WO2021027097A1 - 硬化层聚合物薄膜和制备方法 - Google Patents

硬化层聚合物薄膜和制备方法 Download PDF

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WO2021027097A1
WO2021027097A1 PCT/CN2019/115637 CN2019115637W WO2021027097A1 WO 2021027097 A1 WO2021027097 A1 WO 2021027097A1 CN 2019115637 W CN2019115637 W CN 2019115637W WO 2021027097 A1 WO2021027097 A1 WO 2021027097A1
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polymer film
hardened layer
germanium
polymer
layer polymer
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赵远
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武汉华星光电半导体显示技术有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08J2385/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Derivatives of such polymers

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  • the invention relates to a thin film material, in particular to a hardened layer thin film material.
  • the screen surface of electronic products such as mobile phones or tablet computers generally needs to be attached with a protective film to protect the screen from scratches and maintain the smoothness of the screen.
  • the protective film is generally made of anti-friction hardened materials.
  • the hardened layer material needs to have good mechanical, thermodynamic and optical properties. At the same time, it is also required to be easy to process and have good adhesion to the plastic substrate.
  • the present invention provides an improved hardened layer polymer film, which is a single-component hardened layer, and this hardened layer is germanium with a ladder structure composed of an inorganic double-stranded skeleton with organic side chains. Oxygen compounds, this hardened layer is an organic-inorganic hybrid material, has excellent optical transparency, thermal stability and good mechanical properties.
  • the improved hardened layer polymer film which is a germanium-oxygen polymer, is composed of an inorganic double-stranded skeleton with organic side chains.
  • the structure of the germanium-oxygen polymer is P1 or P2, wherein the P1 is
  • the P2 is among them.
  • the inorganic double-stranded skeleton of the germanium-oxygen polymer has a ladder structure.
  • the germanium-oxygen polymer has monomers with different side chain structures through polymerization reaction.
  • the present invention also provides a method for preparing the improved hardened layer polymer film, which includes the following steps:
  • Step 10) Mix potassium carbonate, deionized water and tetrahydrofuran into a round-bottom flask, and pump them through several times;
  • Step 11 Under nitrogen gas, add carbazolyl trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium, and stir at room temperature until the molecular weight reaches the maximum;
  • Step 12 Remove the organic solvent, dissolve the organic part in dichloromethane, and extract 2-3 times with deionized water;
  • Step 13) Add anhydrous magnesium sulfate, stir overnight, filter, and remove the methylene chloride in the organic phase to obtain a white solid polymer P1: among them
  • Step 20 Mix potassium carbonate, deionized water and tetrahydrofuran into a round-bottom flask, and pump them through several times;
  • Step 21 Under nitrogen gas, add 9-fluorene trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium, and stir at room temperature for five days;
  • Step 22 Remove the organic solvent, dissolve the organic part in dichloromethane, and extract three times with deionized water;
  • Step 23 Add anhydrous magnesium sulfate, stir overnight, filter, and remove the methylene chloride in the organic phase to obtain solid polymer P2: among them
  • Step 3) preparing a hardened layer polymer film
  • Step 31 Dissolving polymer P1 or P2 in tetrahydrofuran containing photoinitiator, shaking or ultrasonic vibration for one hour to obtain a colorless viscous solution;
  • Step 32 Coat the solution evenly on the surface of glass or PET, dry overnight at room temperature, and then vacuum dry at 40°C for 2-4 hours;
  • Step 33 Irradiate the PET or glass surface film with a UV lamp to obtain a polymer film.
  • the hardened layer polymer film of the present invention improves the structure of the polymer. It is adjusted to a single-component hardened layer by polymerization reaction of the original multi-component hardened layer solution and additives.
  • This hardened layer is A germanium-oxygen polymer with a ladder structure composed of an inorganic double-stranded skeleton with organic side chains. Two kinds of germanium oxygen compounds with different side chain structures are produced by polymerization reaction.
  • This hardened layer uses rigid inorganic groups-germanium oxygen chains as the backbone structure of the polymer, which can effectively improve the hardness of the polymer film while the side chains
  • the fluorenyl and carbazole groups containing long-chain alkyl chains can further adjust the hardness, and the mercapto group can effectively improve the optical properties of the polymer.
  • the hardened layer is an organic-inorganic hybrid material, which improves the hardness, friction resistance and thermal stability of the polymer film of the hardened layer, and has excellent optical transparency, thermal stability and good mechanical properties.
  • the present invention provides an improved hardened layer polymer film, which is a single-component hardened layer.
