CN115850861A - A kind of polypropylene hydrophobic material and its preparation method and application - Google Patents
A kind of polypropylene hydrophobic material and its preparation method and application Download PDFInfo
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- ZGYICYBLPGRURT-UHFFFAOYSA-N tri(propan-2-yl)silicon Chemical compound CC(C)[Si](C(C)C)C(C)C ZGYICYBLPGRURT-UHFFFAOYSA-N 0.000 claims description 4
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 claims description 4
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 claims description 3
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- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 1
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Abstract
本发明属于高分子材料领域,尤其涉及一种聚丙烯疏水材料及其制备方法和应用。本发明提供的聚丙烯疏水材料由原料物经熔融共混挤出制成,以质量份数计,所述原料物包括:聚丙烯树脂基料100份,聚丙烯‑氟碳树脂0.5~30份,扩散剂0.1~20份,疏水稳定剂0.1~10份,疏水接枝改性剂5~20份,疏水接枝增容剂0.1~5份;所述聚丙烯‑氟碳树脂中的聚丙烯树脂和氟碳树脂在微观热力学相态结构上为双连续相结构。本发明提供的聚丙烯疏水材料通过熔融共混挤出工艺制得,工艺过程简单,可实现连续化生产,材料内外结构及性能均一,特别适用于精细结构件的生产。
The invention belongs to the field of polymer materials, in particular to a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is made of raw materials through melt blending and extrusion, and the raw materials include: 100 parts of polypropylene resin base material, 0.5-30 parts of polypropylene-fluorocarbon resin , 0.1 to 20 parts of a diffusing agent, 0.1 to 10 parts of a hydrophobic stabilizer, 5 to 20 parts of a hydrophobic graft modifier, and 0.1 to 5 parts of a hydrophobic graft compatibilizer; the polypropylene in the polypropylene-fluorocarbon resin Resin and fluorocarbon resin are bicontinuous phase structures in microscopic thermodynamic phase structure. The polypropylene hydrophobic material provided by the invention is obtained through a melt blending extrusion process, the process is simple, continuous production can be realized, the internal and external structure and performance of the material are uniform, and it is especially suitable for the production of fine structural parts.
Description
技术领域technical field
本发明属于高分子材料领域,尤其涉及一种聚丙烯疏水材料及其制备方法和应用。The invention belongs to the field of polymer materials, in particular to a polypropylene hydrophobic material and its preparation method and application.
背景技术Background technique
固体材料的疏水性是固体材料对液体表现出来的特殊的润湿性,一般指水滴在固体表面呈球状,接触角大于120度,滚动角小于10度。因为水滴在疏水材料表面滚落时可带走污染物,使材料表面保持清洁。因此疏水材料具有防水、防腐蚀、防冰以及防附着等多重特性。各国学者先后通过湿化学法、等离子照射、溶胶-凝胶法、层层自组装法、刻蚀法、化学气相沉积法、物理气相沉积法、水热法、模板法等方法研究了疏水材料的组成及结构。The hydrophobicity of solid materials is the special wettability of solid materials to liquids. Generally, water droplets are spherical on the solid surface, with a contact angle greater than 120 degrees and a roll angle less than 10 degrees. Because water droplets can carry away pollutants when they roll off the surface of hydrophobic materials, the surface of the material is kept clean. Therefore, the hydrophobic material has multiple characteristics such as waterproof, anti-corrosion, anti-icing and anti-adhesion. Scholars from various countries have successively studied the properties of hydrophobic materials through wet chemical methods, plasma irradiation, sol-gel methods, layer-by-layer self-assembly methods, etching methods, chemical vapor deposition methods, physical vapor deposition methods, hydrothermal methods, and template methods. composition and structure.
