WO2018166441A1 - 一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用 - Google Patents

一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用 Download PDF

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WO2018166441A1
WO2018166441A1 PCT/CN2018/078813 CN2018078813W WO2018166441A1 WO 2018166441 A1 WO2018166441 A1 WO 2018166441A1 CN 2018078813 W CN2018078813 W CN 2018078813W WO 2018166441 A1 WO2018166441 A1 WO 2018166441A1
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dvb
peg
nanospheres
microspheres
nano
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戴李宗
朱继红
陈尚月
李云同
袁丛辉
陈国荣
曾碧榕
许一婷
罗伟昂
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Xiamen University
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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/02—Polyalkylene oxides
    • 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
    • C08J2425/00—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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2425/02—Homopolymers or copolymers of hydrocarbons
    • C08J2425/04—Homopolymers or copolymers of styrene
    • C08J2425/08—Copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the invention relates to the crystallization of organic polymer compounds and the field of nano composite materials, in particular to a method for inducing orderly arrangement of nano microspheres by polymer crystallization and its application in preparing composite membranes.
  • Nanomaterials and nanocomposites due to their unique structure and excellent performance, are widely used in many fields such as optoelectronics, microelectronics, and aerospace.
  • nano-microspheres As a typical structure of nanomaterials, nano-microspheres have the advantages of structural structure controllable and have many applications in optics and surface science. There are many ways to arrange nano-microspheres in order, but each has its own advantages and disadvantages.
  • scientists are constantly trying to find a method that is easy to operate and has a wide range of practicalities.
  • PS-DVB polystyrene-divinylbenzene
  • the PEG crystal in the mixed solution may be assisted by a dropping method, comprising: dropping the mixed solution on a pre-treated glass substrate laid flat, and then placing the glass substrate in 20 ⁇ After drying at 40 ° C, the PS-DVB nanospheres were ordered by PEG crystallisation according to the growth direction of the PEG crystal, and a composite film formed by PS-DVB nanospheres in the order of PEG crystal growth was obtained on the glass substrate.
  • a dropping method comprising: dropping the mixed solution on a pre-treated glass substrate laid flat, and then placing the glass substrate in 20 ⁇ After drying at 40 ° C, the PS-DVB nanospheres were ordered by PEG crystallisation according to the growth direction of the PEG crystal, and a composite film formed by PS-DVB nanospheres in the order of PEG crystal growth was obtained on the glass substrate.
  • the initiator is potassium persulfate (KPS).
  • the present invention has the following beneficial effects:
  • the present invention provides a novel manner of inducing the orderly arrangement of nanospheres, that is, the use of polymer crystallization to induce nano-spheres to be arranged in an orderly manner according to the growth direction of dendrites, the method is simple in operation and wide in applicability; Further modifying the ordered nano-microspheres can apply the composite material to different fields; and replacing the crystalline polymer substrate guiding the ordered arrangement of the nano-spheres makes the nano-composite expected to have nano-micro Ball modified and reinforced film material or body material.
  • Figure 1 is a scanning electron micrograph of PS-DVB (polystyrene-divinylbenzene) nanospheres obtained in Example 1 of the present invention.
  • Example 2 is an optical micrograph (a) and a scanning electron micrograph (b) of a solution state PEG crystal obtained in Example 1 of the present invention.
  • Example 3 is a polarizing microscope (a) and a scanning electron microscope (b) showing the orderly arrangement of PS-DVB microspheres in solution state PEG crystal obtained in Example 1 of the present invention.
  • the vertical deposition method was used to assist the PEG crystallization to induce the ordering of PS-DVB nanospheres: 4ml of 30% PEG2000 aqueous solution was prepared, and then 1mL of the PS-DVB with a concentration of 10% and a particle size of 450nm obtained in step 2) was obtained.
  • the nanosphere emulsion was mixed with an aqueous solution of PEG2000 to obtain a mixed solution, which was stored in a 50 mL centrifuge tube.
  • the droplet-method assisted PEG crystallization was used to induce the ordering of PS-DVB nanospheres: 4 ml of 10% PEG2000 aqueous solution was prepared, and then 1 mL of the PS obtained in step 2) and having a concentration of 10% and a particle diameter of 420 nm was added thereto.
