阅读说明：本技术 一种改进的硬化层聚合物薄膜和制备方法 (Improved hardened layer polymer film and preparation method thereof ) 是由 赵远 于 2019-08-12 设计创作，主要内容包括：本发明提供了一种改进的硬化层聚合物薄膜,其为单一组分的硬化层,其结构式为：<Image he="256" wi="335" file="DDA0002162898140000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>这种硬化层是由具有有机侧链的无机双链骨架构成的梯状结构的锗氧化合物,通过具有不同侧链结构的两种锗氧化合物经过聚合反应生成,这种硬化层属于有机-无机杂化材料,提升了硬化层聚合物薄膜的硬度、抗摩擦性能和热稳定性,具有优异的光学透明性、热稳定性和良好的机械性能。(The invention provides an improved hardened layer polymer film, which is a single-component hardened layer and has a structural formula as follows: the hardened layer is a germanium oxide compound with a ladder-shaped structure formed by an inorganic double-chain framework with organic side chains, is generated by polymerization reaction of two germanium oxide compounds with different side chain structures, belongs to an organic-inorganic hybrid material, improves the hardness, the anti-friction performance and the thermal stability of a polymer film of the hardened layer, and has excellent optical transparency, thermal stability and good mechanical performance.)

1. An improved hardened layer polymer film characterized by: the polymer film is germanium oxygen polymer, and the structural formula is as follows:

wherein the content of the first and second substances,

the ranges of m and n are both 20-80.

2. The improved hardened layer polymer film of claim 1, wherein: the polymer film is composed of an inorganic double-stranded framework with organic side chains.

3. The improved hardened layer polymer film of claim 1, wherein: the side chain of the germanium oxygen polymer contains long-chain sulfydryl.

4. The improved hardened layer polymer film of claim 1, wherein: the inorganic double-chain framework of the germanium-oxygen polymer is of a ladder-shaped structure.

5. The improved hardened layer polymer film of claim 1, wherein: the germanium-oxygen polymer is prepared by polymerizing monomers with different side chain structures.

6. A method of producing the improved hardened layer polymer film, characterized by comprising the steps of:

step 1) preparation of polymer P1:wherein the content of the first and second substances,

step 10), mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 11), adding carbazolyl trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium under the condition of filling nitrogen, and stirring at room temperature until the molecular weight reaches the maximum;

step 12) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting for 2-3 times by using deionized water;

step 13) anhydrous magnesium sulfate was added, stirred overnight, filtered, and the dichloromethane in the organic phase was removed to give a white solid polymer P1:wherein

Step 2) preparation of polymer P2:wherein

Step 20) mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 21) adding 9-fluorenyltrimethoxy germanium and 3-mercapto-n-propyltrimethoxy germanium under the condition of filling nitrogen, and stirring at room temperature until the molecular weight reaches the maximum;

step 22) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting with deionized water for three times;

step 23) anhydrous magnesium sulfate was added, stirred overnight, filtered, and the dichloromethane in the organic phase was removed to give a solid polymer P2:wherein

Step 3) preparing a hardened layer polymer film;

step 31) dissolving the polymer P1 or P2 in tetrahydrofuran containing a photoinitiator, and shaking or ultrasonically shaking for one hour to obtain a colorless viscous solution;

step 32) uniformly coating the solution on the surface of glass or PET, drying at room temperature overnight, and then, drying in vacuum at 40 ℃ for 2-4 hours;

step 33) irradiating the film on the surface of the PET or glass with a UV lamp to obtain a polymer film.

7. The method of producing the improved polymer film for a hardened layer of claim 6, wherein: in the step 10), 0.04g to 0.06g, 0.29mmol to 0.43mmol of potassium carbonate, 4.8g to 5.0g of deionized water, 0.267mol to 0.278mol of deionized water and 20mL of tetrahydrofuran are added into a 100mL round-bottom flask and pumped through for three times.

8. The method of producing the improved polymer film for a hardened layer of claim 6, wherein: in the step 11), 0.48mol to 0.50mol of carbazolyl trimethoxy germanium and 0.32mol to 0.35mol of 3-mercapto-n-propyl trimethoxy germanium are added under nitrogen, and stirred for five days at room temperature.

9. The method of producing the improved polymer film for a hardened layer of claim 6, wherein: in step 12), the organic solvent was removed, the residual organic portion was dissolved in 50ml of dichloromethane, extracted three times with deionized water, and then 10g of anhydrous magnesium sulfate was added, stirred for 24 hours, and filtered to obtain a white solid polymer P1.