  • This hardened layer is a germanium oxygen compound with a ladder structure composed of an inorganic double-stranded skeleton with organic side chains.
  • the layer is an organic-inorganic hybrid material with excellent optical transparency, thermal stability and good mechanical properties.
  • the improved hardened layer polymer film which is a germanium-oxygen polymer
  • the inorganic double-stranded skeleton of the germanium-oxygen polymer has a ladder structure.
  • the germanium-oxygen polymer has monomers with different side chain structures through polymerization reaction.
  • the structure of the germanium-oxygen polymer is P1 or P2, wherein the P1 is
  • Both m and n range from 20 to 80, and are formed by polymerization of carbazolyl trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium.
  • m and n are both in the range of 20 to 80, which are formed by polymerizing 9-fluorene trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium.
  • the polymer film of the hardened layer is obtained by polymerization reaction through the following reaction formula:
  • the composition of the polymer film of the hardened layer is polymer P1 or P2.
  • P1 is polymerized by carbazolyl trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium
  • P2 is composed of 9-fluorene trimethoxy germanium and 3 -Mercapto n-propyl trimethoxy germanium polymerized.
  • K 2 CO 3 /THF/H 2 O represents the reactant
  • RT represents the reaction temperature of 25°C.
  • the present invention also provides a method for preparing the improved hardened layer polymer film, which includes the following steps:
  • Step 10) Mix potassium carbonate, deionized water and tetrahydrofuran into a round-bottom flask, and pump them through several times;
  • Step 11 Under nitrogen gas, add carbazolyl trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium, and stir at room temperature until the molecular weight reaches the maximum;
  • Step 12 Remove the organic solvent, dissolve the organic part in dichloromethane, and extract 2-3 times with deionized water;
  • Step 13) Add anhydrous magnesium sulfate, stir overnight, filter, and remove the methylene chloride in the organic phase to obtain a white solid polymer P1: among them
  • Step 20 Mix potassium carbonate, deionized water and tetrahydrofuran into a round-bottom flask, and pump them through several times;
  • Step 21 Under nitrogen gas, add 9-fluorene trimethoxy germanium and 3-mercapto n-propyl trimethoxy germanium, and stir at room temperature until the molecular weight reaches the maximum;
  • Step 22 Remove the organic solvent, dissolve the organic part in dichloromethane, and extract three times with deionized water;
  • Step 23 Add anhydrous magnesium sulfate, stir overnight, filter, and remove the methylene chloride in the organic phase to obtain solid polymer P2: among them
  • Step 3) preparing a hardened layer polymer film
  • Step 31 Dissolving polymer P1 or P2 in tetrahydrofuran containing photoinitiator, shaking or ultrasonic vibration for one hour to obtain a colorless viscous solution;
  • Step 32 Coat the solution evenly on the surface of glass or PET, dry overnight at room temperature, and then vacuum dry at 40°C for 2-4 hours;
  • Step 33 Irradiate the PET or glass surface film with a UV lamp to obtain a polymer film.
  • the potassium carbonate is taken 0.04g-0.06g, 0.29mmol-0.43mmol
  • deionized water is taken 4.8g-5.0g, 0.267mol-0.278mol
  • tetrahydrofuran (20ml) is added to a 100mL circle
  • the bottom flask was pumped three times to remove oxygen.
  • potassium carbonate can be replaced by cesium carbonate or sodium carbonate
  • tetrahydrofuran can be replaced by ether.
  • step 11 under nitrogen, to eliminate the influence of oxygen on the polymerization reaction, add 0.48mol-0.50mol carbazolyl trimethoxy germanium and 0.32mol-0.35mol 3-mercapto n-propyltrimethoxy germanium, and stir at room temperature within five days, the following reactions occurred:
  • step 12 the organic solvent tetrahydrofuran is removed, the organic part (P1 containing impurities) is dissolved in dichloromethane (as a solvent), 50ml of dichloromethane is taken, extracted with deionized water three times, and the impurities are taken out to obtain a polymer containing Then, add 10 g of anhydrous magnesium sulfate to the dichloromethane solution of P1, remove the small amount of water contained therein, stir for 24 hours, and filter to obtain the white solid polymer P1.
  • step 3 the obtained polymer P1 or P2 is dissolved in 3wt% photoinitiator (Irgacure-250) and 50wt% tetrahydrofuran (THF), shaken or ultrasonically shaken for one hour, and mixed uniformly to obtain a colorless stick Thick solution, evenly spread the solution on the surface of glass or PET, dry overnight at room temperature, then vacuum dry at 40°C for two hours, then irradiate the PET or glass surface film with a UV lamp for 2 hours, and perform surface treatment to obtain polymerization ⁇ The film.