  • the vertical deposition method was used to assist the PEG crystallization to induce the ordering of PS-DVB nanospheres: 4ml of 10% PEG2000 aqueous solution was prepared, and then 1mL of the PS-DVB with the concentration of 10% and the particle size of 420nm obtained in step 2) was obtained.
  • the nanosphere emulsion was mixed with an aqueous solution of PEG2000 to obtain a mixed solution, which was stored in a 50 mL centrifuge tube.
  • the vertical deposition method was used to assist the PEG crystallization to induce the ordering of PS-DVB nanospheres: 4ml of 5% aqueous solution of PEG2000 was prepared, and then 1mL of PS-DVB with the concentration of 8% and 400nm diameter obtained in step 2) was obtained. The nanosphere emulsion was mixed with an aqueous solution of PEG2000 to obtain a mixed solution, which was stored in a 50 mL centrifuge tube.
  • the droplet-method-assisted PEG crystallization was used to induce the ordering of PS-DVB nanospheres: 4 ml of a 1% concentration of PEG2000 aqueous solution was prepared, and then 1 mL of the PS obtained in step 2) and having a concentration of 10% and a particle diameter of 400 nm was added thereto.
  • the vertical deposition method was used to assist PEG crystallization to induce the ordering of PS-DVB nanospheres: 4 ml of 1% PEG2000 aqueous solution was prepared, and then 1 mL of the PS-DVB with a concentration of 10% and a particle diameter of 400 nm obtained in step 2) was obtained. The nanosphere emulsion was mixed with an aqueous solution of PEG2000 to obtain a mixed solution, which was stored in a 50 mL centrifuge tube.

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Abstract

本发明公开了一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用。首先，采用无皂乳液聚合法制备不同尺寸的单分散PS-DVB纳米微球；采用上述所制备的PS-DVB纳米微球作为原料，加入不同浓度的PEG水溶液，利用溶液态PEG结晶诱导纳米微球有序排列；并利用扫描电镜和偏光显微镜进行表征。该方法操作简捷，适用性广。通过对有序排列的微球进一步修饰，可将该复合材料应用到不同的领域中；而更换诱导微球有序排列的结晶聚合物基材，则使该纳米复合材料有望成为具有纳米微球修饰和增强的薄膜材料或体型材料。

Description

一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用 技术领域
本发明涉及有机高分子化合物的结晶以及纳米复合材料领域，特别是涉及一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜的上的应用。
背景技术
纳米材料和纳米复合材料，因其结构的独特性，优异的各项性能，在光电、微电子、航天航空等众多领域都有广泛应用。纳米微球作为纳米材料的一个典型结构，其有序排列体具有结构构筑可控的优点，在光学以及表面学中有诸多应用。纳米微球有序排列的方法有很多，但都有各自的优缺点，科学家们正不断尝试发现一种操作简便、实用性广的方法。
发明内容
本发明的目的在于克服现有技术的不足之处，提供了一种新的方式诱导纳米微球有序排列，即通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用。
