of the fluorinated silica nanoparticles in the dispersion liquid B is 2mg/ml-10mg/ml, and the particle size of the fluorinated silica nanoparticles is 20-30 nm.

Further, the pumping rate of the conjugate spinning of the solution A and the dispersion B is kept consistent and is 1.5mL/h-2 mL/h.

Further, the pump outlets of the solution A and the dispersion B are relatively pumped out for spinning.

Further, the solution a and the dispersion B were pumped out by a syringe, and the flow rate was controlled by a micro flow control pump.

Further, the electrostatic spinning applied voltage is negative polarity-2 kV, and positive polarity 20 kV.

The invention provides a flexible super-stretch super-hydrophobic electronic device substrate prepared by the method of the first aspect.

The invention provides the application of the flexible super-stretch super-hydrophobic electronic device substrate as a flexible electronic device substrate.

The method provided by the invention can be used for preparing the substrate of the ultra-stretching flexible electronic device, and the principle is as follows: the electro-spinnability of the styrene-isoprene-styrene block copolymer solution can be improved by adding a preferred mixed solvent of toluene and dimethylformamide, especially a small amount of dimethylformamide; meanwhile, due to the high boiling point and the low saturated vapor pressure, the styrene-isoprene-styrene segmented copolymer fiber obtained by electrostatic spinning also contains a small amount of solvent residues on a collector, so that the self-welding between the fiber and the fiber node can be realized, and the firmness of the fiber node is improved; meanwhile, the fluorinated silica nanoparticles at the other end of the conjugated spinning can be self-assembled and embedded into the styrene-isoprene-styrene segmented copolymer fibers under the action of an electric field force to form a composite structure, and the fluorinated silica nanoparticles have low surface energy and simultaneously increase the fiber roughness, so that super-hydrophobicity can be realized.

Compared with the prior art, the invention has the following beneficial effects:

1. the processing of the substrate of the super-stretching super-hydrophobic flexible electronic device can be realized through conjugate spinning, wherein self-welding can be realized among elastomer fiber nodes; the nanoparticles can realize self-assembly with the fibers; finally forming a film with excellent mechanical property and hydrophobicity;

2. the raw material cost of the invention is low, and the conjugate electrostatic spinning processing method has the potential of large-scale industrial application.

3. The flexible electronic device substrate provided by the invention has high stretching rate and good hydrophobicity, can be applied to manufacturing electronic device substrate films, and has a great application prospect and application value.

Drawings

FIG. 1 is a flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1;

FIG. 2 shows the super-hydrophobic property of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1;

FIG. 3 is a gas permeability test of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1;

FIG. 4 is a micro-topography of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1;

FIG. 5 shows the micro-morphology of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1 under 1000% tensile strain.

Detailed Description

The invention is further illustrated by the following examples, without restricting the content of the invention to these.

Example 1

The preparation method of the flexible super-stretched super-hydrophobic electronic device substrate film comprises the following steps:

1) weighing 2g of styrene-isoprene-styrene block copolymer elastomer, and filling into a 20ml glass bottle with a magnetic stirrer; adding 1.5ml of dimethylformamide and 7.5ml of toluene into a glass bottle, and magnetically stirring for 4 hours to obtain a styrene-isoprene-styrene block copolymer electrospinning solution;

2) weighing 100mg of fluorinated silica nanoparticles, and filling into a 20ml glass bottle; adding 10ml of ethanol; putting the glass bottle into an ultrasonic machine, and ultrasonically dispersing for 1 hour to obtain fluorinated silicon dioxide dispersion liquid;

3) respectively transferring the fluorinated silica dispersion liquid and the styrene-isoprene-styrene block copolymer electrospinning solution into two 20ml syringes, wherein the syringes are connected with an electrospinning needle head through a pipeline and are placed into a push pump;

4) installing two syringe needles at the moving end terminal of the electrostatic spinning machine face to face, and covering an electrostatic spinning machine roller with an aluminum foil; starting an injector push pump and an electrostatic spinning machine power supply to carry out conjugate electrostatic spinning; both pump-out rates were 2 ml/h.

5) And (3) continuing the conjugation electrostatic spinning for 4h, and taking down the film on the roller collector covered by the aluminum foil after finishing the conjugation electrostatic spinning to obtain the flexible super-stretched super-hydrophobic film which can be used as a substrate of an electronic device.