  • 3wt% photoinitiator Irgacure-250
  • 50wt% tetrahydrofuran THF
  • the light intensity of the UV lamp is 3J/cm 2
  • the output energy optical density is 100 mW/cm 2 .

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

一种硬化层聚合物薄膜，其为单一组分的硬化层，其结构式为：(I)；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。

Description

[根据细则37.2由ISA制定的发明名称]　硬化层聚合物薄膜和制备方法 技术领域
本发明涉及薄膜材料，特别是涉及一种硬化层薄膜材料。
背景技术
手机或平板电脑等电子产品的屏幕表面一般都需要贴附保护膜，对屏幕进行保护防止刮花，保持屏幕的光滑性。保护膜一般采用抗摩擦的硬化材料制成，硬化层材料需要具有良好的机械性能、热力学性能和光学性能，同时，还要求容易加工，对塑料基底具有良好的粘附性。
技术问题
迄今为止，许多有机材料，比如聚甲基丙烯酸酯和聚碳酸酯，由于具有良好的光学性能，容易加工而被广泛研究。但是，许多有机塑料的抗摩擦性能比较差，热稳定性较差，因此，难以在工业上应用。为了得到具有优异性能的硬化层，可以加入添加剂和无机前体。但是，在多组分的硬化层溶液中加入添加剂会产生第二组分无法完全分散等问题。
技术解决方案
为解决上述技术问题，本发明提供一种改进的硬化层聚合物薄膜， 其为单一组分的硬化层，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，这种硬化层属于有机-无机杂化材料，具有优异的光学透明性、热稳定性和良好的机械性能。
在本发明中，改进的硬化层聚合物薄膜，其为锗氧聚合物，由具有有机侧链的无机双链骨架构成。所述锗氧聚合物的结构为P1或P2，其中，所述P1为
Figure PCTCN2019115637-appb-000001
其中
Figure PCTCN2019115637-appb-000002
所述P2为
Figure PCTCN2019115637-appb-000003
其中
Figure PCTCN2019115637-appb-000004
优选地，所述锗氧聚合物的无机双链骨架为梯状结构的。所述锗氧聚合物具有不同侧链结构的单体经过聚合反应生成。
本发明还提供了一种制备所述改进的硬化层聚合物薄膜的方法，其包括以下步骤：
步骤1)制备聚合物P1：
Figure PCTCN2019115637-appb-000005
其中，
Figure PCTCN2019115637-appb-000006
步骤10)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
步骤11)在充入氮气下，加入咔唑基三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌至分子量达到最大；
步骤12)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取2-3次；
步骤13)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的二氯甲烷，即可得到白色固体聚合物P1：
Figure PCTCN2019115637-appb-000007
其中
Figure PCTCN2019115637-appb-000008
步骤2)制备聚合物P2：
Figure PCTCN2019115637-appb-000009
其中
Figure PCTCN2019115637-appb-000010
步骤20)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
步骤21)在充入氮气下，加入9-芴三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌五天；
步骤22)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取三次；
步骤23)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的二氯甲烷，即可得到固体聚合物P2：
Figure PCTCN2019115637-appb-000011
其中
Figure PCTCN2019115637-appb-000012
步骤3)制备硬化层聚合物薄膜；
步骤31)将聚合物P1或者P2溶于含有光引发剂的四氢呋喃中，摇晃或者超声震动一小时，得到无色粘稠溶液；
步骤32)将溶液均匀涂在玻璃或者PET表面上，室温下干燥过夜，然后，40℃真空干燥2-4小时；
步骤33)用UV灯照射PET或者玻璃表面的薄膜，获得聚合物薄膜。
有益效果
与现有技术相比，本发明硬化层聚合物薄膜改进了聚合物的结构，由原来的多组分的硬化层溶液和添加剂聚合反应，调整为单一组分的硬化层，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 构的锗氧聚合物。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，这种硬化层用刚性无机基团-锗氧链作为聚合物的骨架结构，可以有效提升聚合物的薄膜的硬度，同时侧链中的含有长链烷基链的芴基和咔唑基可以进一步对其硬度进行调节，而其中的巯基则可以有效改善聚合物的光学性能。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。