聚丙烯(PP)是五大通用树脂中的一种,由于其加工性能好,弯曲和拉伸强度高,所以在包装生产、家电制造、日用品等领域都有着广泛的应用。研究和制备疏水聚丙烯,是聚丙烯功能化改性的一个重要方面。涂覆法和表面处理法是制备表面高度疏水聚丙烯材料的常用方法,但这些方法存在诸多缺点,如工艺复杂,改性条件苛刻等;溶液涂覆改性,所用大多数溶剂为有毒试剂,对人体有害,而且生产的废水还容易造成环境污染;涂覆使用的试剂价格昂贵,生产成本也较高,因此不能满足工业化大批量生产的需要;表面处理法则是在聚丙烯材料表面刻蚀上微纳米的粗糙结构,同时接枝上低表面能的长链高分子,虽然制备出的片材接触角很高,甚至达到了超疏水,但是工艺复杂限制其发展。Polypropylene (PP) is one of the five general-purpose resins. Due to its good processability and high bending and tensile strength, it is widely used in packaging production, home appliance manufacturing, and daily necessities. Research and preparation of hydrophobic polypropylene is an important aspect of functional modification of polypropylene. Coating method and surface treatment method are common methods to prepare highly hydrophobic polypropylene materials, but these methods have many disadvantages, such as complex process, harsh modification conditions, etc.; solution coating modification, most of the solvents used are toxic reagents, Harmful to the human body, and the waste water produced is easy to cause environmental pollution; the reagents used for coating are expensive, and the production cost is also high, so it cannot meet the needs of industrialized mass production; the surface treatment method is to etch on the surface of polypropylene materials Micro-nano rough structure, while grafting long-chain polymers with low surface energy, although the contact angle of the prepared sheet is very high, even reaching super-hydrophobicity, but the complicated process limits its development.
发明内容Contents of the invention
有鉴于此,本发明的目的在于提供一种聚丙烯疏水材料及其制备方法和应用,本发明提供的聚丙烯疏水材料通过熔融共混挤出工艺制得,工艺过程简单,可实现连续化生产,材料内外结构及性能均一,特别适用于精细结构件的生产。In view of this, the object of the present invention is to provide a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is obtained through a melt blending extrusion process. The process is simple and continuous production can be realized. , The internal and external structure and performance of the material are uniform, especially suitable for the production of fine structural parts.
本发明提供了一种聚丙烯疏水材料,由原料物经熔融共混挤出制成,以质量份数计,所述原料物包括:The invention provides a polypropylene hydrophobic material, which is made of raw materials through melt blending and extrusion, and in parts by mass, the raw materials include:
所述聚丙烯-氟碳树脂中的聚丙烯树脂和氟碳树脂在微观热力学相态结构上为双连续相结构;所述聚丙烯-氟碳树脂中的聚丙烯树脂与氟碳树脂的质量比为100:(80~150)。The polypropylene resin in the polypropylene-fluorocarbon resin and the fluorocarbon resin are bicontinuous phase structures on the microscopic thermodynamic phase structure; the mass ratio of the polypropylene resin in the polypropylene-fluorocarbon resin to the fluorocarbon resin is 100: (80-150).
优选的,所述氟碳树脂为聚偏氟乙烯和四氟乙烯-六氟丙烯共聚物;所述聚偏氟乙烯和四氟乙烯-六氟丙烯共聚物的质量比为1:(0.5~2)。Preferably, the fluorocarbon resin is polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer; the mass ratio of polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer is 1:(0.5~2 ).
优选的,所述扩散剂为聚氯乙烯、氯化聚乙烯和氯磺化聚乙烯中的一种或多种。Preferably, the diffusing agent is one or more of polyvinyl chloride, chlorinated polyethylene and chlorosulfonated polyethylene.
优选的,所述疏水稳定剂为聚二甲基硅氧烷、三异丙基硅烷、三氟丙基甲基二甲氧基硅烷、聚全氟烷基硅氧烷、氟代烷基硅烷、十七氟癸基三甲氧基硅烷和十七氟癸基三乙氧基硅烷中的一种或多种。Preferably, the hydrophobic stabilizer is polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkylsiloxane, fluoroalkylsilane, One or more of heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane.
优选的,所述疏水接枝改性剂为2-(三氟甲基)丙烯酸、全氟烷基乙基甲基丙烯酸、聚甲基丙烯酸(N-全氟环烷基)酰胺酯、聚丙烯酸全氟辛基甲酯和氟化异氰酸酯中的一种或多种。Preferably, the hydrophobic graft modifier is 2-(trifluoromethyl)acrylic acid, perfluoroalkyl ethyl methacrylic acid, polymethacrylic acid (N-perfluorocycloalkyl)amide ester, polyacrylic acid One or more of perfluorooctyl methyl ester and fluorinated isocyanate.
优选的,所述疏水接枝增容剂为马来酸酐接枝聚乙烯树脂、马来酸酐接枝聚丙烯树脂、马来酸酐接枝氯化聚乙烯树脂和马来酸酐接枝氯化聚丙烯树脂中的一种或多种。Preferably, the hydrophobic graft compatibilizer is maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted chlorinated polyethylene resin and maleic anhydride grafted chlorinated polypropylene One or more of the resins.