本发明解决其技术问题所采用的技术方案之一是：
一种通过聚合物结晶诱导纳米微球有序排列的方法，首先通过无皂乳液法制备PS-DVB纳米微球，然后利用溶液态PEG结晶诱导PS-DVB纳米微球有序排列；具体包括以下步骤：
1)将PS(苯乙烯)和DVB(二乙烯基苯)混合，加入去离子水，在氮气保护、搅拌、冷凝回流的条件下，调整温度至75～85℃，然后向其中逐滴加入浓度为0.002～0.003g/ml的引发剂水溶液，反应8～10h；所述PS、DVB、引发剂水溶液的体积比为1～2:0.02～0.03:9～11；
2)步骤1)反应得到的产物洗涤后，得到PS-DVB(聚苯乙烯-二乙烯基苯)纳米微球，粒径为400～500nm；通过控制DVB的用量可以得到不同尺寸的单分散PS-DVB纳米微球；将其配制为浓度8～12％的PS-DVB纳米微球乳液；
3)将步骤2)得到的浓度为8～12％(质量体积百分比)的PS-DVB纳米微球乳 液与1～30％的PEG水溶液按照体积比1:3～5的比例混合，得到混合溶液；通过混合溶液中PEG结晶以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列。
具体地，所述步骤3)中，混合溶液中PEG结晶可以由滴膜法辅助，包括：将所述混合溶液滴在平放的经预处理的玻璃基底上，然后将玻璃基底置于20～40℃下干燥，通过PEG结晶诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，并在玻璃基底上得到由PS-DVB纳米微球按照PEG晶体生长方向有序排列形成的复合膜。
具体地，所述步骤3)中，混合溶液中PEG结晶可以由垂直沉积法辅助，包括：将经预处理的玻璃基底垂直插入所述混合溶液中，置于30～50℃下干燥22～26h，通过PEG结晶诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，并在玻璃基底上得到由PS-DVB纳米微球按照PEG晶体生长方向有序排列形成的复合膜。
在本发明的一个优选实验方案中，所述引发剂为过硫酸钾(KPS)。
在本发明的一个优选实验方案中，所述PEG为分子量2000的聚合物，即PEG2000。
本发明解决其技术问题所采用的技术方案之二是：
上述方法在制备复合膜等复合材料上的用途。
相较于现有技术，本发明具有以下有益效果：
(1)本发明提供了一种新的诱导纳米微球有序排列的方式，即利用聚合物结晶诱导纳米微球按照树枝状晶体生长方向有序排列，该方法操作简捷，适用性广；通过对有序排列的纳米微球进一步修饰，可将该复合材料应用到不同的领域中；而更换引导纳米微球有序排列的结晶聚合物基材，则使该纳米复合材料有望成为具有纳米微球修饰和增强的薄膜材料或体型材料。
(2)本发明的PS-DVB(聚苯乙烯-二乙烯基苯)纳米微球是采用无皂乳液聚合法制备得到的，纳米微球表面洁净，后处理简单；制备方法简单，工艺成熟，成本低廉。
(3)本发明诱导PS-DVB微球有序排列的方法是通过溶液态PEG结晶来实现的，可操作性强，装置简单，可重复性好。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1是本发明实施例1得到的PS-DVB(聚苯乙烯-二乙烯基苯)纳米微球的扫描电镜图。
图2是本发明实施例1得到的溶液态PEG晶体的光学显微镜图(a)和扫描电镜图(b)。
图3是本发明实施例1得到的溶液态PEG结晶诱导PS-DVB微球有序排列的偏光显微镜图(a)和扫描电镜图(b)。
具体实施方式
下面通过实施例具体说明本发明的内容：
实施例1
1)在150mL三口瓶中加入2mL PS和0.03mL DVB，并加入40mL去离子水，固定装置，通入冷凝水和氮气，之后加入磁子进行搅拌，调整温度至稳定到80℃后用针筒向其中逐滴加入10ml含0.03g KPS的水溶液，反应8h；
2)将步骤1)反应得到的产物用无水乙醇洗涤2次，再用去离子水洗涤1次，得到粒径为450nm的PS-DVB纳米微球，将其配成10％的PS-DVB纳米微球乳液，置于50mL离心管中备用；
3)通过滴膜法或垂直沉积法辅助混合溶液中PEG结晶，以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，具体地：
采用滴膜法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为30％的PEG2000水溶液，然后在其中加入1mL步骤2)中得到的浓度为10％、粒径为450nm的PS-DVB纳米微球乳液，充分混合后，得到混合溶液；用滴管取一滴混合溶液，滴在预处理好(浓硫酸浸泡后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)的玻璃基底上，然后平稳放入30℃的烘箱中干燥，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
采用垂直沉积法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为30％的PEG2000水溶液，之后将1mL步骤2)中得到的浓度为10％、粒径为450nm的PS-DVB纳米微球乳液与PEG2000水溶液混合，得到混合溶液，并保存在50mL离心管中。将处理好的玻璃基底(浓硫酸浸泡24h后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)用氮气吹干后，垂直插入该混合溶液中，于40℃烘箱中干燥24h，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