本发明的最佳实施方式
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
本发明提供一种改进的硬化层聚合物薄膜，其为单一组分的硬化层，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，这种硬化层属于有机-无机杂化材料，具有优异的光学透明性、热稳定性和良好的机械性能。
在本发明中，改进的硬化层聚合物薄膜，其为锗氧聚合物，由具有有机侧链的无机双链骨架构成。优选地，所述锗氧聚合物的无机双链骨架为梯状结构的。所述锗氧聚合物具有不同侧链结构的单体经过聚合反应生成。
所述锗氧聚合物的结构为P1或者P2，其中，所述P1为
Figure PCTCN2019115637-appb-000013
其中
Figure PCTCN2019115637-appb-000014
m和n的范围均为20～80，由咔唑基三甲氧基锗和3-巯基正丙基三甲氧基锗聚合而成。
所述P2为
Figure PCTCN2019115637-appb-000015
其中，
Figure PCTCN2019115637-appb-000016
其中，m和n的范围均为20～80，由9-芴三甲氧基锗和3-巯基正丙基三甲氧基锗聚合而成。
所述硬化层聚合物薄膜，经过以下反应式进行聚合反应获得：
Figure PCTCN2019115637-appb-000017
硬化层聚合物薄膜的组分为聚合物P1或者P2，P1由咔唑基三甲氧基锗和3-巯基正丙基三甲氧基锗聚合而成，P2由9-芴三甲氧基锗和3-巯基正丙基三甲氧基锗聚合而成。K 2CO 3/THF/H 2O代表反应物，R.T.表示反应温度为25℃。
本发明还提供了一种制备所述改进的硬化层聚合物薄膜的方法，其 包括以下步骤：
步骤1)制备聚合物P1：
Figure PCTCN2019115637-appb-000018
其中
Figure PCTCN2019115637-appb-000019
步骤10)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
步骤11)在充入氮气下，加入咔唑基三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌至分子量达到最大；
步骤12)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取2-3次；
步骤13)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的二氯甲烷，即可得到白色固体聚合物P1：
Figure PCTCN2019115637-appb-000020
其中
Figure PCTCN2019115637-appb-000021
步骤2)制备聚合物P2：
Figure PCTCN2019115637-appb-000022
其中
Figure PCTCN2019115637-appb-000023
步骤20)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
步骤21)在充入氮气下，加入9-芴三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌至分子量达到最大；
步骤22)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取三次；
步骤23)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的二氯甲烷，即可得到固体聚合物P2：
Figure PCTCN2019115637-appb-000024
其中
Figure PCTCN2019115637-appb-000025
步骤3)制备硬化层聚合物薄膜；
步骤31)将聚合物P1或者P2溶于含有光引发剂的四氢呋喃中，摇晃或者超声震动一小时，得到无色粘稠溶液；
步骤32)将溶液均匀涂在玻璃或者PET表面上，室温下干燥过夜，然后，40℃真空干燥2-4小时；
步骤33)用UV灯照射PET或者玻璃表面的薄膜，获得聚合物薄膜。
优选地，步骤10)中，所述碳酸钾取0.04g-0.06g， 0.29mmol-0.43mmol，去离子水取4.8g-5.0g，0.267mol-0.278mol，和四氢呋喃(20ml)加入100mL的圆底烧瓶中，抽通三次，除去其中的氧气。其中，碳酸钾可以由碳酸铯或者碳酸钠来代替，四氢呋喃可以由乙醚代替。
步骤11)中，在氮气下，排除氧气对聚合反应的影响，加入0.48mol-0.50mol咔唑基三甲氧基锗和0.32mol-0.35mol 3-巯基正丙基三甲氧基锗，室温下搅拌五天，发生以下反应：
Figure PCTCN2019115637-appb-000026
步骤12)中，除去有机溶剂四氢呋喃，将有机部分(含有杂质的P1)溶于二氯甲烷(作为溶剂)，取50ml二氯甲烷，用去离子水萃取三次，取出其中杂质，得到含有聚合物P1的二氯甲烷溶液，然后，加入10g无水硫酸镁，去其中含有的少量水，搅拌24小时，过滤，即可得到白色固体聚合物P1。
步骤3)中，将所得到的聚合物P1或者P2溶于含有3wt％光引发剂(Irgacure-250)和50wt％四氢呋喃(THF)中，摇晃或者超声震动一小时，混合均匀，得到无色粘稠溶液,将溶液均匀涂在玻璃或者PET表面，室温下干燥过夜，然后，在40℃真空干燥两小时，之后用UV灯照射PET或者玻璃表面的薄膜2小时，进行表面处理，即可得 到聚合物薄膜。