本发明提供了一种上述技术方案所述聚丙烯疏水材料的制备方法,包括以下步骤:The present invention provides a kind of preparation method of polypropylene hydrophobic material described in above-mentioned technical scheme, comprises the following steps:
将聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂、疏水稳定剂、疏水接枝改性剂和疏水接枝增容剂在螺杆挤出机中进行熔融共混后挤出,得到聚丙烯疏水材料。The polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer are melt-blended in a screw extruder and then extruded to obtain a polymer Acrylic hydrophobic material.
优选的,所述螺杆挤出机沿物料挤出方向顺序设置有主加料口、第一支加料口和第二支加料口;制备过程中,所述聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂和疏水接枝增容剂通过所述主加料口加入螺杆挤出机中,所述疏水接枝改性剂通过所述第一支加料口加入,所述疏水稳定剂通过所述第二支加料口加入。Preferably, the screw extruder is sequentially provided with a main feeding port, a first feeding port and a second feeding port along the material extrusion direction; during the preparation process, the polypropylene resin base material, polypropylene-fluorocarbon Resin, diffusion agent and hydrophobic graft compatibilizer are added into the screw extruder through the main feed port, the hydrophobic graft modifier is added through the first feed port, and the hydrophobic stabilizer is fed through the The second feeding port is added.
本发明提供了一种疏水制件,所述疏水制件的材料为上述技术方案所述的聚丙烯疏水材料。The present invention provides a hydrophobic product, and the material of the hydrophobic product is the polypropylene hydrophobic material described in the above technical solution.
优选的,所述疏水制件的表面经过等离子体溅射处理和/或静电负电荷溅射处理。Preferably, the surface of the hydrophobic article is treated by plasma sputtering and/or electrostatic negative charge sputtering.
与现有技术相比,本发明提供了一种聚丙烯疏水材料及其制备方法和应用。本发明提供的聚丙烯疏水材料由原料物经熔融共混挤出制成,以质量份数计,所述原料物包括:聚丙烯树脂基料100份,聚丙烯-氟碳树脂0.5~30份,扩散剂0.1~20份,疏水稳定剂0.1~10份,疏水接枝改性剂5~20份,疏水接枝增容剂0.1~5份;所述聚丙烯-氟碳树脂中的聚丙烯树脂和氟碳树脂在微观热力学相态结构上为双连续相结构;所述聚丙烯-氟碳树脂中的聚丙烯树脂与氟碳树脂的质量比为100:(80~150)。本发明通过构建双连续相结构,可以避免共混过程中低表面能物质形成海岛结构、核壳结构等非连续相,提高共混体系中低表面能物质在微观界面层的分散浓度;通过利用双连续相结构中微流体通道,进行熔融共混接枝反应,不仅可以提高共混体系中的两相在热力学上的相容性,还可以进一步提高共混体系中低表面能物质在微观界面层的分散浓度,从而使材料达到疏水、超疏水的应用要求。另外,本发明提供的聚丙烯疏水材料可以直接通过挤出成型、注塑成型、中空成型、吹塑成型、模压成型、压延成型等工艺制备成制件,特别适用于需要疏水性能的精细结构件的连续化生产。此外,在本发明提供的优选技术方案中,还可以对制件表面进行等离子体溅射处理和/或静电负电荷溅射处理,以进一步提高制件的疏水性能。实验结果表明:本发明提供的聚丙烯疏水材料的水接触角≥118°,经表面处理的制件的水接触角最高可达135°。Compared with the prior art, the invention provides a polypropylene hydrophobic material and its preparation method and application. The polypropylene hydrophobic material provided by the present invention is made of raw materials through melt blending and extrusion, and the raw materials include: 100 parts of polypropylene resin base material, 0.5-30 parts of polypropylene-fluorocarbon resin , 0.1 to 20 parts of a diffusing agent, 0.1 to 10 parts of a hydrophobic stabilizer, 5 to 20 parts of a hydrophobic graft modifier, and 0.1 to 5 parts of a hydrophobic graft compatibilizer; the polypropylene in the polypropylene-fluorocarbon resin The resin and the fluorocarbon resin have a bicontinuous phase structure on the microscopic thermodynamic phase structure; the mass ratio of the polypropylene resin to the fluorocarbon resin in the polypropylene-fluorocarbon resin is 100:(80-150). The present invention can avoid discontinuous phases such as sea-island structure and core-shell structure formed by low surface energy substances in the blending process by constructing a double continuous phase structure, and improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system; by using The microfluidic channel in the bicontinuous phase structure, and the melt blending grafting reaction can not only improve the thermodynamic compatibility of the two phases in the blend system, but also further improve the low surface energy substances in the blend system at the micro interface. The dispersion concentration of the layer can make the material meet the application requirements of hydrophobic and superhydrophobic. In addition, the polypropylene hydrophobic material provided by the present invention can be directly prepared into finished parts by processes such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering, etc., and is especially suitable for fine structural parts that require hydrophobic properties Continuous production. In addition, in the preferred technical solution provided by the present invention, plasma sputtering treatment and/or electrostatic negative charge sputtering treatment can also be performed on the surface of the workpiece, so as to further improve the hydrophobic performance of the workpiece. Experimental results show that: the water contact angle of the polypropylene hydrophobic material provided by the present invention is more than or equal to 118°, and the water contact angle of the surface-treated workpiece can reach up to 135°.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案,下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据提供的附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can also obtain other drawings according to the provided drawings without creative work.