10. The method of producing the improved polymer film for a hardened layer of claim 6, wherein: in step 3), the resulting polymer was dissolved in 50 wt% tetrahydrofuran containing 3 wt% of a photoinitiator, shaken or ultrasonically shaken for one hour to give a colorless viscous solution, the solution was uniformly coated on a glass or PET surface, dried overnight at room temperature, then vacuum-dried at 40 ℃ for two hours, and then dried with a light density of 100Mw/cm²The total UV output energy is 3J/cm²The UV lamp irradiates the PET or glass surface film to obtain the polymer film.

Technical Field

The invention relates to a film material, in particular to a hardened layer film material.

Background

Generally, a protective film needs to be attached to the surface of a screen of an electronic product such as a mobile phone or a tablet personal computer, so that the screen is protected to prevent scratching, and the smoothness of the screen is kept. The protective film is generally made of a hardened material resistant to friction, and the hardened material is required to have good mechanical, thermodynamic and optical properties, and at the same time, to be easily processed and to have good adhesion to the plastic substrate.

To date, many organic materials, such as polymethacrylates and polycarbonates, have been extensively studied due to their good optical properties and ease of processing. However, many organic plastics have poor anti-friction properties and poor thermal stability, and thus, are difficult to be industrially applied. In order to obtain a hardened layer having excellent properties, additives and inorganic precursors may be added. However, the addition of additives to a multi-component hardened layer solution causes problems such as incomplete dispersion of the second component.

Disclosure of Invention

In order to solve the above-mentioned technical problems, the present invention provides an improved hardened layer polymer thin film which is a single-component hardened layer, the hardened layer being a germanium oxide compound having a ladder structure composed of an inorganic double-chain skeleton having organic side chains, the hardened layer being an organic-inorganic hybrid material having excellent optical transparency, thermal stability and good mechanical properties.

In the present invention, an improved hardened layer polymer film, which is a germanium-oxygen polymer, is composed of an inorganic double-stranded skeleton having organic side chains. The germanium oxygen polymer has a structure of P1 or P2, wherein the P1 is

WhereinSaid P2 isWherein

Preferably, the inorganic double-chain skeleton of the germanium oxide polymer is of a ladder-like structure. The germanium-oxygen polymer is prepared by polymerizing monomers with different side chain structures.

The present invention also provides a method for preparing the improved polymer film for a hardened layer, which comprises the following steps:

step 1) preparation of polymer P1:wherein the content of the first and second substances,

step 10), mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 11), adding carbazolyl trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium under the condition of filling nitrogen, and stirring at room temperature until the molecular weight reaches the maximum;

step 12) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting for 2-3 times by using deionized water;

step 13) anhydrous magnesium sulfate was added, stirred overnight, filtered, and the dichloromethane in the organic phase was removed to give a white solid polymer P1:wherein

Step 2) preparation of polymer P2:wherein

Step 20) mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 21) adding 9-fluorenyltrimethoxy germanium and 3-mercapto-n-propyltrimethoxy germanium under the condition of charging nitrogen, and stirring for five days at room temperature;

step 22) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting with deionized water for three times;

step 23) anhydrous magnesium sulfate was added, stirred overnight, filtered, and the dichloromethane in the organic phase was removed to give a solid polymer P2:wherein

Step 3) preparing a hardened layer polymer film;

step 31) dissolving the polymer P1 or P2 in tetrahydrofuran containing a photoinitiator, and shaking or ultrasonically shaking for one hour to obtain a colorless viscous solution;

step 32) uniformly coating the solution on the surface of glass or PET, drying at room temperature overnight, and then, drying in vacuum at 40 ℃ for 2-4 hours;

step 33) irradiating the film on the surface of the PET or glass with a UV lamp to obtain a polymer film.

Compared with the prior art, the hardened layer polymer film improves the structure of the polymer, is adjusted into a single-component hardened layer by the polymerization reaction of the original multi-component hardened layer solution and the additive, and the hardened layer is a germanium-oxygen polymer with a ladder-shaped structure consisting of an inorganic double-chain framework with organic side chains. The two germanium oxide compounds with different side chain structures are generated through polymerization reaction, the rigid inorganic group-germanium oxide chain is used as a skeleton structure of the polymer in the hardening layer, the hardness of a film of the polymer can be effectively improved, meanwhile, the fluorenyl group and the carbazolyl group which contain long-chain alkyl chains in the side chains can further adjust the hardness, and the mercapto group can effectively improve the optical performance of the polymer. The hardened layer belongs to an organic-inorganic hybrid material, improves the hardness, the anti-friction performance and the thermal stability of a polymer film of the hardened layer, and has excellent optical transparency, thermal stability and good mechanical performance.

Detailed Description

The present invention provides an improved hardened layer polymer film which is a single-component hardened layer of a germanium oxide compound having a ladder structure composed of an inorganic double-stranded skeleton having organic side chains, which is an organic-inorganic hybrid material having excellent optical transparency, thermal stability and good mechanical properties.