实施例2
1)在150mL三口瓶中加入2mL PS和0.03mL DVB，并加入40mL去离子水，固定装置，通入冷凝水和氮气，之后加入磁子进行搅拌，调整温度至稳定到80℃后用针筒向其中逐滴加入10ml含0.03g KPS的水溶液，反应10h；
2)将步骤1)反应得到的产物用无水乙醇洗涤2次，再用去离子水洗涤1次，得到粒径为450nm的PS-DVB纳米微球，将其配成12％的PS-DVB纳米微球乳液，置于50mL离心管中备用；
3)通过滴膜法或垂直沉积法辅助混合溶液中PEG结晶，以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，具体地：
采用滴膜法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为20％的PEG2000水溶液，然后在其中加入1mL步骤2)中得到的浓度为12％、粒径为450nm的PS-DVB纳米微球乳液，充分混合后，得到混合溶液；用滴管取一滴混合溶液，滴在预处理好(浓硫酸浸泡后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)的玻璃基底上，然后平稳放入30℃的烘箱中干燥，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
采用垂直沉积法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为20％的PEG2000水溶液，之后将1mL步骤2)中得到的浓度为12％、粒径为450nm的PS-DVB纳米微球乳液与PEG2000水溶液混合，得到混合溶液，并保存在50mL离心管中。将处理好的玻璃基底(浓硫酸浸泡24h后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)用氮气吹干后，垂直插入该混合溶液中，于40℃烘箱中干燥24h，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
实施例3
1)在150mL三口瓶中加入2mL PS和0.025mL DVB，并加入40mL去离子水，固定装置，通入冷凝水和氮气，之后加入磁子进行搅拌，调整温度至稳定到80℃后用针筒向其中逐滴加入10ml含0.03g KPS的水溶液，反应10h；
2)将步骤1)反应得到的产物用无水乙醇洗涤2次，再用去离子水洗涤1次，得到粒径为420nm的PS-DVB纳米微球，将其配成10％的PS-DVB纳米微球乳液，置 于50mL离心管中备用；
3)通过滴膜法或垂直沉积法辅助混合溶液中PEG结晶，以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，具体地：
采用滴膜法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为10％的PEG2000水溶液，然后在其中加入1mL步骤2)中得到的浓度为10％、粒径为420nm的PS-DVB纳米微球乳液，充分混合后，得到混合溶液；用滴管取一滴混合溶液，滴在预处理好(浓硫酸浸泡后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)的玻璃基底上，然后平稳放入30℃的烘箱中干燥，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
采用垂直沉积法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为10％的PEG2000水溶液，之后将1mL步骤2)中得到的浓度为10％、粒径为420nm的PS-DVB纳米微球乳液与PEG2000水溶液混合，得到混合溶液，并保存在50mL离心管中。将处理好的玻璃基底(浓硫酸浸泡24h后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)用氮气吹干后，垂直插入该混合溶液中，于40℃烘箱中干燥24h，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
实施例4
1)在150mL三口瓶中加入1mL PS和0.02mL DVB，并加入30mL去离子水，固定装置，通入冷凝水和氮气，之后加入磁子进行搅拌，调整温度至稳定到80℃后用针筒向其中逐滴加入10ml含0.02g KPS的水溶液，反应8h；
2)将步骤1)反应得到的产物用无水乙醇洗涤2次，再用去离子水洗涤1次，得到粒径为400nm的PS-DVB纳米微球，将其配成8％的PS-DVB纳米微球乳液，置于50mL离心管中备用；
3)通过滴膜法或垂直沉积法辅助混合溶液中PEG结晶，以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，具体地：
采用滴膜法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为5％的PEG2000水溶液，然后在其中加入1mL步骤2)中得到的浓度为8％、粒径为400nm的PS-DVB纳米微球乳液，充分混合后，得到混合溶液；用滴管取一滴混合溶液，滴 在预处理好(浓硫酸浸泡后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)的玻璃基底上，然后平稳放入30℃的烘箱中干燥，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