图1是本本发明实施例1提供的注塑制品在室温条件下的表面SEM图;Fig. 1 is the surface SEM image of the injection molded product provided by Example 1 of the present invention at room temperature;
图2是本本发明对比例1提供的注塑制品在室温条件下的表面SEM图。Fig. 2 is a SEM image of the surface of the injection molded product provided in Comparative Example 1 of the present invention at room temperature.
具体实施方式Detailed ways
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。The following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
本发明提供了一种聚丙烯疏水材料,由原料物经熔融共混挤出制成,以质量份数计,所述原料物包括:The invention provides a polypropylene hydrophobic material, which is made of raw materials through melt blending and extrusion, and in parts by mass, the raw materials include:
在本发明提供的聚丙烯疏水材料中,所述聚丙烯树脂基料优选为牌号为M800E的聚丙烯树脂,上述牌号的聚丙烯树脂由中国石化上海石油化工股份有限公司提供。In the polypropylene hydrophobic material provided by the present invention, the polypropylene resin base material is preferably a polypropylene resin with a grade of M800E, and the polypropylene resin of the above grade is provided by Sinopec Shanghai Petrochemical Co., Ltd.
在本发明提供的聚丙烯疏水材料中,所述聚丙烯-氟碳树脂由聚丙烯树脂与氟碳树脂经过熔融共混挤出制成,所述聚丙烯-氟碳树脂中的聚丙烯树脂和氟碳树脂在微观热力学相态结构上为双连续相结构。In the polypropylene hydrophobic material provided by the present invention, the polypropylene-fluorocarbon resin is made of polypropylene resin and fluorocarbon resin through melt blending and extrusion, and the polypropylene resin and fluorocarbon resin in the polypropylene-fluorocarbon resin Fluorocarbon resin is a bicontinuous phase structure in the microscopic thermodynamic phase structure.
在本发明提供的聚丙烯疏水材料中,所述聚丙烯-氟碳树脂中的聚丙烯树脂的具体牌号优选与前文介绍的聚丙烯树脂基料一致。In the polypropylene hydrophobic material provided by the present invention, the specific grade of the polypropylene resin in the polypropylene-fluorocarbon resin is preferably consistent with the polypropylene resin base material introduced above.