其中，所述UV灯的光强度为3J/cm 2，输出能量光密度为100mW/cm 2。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (11)

  1. 一种改进的硬化层聚合物薄膜，其中：所述聚合物薄膜为锗氧聚合物，其结构式：
    Figure PCTCN2019115637-appb-100001
    其中，
    Figure PCTCN2019115637-appb-100002
    m和n的范围均为20～80；
    其中，所述聚合物薄膜由具有有机侧链的无机双链骨架构成，所述锗氧聚合物侧链含有长链巯基。
  2. 一种改进的硬化层聚合物薄膜，其中：所述聚合物薄膜为锗氧聚合物，其结构式：
    Figure PCTCN2019115637-appb-100003
    其中，
    Figure PCTCN2019115637-appb-100004
    m和n的范围均为20～80。
  3. 根据权利要求2所述的改进的硬化层聚合物薄膜，其中：所述聚合物薄膜由具有有机侧链的无机双链骨架构成。
  4. 根据权利要求2所述的改进的硬化层聚合物薄膜，其中：所 述锗氧聚合物侧链含有长链巯基。
  5. 根据权利要求2所述的改进的硬化层聚合物薄膜，其中：所述锗氧聚合物的无机双链骨架为梯状结构的。
  6. 根据权利要求2所述的改进的硬化层聚合物薄膜，其中：所述锗氧聚合物具有不同侧链结构的单体经过聚合反应生成。
  7. 一种制备所述改进的硬化层聚合物薄膜的方法，其中包括以下步骤：
    步骤1)制备聚合物P1：
    Figure PCTCN2019115637-appb-100005
    其中，
    Figure PCTCN2019115637-appb-100006
    步骤10)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
    步骤11)在充入氮气下，加入咔唑基三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌至分子量达到最大；
    步骤12)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取2-3次；
    步骤13)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的 二氯甲烷，即可得到白色固体聚合物P1：
    Figure PCTCN2019115637-appb-100007
    其中
    Figure PCTCN2019115637-appb-100008
    步骤2)制备聚合物P2：
    Figure PCTCN2019115637-appb-100009
    其中
    Figure PCTCN2019115637-appb-100010
    步骤20)将碳酸钾、去离子水和四氢呋喃相互混合加入圆底烧瓶中，并抽通多次；
    步骤21)在充入氮气下，加入9-芴三甲氧基锗和3-巯基正丙基三甲氧基锗，室温下搅拌至分子量达到最大；
    步骤22)除去有机溶剂，将有机部分溶于二氯甲烷，用去离子水萃取三次；
    步骤23)加入无水硫酸镁，搅拌过夜，过滤，除去有机相中的二氯甲烷，即可得到固体聚合物P2：
    Figure PCTCN2019115637-appb-100011
    其中
    Figure PCTCN2019115637-appb-100012
    步骤3)制备硬化层聚合物薄膜；
    步骤31)将聚合物P1或P2溶于含有光引发剂的四氢呋喃中，摇晃或者超声震动一小时，得到无色粘稠溶液；
    步骤32)将溶液均匀涂在玻璃或者PET表面上，室温下干燥过夜，然后，40℃真空干燥2-4小时；
    步骤33)用UV灯照射PET或者玻璃表面的薄膜，获得聚合物薄膜。
  8. 根据权利要求7所述制备所述改进的硬化层聚合物薄膜的方法，其中：步骤10)中，所述碳酸钾取0.04g-0.06g，0.29mmol-0.43mmol，去离子水取4.8g-5.0g，0.267mol-0.278mol，和20ml四氢呋喃加入100mL的圆底烧瓶中，抽通三次。
  9. 根据权利要求7所述制备所述改进的硬化层聚合物薄膜的方法，其中：步骤11)中，在氮气下加入0.48mol-0.50mol咔唑基三甲氧基锗和0.32mol-0.35mol 3-巯基正丙基三甲氧基锗，室温下搅拌五天。
  10. 根据权利要求7所述制备所述改进的硬化层聚合物薄膜的方法，其中：步骤12)中，除去有机溶剂，将残余有机部分溶于50ml 二氯甲烷，用去离子水萃取三次，然后加入10g无水硫酸镁，搅拌24小时，过滤，即可得到白色固体聚合物P1。
  11. 根据权利要7所述制备所述改进的硬化层聚合物薄膜的方法，其中：步骤3)中，将所得到的聚合物溶于含有3wt％光引发剂的50wt％四氢呋喃中，摇晃或者超声震动一小时，得到无色粘稠溶液,将溶液均匀涂在玻璃或者PET表面，室温下干燥过夜，然后,在40℃真空干燥两小时,之后用光密度为100Mw/cm 2，总UV输出能量为3J/cm 2的UV灯照射PET或者玻璃表面的薄膜，即可得到聚合物薄膜。
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