In the present invention, an improved hardened layer polymer film, which is a germanium-oxygen polymer, is composed of an inorganic double-stranded skeleton having organic side chains. Preferably, the inorganic double-chain skeleton of the germanium oxide polymer is of a ladder-like structure. The germanium-oxygen polymer is prepared by polymerizing monomers with different side chain structures.

The germanium oxygen polymer has a structure of P1 or P2, wherein P1 is

WhereinThe ranges of m and n are both 20-80, and the compound is polymerized from carbazolyl trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium.

Said P2 isWherein the content of the first and second substances,wherein m and n are both 20-80 and are polymerized from 9-fluorenyltrimethoxygermanium and 3-mercapto-n-propyltrimethoxygermanium.

The hardened layer polymer film is obtained by carrying out polymerization reaction according to the following reaction formula:

the component of the hardening layer polymer film is polymer P1 or P2, P1 is formed by polymerizing carbazolyl trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium, and P2 is formed by polymerizing 9-fluorene trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium. K₂CO₃/THF/H₂O represents the reactant and r.t. indicates a reaction temperature of 25 ℃.

The present invention also provides a method for preparing the improved polymer film for a hardened layer, which comprises the following steps:

step 1) preparation of polymer P1:wherein

Step 10), mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 11), adding carbazolyl trimethoxy germanium and 3-mercapto-n-propyl trimethoxy germanium under the condition of filling nitrogen, and stirring at room temperature until the molecular weight reaches the maximum;

step 12) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting for 2-3 times by using deionized water;

step 13) anhydrous magnesium sulfate was added, stirred overnight, filtered, and the dichloromethane in the organic phase was removed to give a white solid polymer P1:wherein

Step 2) preparation of polymer P2:wherein

Step 20) mixing potassium carbonate, deionized water and tetrahydrofuran, adding into a round-bottom flask, and pumping through for many times;

step 21) adding 9-fluorenyltrimethoxy germanium and 3-mercapto-n-propyltrimethoxy germanium under the condition of filling nitrogen, and stirring at room temperature until the molecular weight reaches the maximum;

step 22) removing the organic solvent, dissolving the organic part in dichloromethane, and extracting with deionized water for three times;

step 23) Anhydrous magnesium sulfate was added, stirred overnight, filtered and the dichloromethane in the organic phase removedTo obtain a solid polymer P2:wherein

Step 3) preparing a hardened layer polymer film;

step 31) dissolving the polymer P1 or P2 in tetrahydrofuran containing a photoinitiator, and shaking or ultrasonically shaking for one hour to obtain a colorless viscous solution;

step 32) uniformly coating the solution on the surface of glass or PET, drying at room temperature overnight, and then, drying in vacuum at 40 ℃ for 2-4 hours;

step 33) irradiating the film on the surface of the PET or glass with a UV lamp to obtain a polymer film.

Preferably, in step 10), 0.04g to 0.06g of potassium carbonate, 0.29mmol to 0.43mmol of deionized water, 4.8g to 5.0g of deionized water, 0.267mol to 0.278mol of deionized water and tetrahydrofuran (20mL) are added into a 100mL round-bottom flask and pumped through three times to remove oxygen. Wherein potassium carbonate can be replaced by cesium carbonate or sodium carbonate, and tetrahydrofuran can be replaced by diethyl ether.

In the step 11), under nitrogen, excluding the influence of oxygen on the polymerization reaction, adding 0.48-0.50 mol of carbazolyl trimethoxy germanium and 0.32-0.35 mol of 3-mercapto-n-propyl trimethoxy germanium, stirring for five days at room temperature, and carrying out the following reactions:

in step 12), tetrahydrofuran, which is an organic solvent, is removed, an organic portion (P1 containing impurities) is dissolved in dichloromethane (which is a solvent), 50ml of dichloromethane is taken and extracted three times with deionized water, impurities are taken out to obtain a dichloromethane solution containing a polymer P1, 10g of anhydrous magnesium sulfate is added, a small amount of water contained in the dichloromethane solution is removed, stirring is carried out for 24 hours, and filtering is carried out to obtain a white solid polymer P1.

In the step 3), the obtained polymer P1 or P2 is dissolved in a solution containing 3 wt% of photoinitiator (Irgacure-250) and 50 wt% of Tetrahydrofuran (THF), the solution is shaken or ultrasonically vibrated for one hour, and is uniformly mixed to obtain a colorless viscous solution, the solution is uniformly coated on the surface of glass or PET, the solution is dried overnight at room temperature, then the solution is dried for two hours in vacuum at 40 ℃, and then the film on the surface of the PET or glass is irradiated by a UV lamp for 2 hours for surface treatment, so that the polymer film can be obtained.

Wherein the light intensity of the UV lamp is 3J/cm²The output energy optical density is 100mW/cm²。

The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.