在本发明提供的聚丙烯疏水材料中,所述聚丙烯-氟碳树脂中的氟碳树脂优选为聚偏氟乙烯和四氟乙烯-六氟丙烯共聚物;所述聚偏氟乙烯的牌号优选为710,上述牌号的聚偏氟乙烯由法国阿科玛提供;所述四氟乙烯-六氟丙烯共聚物中四氟乙烯结构对应的重复单元与六氟丙烯结构对应的重复单元的质量比为(95:5)~(70:30),更优选为(90:10)~(80:20);所述四氟乙烯-六氟丙烯共聚物的牌号优选为6100,上述牌号的四氟乙烯-六氟丙烯共聚物由美国杜邦提供;所述聚偏氟乙烯和四氟乙烯-六氟丙烯共聚物的质量比优选为1:(0.5~2),具体可为1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、1:1.9或1:2。In the polypropylene hydrophobic material provided by the present invention, the fluorocarbon resin in the polypropylene-fluorocarbon resin is preferably polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer; the grade of the polyvinylidene fluoride is preferably 710, the polyvinylidene fluoride of the above-mentioned brand is provided by France Arkema; The mass ratio of the repeating unit corresponding to the tetrafluoroethylene structure and the repeating unit corresponding to the hexafluoropropylene structure in the tetrafluoroethylene-hexafluoropropylene copolymer is (95:5)~(70:30), more preferably (90:10)~(80:20); the grade of the tetrafluoroethylene-hexafluoropropylene copolymer is preferably 6100, and the tetrafluoroethylene of the above grade - Hexafluoropropylene copolymer is provided by DuPont of the United States; the mass ratio of polyvinylidene fluoride and tetrafluoroethylene-hexafluoropropylene copolymer is preferably 1: (0.5~2), specifically 1:0.5, 1:0.6 , 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1 :1.9 or 1:2.
在本发明提供的聚丙烯疏水材料中,所述聚丙烯-氟碳树脂中的聚丙烯树脂与氟碳树脂的质量比为100:(80~150),具体可为100:80、100:85、100:90、100:95、100:100、100:105、100:110、100:115、100:120、100:125、100:130、100:135、100:140、100:145或100:150。In the polypropylene hydrophobic material provided by the present invention, the mass ratio of the polypropylene resin in the polypropylene-fluorocarbon resin to the fluorocarbon resin is 100:(80-150), specifically 100:80, 100:85 , 100:90, 100:95, 100:100, 100:105, 100:110, 100:115, 100:120, 100:125, 100:130, 100:135, 100:140, 100:145, or 100 :150.
在本发明提供的聚丙烯疏水材料中,以聚丙烯树脂基料在原料物中的含量为100质量份计,所述聚丙烯-氟碳树脂在原料物中的含量具体可为0.5质量份、1质量份、2质量份、3质量份、4质量份、5质量份、6质量份、7质量份、8质量份、9质量份、10质量份、11质量份、12质量份、13质量份、14质量份、15质量份、16质量份、17质量份、18质量份、19质量份、20质量份、21质量份、22质量份、23质量份、24质量份、25质量份、26质量份、27质量份、28质量份、29质量份或30质量份。In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the polypropylene-fluorocarbon resin in the raw material can specifically be 0.5 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass Parts, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass, 20 parts by mass, 21 parts by mass, 22 parts by mass, 23 parts by mass, 24 parts by mass, 25 parts by mass, 26 parts by mass, 27 parts by mass, 28 parts by mass, 29 parts by mass or 30 parts by mass.
在本发明提供的聚丙烯疏水材料中,所述扩散剂优选为聚氯乙烯、氯化聚乙烯和氯磺化聚乙烯中的一种或多种,更优选为聚氯乙烯和氯化聚乙烯;所述聚氯乙烯的牌号优选为SG-5,上述牌号的聚氯乙烯由新疆天业集团有限公司提供;所述氯化聚乙烯的牌号优选为CPE 135A,上述牌号的氯化聚乙烯由山东诚顺化工科技有限公司;所述聚氯乙烯和氯化聚乙烯的质量比优选为1:(0.5~2),具体可为1:0.5、1:0.6、1:0.7、1:0.8、1:0.9、1:1、1:1.1、1:1.2、1:1.3、1:1.4、1:1.5、1:1.6、1:1.7、1:1.8、1:1.9或1:2。In the polypropylene hydrophobic material provided by the present invention, the diffusing agent is preferably one or more of polyvinyl chloride, chlorinated polyethylene and chlorosulfonated polyethylene, more preferably polyvinyl chloride and chlorinated polyethylene The trade mark of described polyvinyl chloride is preferably SG-5, and the polyvinyl chloride of above-mentioned trade mark is provided by Xinjiang Tianye Group Co., Ltd.; The trade mark of described chlorinated polyethylene is preferably CPE 135A, and the chlorinated polyethylene of above-mentioned trade mark is provided by Shandong Chengshun Chemical Technology Co., Ltd.; the mass ratio of polyvinyl chloride and chlorinated polyethylene is preferably 1: (0.5~2), specifically 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, or 1:2.