采用垂直沉积法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为5％的PEG2000水溶液，之后将1mL步骤2)中得到的浓度为8％、粒径为400nm的PS-DVB纳米微球乳液与PEG2000水溶液混合，得到混合溶液，并保存在50mL离心管中。将处理好的玻璃基底(浓硫酸浸泡24h后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)用氮气吹干后，垂直插入该混合溶液中，于40℃烘箱中干燥24h，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
实施例5
1)在150mL三口瓶中加入1mL PS和0.02mL DVB，并加入40mL去离子水，固定装置，通入冷凝水和氮气，之后加入磁子进行搅拌，调整温度至稳定到80℃后用针筒向其中逐滴加入10ml含0.02g KPS的水溶液，反应8h；
2)将步骤1)反应得到的产物用无水乙醇洗涤2次，再用去离子水洗涤1次，得到粒径为400nm的PS-DVB纳米微球，将其配成10％的PS-DVB纳米微球乳液，置于50mL离心管中备用；
3)通过滴膜法或垂直沉积法辅助混合溶液中PEG结晶，以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，具体地：
采用滴膜法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为1％的PEG2000水溶液，然后在其中加入1mL步骤2)中得到的浓度为10％、粒径为400nm的PS-DVB纳米微球乳液，充分混合后，得到混合溶液；用滴管取一滴混合溶液，滴在预处理好(浓硫酸浸泡后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)的玻璃基底上，然后平稳放入30℃的烘箱中干燥，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
采用垂直沉积法辅助PEG结晶诱导PS-DVB纳米微球有序排列：配制4ml浓度为1％的PEG2000水溶液，之后将1mL步骤2)中得到的浓度为10％、粒径为400nm 的PS-DVB纳米微球乳液与PEG2000水溶液混合，得到混合溶液，并保存在50mL离心管中。将处理好的玻璃基底(浓硫酸浸泡24h后，分别用去离子水和无水乙醇清洗，用玻璃刀切到合适的尺寸，浸泡在无水乙醇中备用)用氮气吹干后，垂直插入该混合溶液中，于40℃烘箱中干燥24h，得到生长后的复合膜；在该复合膜上，PS-DVB纳米微球按照PEG树枝状晶体生长方向有序排列。
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (6)

  1. 一种通过聚合物结晶诱导纳米微球有序排列的方法，其特征在于：包括：
    1)将PS和DVB混合，加入去离子水，在氮气保护、搅拌、冷凝回流的条件下，调整温度至75～85℃，然后向其中逐滴加入浓度为0.002～0.003g/ml的引发剂过硫酸钾水溶液，反应8～10h；所述PS、DVB、引发剂水溶液的体积比为1～2:0.02～0.03:9～11；
    2)步骤1)反应得到的产物洗涤后，得到PS-DVB纳米微球，将其配制成浓度为8～12％的PS-DVB纳米微球乳液；
    3)将步骤2)得到的浓度为8～12％的PS-DVB纳米微球乳液与1～30％的PEG水溶液按照体积比1:3～5的比例混合，得到混合溶液；通过混合溶液中PEG结晶以诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列。
  2. 根据权利要求1所述的通过聚合物结晶诱导纳米微球有序排列的方法，其特征在于：所述步骤3)中，混合溶液中PEG结晶由滴膜法辅助，包括：将所述混合溶液滴在平放的经预处理的玻璃基底上，然后将玻璃基底置于20～40℃下干燥，通过PEG结晶诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，并在玻璃基底上得到由PS-DVB纳米微球按照PEG晶体生长方向有序排列形成的复合膜。
  3. 根据权利要求1所述的通过聚合物结晶诱导纳米微球有序排列的方法，其特征在于：所述步骤3)中，混合溶液中PEG结晶由垂直沉积法辅助，包括：将经预处理的玻璃基底垂直插入所述混合溶液中，置于30～50℃下干燥22～26h，通过PEG结晶诱导PS-DVB纳米微球按照PEG晶体生长方向有序排列，并在玻璃基底上得到由PS-DVB纳米微球按照PEG晶体生长方向有序排列形成的复合膜。
  4. 根据权利要求1所述的通过聚合物结晶诱导纳米微球有序排列的方法，其特征在于：所述PEG为PEG2000。
  5. 根据权利要求1所述的通过聚合物结晶诱导纳米微球有序排列的方法，其特征在于：所述PS-DVB纳米微球的粒径为400～500nm。
  6. 一种根据权利要求2或3所述的方法在制备复合膜上的用途。
PCT/CN2018/078813 2017-03-13 2018-03-13 一种通过聚合物结晶诱导纳米微球有序排列的方法及其在制备复合膜上的应用 Ceased WO2018166441A1 (zh)

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