Example 2

The preparation method of the flexible super-stretched super-hydrophobic electronic device substrate film comprises the following steps:

1) weighing 2g of styrene-isoprene-styrene block copolymer elastomer, and filling into a 20ml glass bottle with a magnetic stirrer; adding 1.5ml of dimethylformamide and 7.5ml of toluene into a glass bottle, and magnetically stirring for 4 hours to obtain a styrene-isoprene-styrene block copolymer electrospinning solution;

2) weighing 20mg of fluorinated silica nanoparticles, and filling into a 20ml glass bottle; adding 10ml of ethanol; putting the glass bottle into an ultrasonic machine, and ultrasonically dispersing for 1 hour to obtain fluorinated silicon dioxide dispersion liquid;

3) respectively transferring the fluorinated silica dispersion liquid and the styrene-isoprene-styrene block copolymer electrospinning solution into two 20ml syringes, wherein the syringes are connected with an electrospinning needle head through a pipeline and are placed into a push pump;

4) installing two syringe needles at the moving end terminal of the electrostatic spinning machine face to face, and covering an electrostatic spinning machine roller with an aluminum foil; starting an injector push pump and an electrostatic spinning machine power supply to carry out conjugate electrostatic spinning; both pump-out rates were 2 ml/h.

5) And (3) continuing the conjugation electrostatic spinning for 4h, and taking down the film on the roller collector covered by the aluminum foil after finishing the conjugation electrostatic spinning to obtain the flexible super-stretched super-hydrophobic film which can be used as a substrate of an electronic device.

Example 3

The preparation method of the flexible super-stretched super-hydrophobic electronic device substrate film comprises the following steps:

1) weighing 2g of styrene-isoprene-styrene block copolymer elastomer, and filling into a 20ml glass bottle with a magnetic stirrer; adding 1.5ml of dimethylformamide and 7.5ml of toluene into a glass bottle, and magnetically stirring for 4 hours to obtain a styrene-isoprene-styrene block copolymer electrospinning solution;

2) weighing 60mg of fluorinated silica nanoparticles, and filling into a 20ml glass bottle; adding 10ml of ethanol; putting the glass bottle into an ultrasonic machine, and ultrasonically dispersing for 1 hour to obtain fluorinated silicon dioxide dispersion liquid;

3) respectively transferring the fluorinated silica dispersion liquid and the styrene-isoprene-styrene block copolymer electrospinning solution into two 20ml syringes, wherein the syringes are connected with an electrospinning needle head through a pipeline and are placed into a push pump;

4) installing two syringe needles at the moving end terminal of the electrostatic spinning machine face to face, and covering an electrostatic spinning machine roller with an aluminum foil; starting an injector push pump and an electrostatic spinning machine power supply to carry out conjugate electrostatic spinning; both pump-out rates were 1.5 ml/h.

5) And (3) continuing the conjugation electrostatic spinning for 4h, and taking down the film on the roller collector covered by the aluminum foil after finishing the conjugation electrostatic spinning to obtain the flexible super-stretched super-hydrophobic film which can be used as a substrate of an electronic device.

Example 4

And (3) performance testing:

1. apparent form

FIG. 1 is a flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1, which is white overall and still maintains good mechanical structure stability (no occurrence of holes) when stretched 1000% in the transverse direction.

2. Hydrophobic Performance test

FIG. 2 shows the super-hydrophobic property of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1, wherein the static contact angle of the film reaches 152 degrees, and the film belongs to a super-hydrophobic film.

3. Air permeability test

FIG. 3 is a gas permeability test of the flexible super-stretched super-hydrophobic electronic device base film prepared in example 1. The substrate is covered in an inner beaker filled with hot water, a large beaker is sleeved outside the inner beaker, and water vapor can penetrate through the prepared super-stretching super-hydrophobic substrate and reach the inner wall of the outer beaker to be condensed to form small water drops, so that the prepared film is proved to have good air permeability.

4. Micro-morphology

Fig. 4 is a microscopic topography of the flexible super-stretched super-hydrophobic electronic device substrate film prepared in example 1, and it can be seen that fluorinated silica nanoparticles are uniformly distributed on the surface of the styrene-isoprene-styrene block copolymer fiber and can be embedded into the fiber, confirming that the fiber-nanoparticle composite material is obtained by processing in this example.

Fig. 5 shows the microscopic morphology of the flexible super-stretch super-hydrophobic electronic device substrate film prepared in example 1 under 1000% tensile strain, and it can be seen that the styrene-isoprene-styrene block copolymer fibers are arranged along the stretching direction, the fibers are not broken, and the fluorinated silica nanoparticles are not dropped, which confirms the strong tensile property and the structural stability of the prepared substrate.

The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.