在本发明提供的聚丙烯疏水材料中,以聚丙烯树脂基料在原料物中的含量为100质量份计,所述扩散剂在原料物中的含量具体可为0.1质量份、0.5质量份、1质量份、1.5质量份、2质量份、3质量份、4质量份、5质量份、6质量份、7质量份、8质量份、9质量份、10质量份、11质量份、12质量份、13质量份、14质量份、15质量份、16质量份、17质量份、18质量份、19质量份或20质量份。In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the diffusing agent in the raw material can specifically be 0.1, 0.5, 1 part by mass, 1.5 parts by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass or 20 parts by mass.
在本发明提供的聚丙烯疏水材料中,所述疏水稳定剂优选为聚二甲基硅氧烷、三异丙基硅烷、三氟丙基甲基二甲氧基硅烷、聚全氟烷基硅氧烷、氟代烷基硅烷、十七氟癸基三甲氧基硅烷和十七氟癸基三乙氧基硅烷中的一种或多种;所述聚二甲基硅氧烷的分子量优选为400~1000,具体可为400、500、600、700、800、900或1000。In the polypropylene hydrophobic material provided by the present invention, the hydrophobic stabilizer is preferably polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkylsilane One or more of oxane, fluoroalkylsilane, heptadecafluorodecyltrimethoxysilane and heptadecafluorodecyltriethoxysilane; the molecular weight of the polydimethylsiloxane is preferably 400-1000, specifically 400, 500, 600, 700, 800, 900 or 1000.
在本发明提供的聚丙烯疏水材料中,以聚丙烯树脂基料在原料物中的含量为100质量份计,所述疏水稳定剂在原料物中的含量具体可为0.1质量份、0.5质量份、1质量份、1.5质量份、2质量份、2.5质量份、3质量份、3.5质量份、4质量份、4.5质量份、5质量份、5.5质量份、6质量份、6.5质量份、7质量份、7.5质量份、8质量份、8.5质量份、9质量份、9.5质量份或10质量份。In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic stabilizer in the raw material can be specifically 0.1 parts by mass, 0.5 parts by mass , 1 part by mass, 1.5 parts by mass, 2 parts by mass, 2.5 parts by mass, 3 parts by mass, 3.5 parts by mass, 4 parts by mass, 4.5 parts by mass, 5 parts by mass, 5.5 parts by mass, 6 parts by mass, 6.5 parts by mass, 7 parts by mass Parts by mass, 7.5 parts by mass, 8 parts by mass, 8.5 parts by mass, 9 parts by mass, 9.5 parts by mass or 10 parts by mass.
在本发明提供的聚丙烯疏水材料中,所述疏水接枝改性剂优选为2-(三氟甲基)丙烯酸、全氟烷基乙基甲基丙烯酸、聚甲基丙烯酸(N-全氟环烷基)酰胺酯、聚丙烯酸全氟辛基甲酯和氟化异氰酸酯中的一种或多种。In the polypropylene hydrophobic material provided by the present invention, the hydrophobic graft modifier is preferably 2-(trifluoromethyl)acrylic acid, perfluoroalkyl ethyl methacrylic acid, polymethacrylic acid (N-perfluoromethacrylic acid) One or more of cycloalkyl)amide ester, polyperfluorooctylmethyl acrylate and fluorinated isocyanate.
在本发明提供的聚丙烯疏水材料中,以聚丙烯树脂基料在原料物中的含量为100质量份计,所述疏水接枝改性剂在原料物中的含量具体可为5质量份、6质量份、7质量份、8质量份、9质量份、10质量份、11质量份、12质量份、13质量份、14质量份、15质量份、16质量份、17质量份、18质量份、19质量份或20质量份。In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic graft modifier in the raw material can specifically be 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, 10 parts by mass, 11 parts by mass, 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass parts, 19 parts by mass or 20 parts by mass.
在本发明提供的聚丙烯疏水材料中,所述疏水接枝增容剂优选为马来酸酐接枝聚乙烯树脂、马来酸酐接枝聚丙烯树脂、马来酸酐接枝氯化聚乙烯树脂和马来酸酐接枝氯化聚丙烯树脂中的一种或多种;疏水接枝增容剂中的马来酸酐接率优选为0.3~4%,更优选为1.5~2%。在本发明中,所述疏水接枝增容剂具体可选择牌号为50E803的马来酸酐接枝聚丙烯树脂,上述牌号的马来酸酐接枝聚丙烯树脂由美国杜邦提供。In the polypropylene hydrophobic material provided by the present invention, the hydrophobic graft compatibilizer is preferably maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted chlorinated polyethylene resin and One or more of the maleic anhydride grafted chlorinated polypropylene resins; the maleic anhydride graft rate in the hydrophobic graft compatibilizer is preferably 0.3-4%, more preferably 1.5-2%. In the present invention, the hydrophobic grafting compatibilizer can specifically choose the maleic anhydride grafted polypropylene resin of the grade 50E803, and the maleic anhydride grafted polypropylene resin of the above grade is provided by DuPont of the United States.
在本发明提供的聚丙烯疏水材料中,以聚丙烯树脂基料在原料物中的含量为100质量份计,所述疏水接枝增容剂在原料物中的含量具体可为0.1质量份、0.25质量份、0.5质量份、0.75质量份、1质量份、1.25质量份、1.5质量份、1.75质量份、2质量份、2.25质量份、2.5质量份、2.75质量份、3质量份、3.25质量份、3.5质量份、3.75质量份、4质量份、4.25质量份、4.5质量份、4.75质量份或5质量份。In the polypropylene hydrophobic material provided by the present invention, based on 100 parts by mass of the polypropylene resin base material in the raw material, the content of the hydrophobic graft compatibilizer in the raw material can specifically be 0.1 parts by mass, 0.25 parts by mass, 0.5 parts by mass, 0.75 parts by mass, 1 part by mass, 1.25 parts by mass, 1.5 parts by mass, 1.75 parts by mass, 2 parts by mass, 2.25 parts by mass, 2.5 parts by mass, 2.75 parts by mass, 3 parts by mass, 3.25 parts by mass 3.5 parts by mass, 3.75 parts by mass, 4 parts by mass, 4.25 parts by mass, 4.5 parts by mass, 4.75 parts by mass or 5 parts by mass.
本发明还提供了一种上述技术方案所述的聚丙烯疏水材料的制备方法,包括以下步骤:The present invention also provides a method for preparing the polypropylene hydrophobic material described in the above technical solution, comprising the following steps:
将聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂、疏水稳定剂、疏水接枝改性剂和疏水接枝增容剂在螺杆挤出机中进行熔融共混后挤出,得到聚丙烯疏水材料。The polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer are melt-blended in a screw extruder and then extruded to obtain a polymer Acrylic hydrophobic material.
在本发明提供的制备方法中,所述聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂、疏水稳定剂、疏水接枝改性剂和疏水接枝增容剂的原料信息与用量配比在前文中已经介绍,在此不再赘述。In the preparation method provided by the present invention, the raw material information and dosage formulation of the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent, hydrophobic stabilizer, hydrophobic graft modifier and hydrophobic graft compatibilizer It has been introduced in the previous article and will not be repeated here.
在本发明提供的制备方法中,所使用的聚丙烯-氟碳树脂优选按照以下步骤制备得到:将聚丙烯树脂和氟碳树脂在螺杆挤出机中进行熔融共混后挤出,聚丙烯-氟碳树脂。其中,所述聚丙烯树脂和氟碳树脂的原料信息与用量配比在前文中已经介绍,在此不再赘述;所述聚丙烯树脂和氟碳树脂在加入到螺杆挤出机中之前,优选先预混均匀;所述螺杆挤出机的挤出温度(即,加料斗至模口的温度)优选为150~350℃,更优选为180~330℃;所述螺杆挤出机的螺杆转速优选为120~300rpm,具体可为120rpm、130rpm、140rpm、150rpm、160rpm、180rpm、200rpm、250rpm或300rpm;挤出后,优选进行冷却和切粒,得到聚丙烯-氟碳树脂母粒。In the preparation method provided by the present invention, the polypropylene-fluorocarbon resin used is preferably prepared according to the following steps: the polypropylene resin and the fluorocarbon resin are melt-blended in a screw extruder and then extruded, and the polypropylene-fluorocarbon resin is extruded. Fluorocarbon resin. Wherein, the raw material information and dosage ratio of the polypropylene resin and the fluorocarbon resin have been introduced above, and will not be repeated here; before the polypropylene resin and the fluorocarbon resin are added to the screw extruder, preferably First premix evenly; the extrusion temperature of the screw extruder (that is, the temperature from the hopper to the die) is preferably 150 to 350°C, more preferably 180 to 330°C; the screw speed of the screw extruder It is preferably 120-300rpm, specifically 120rpm, 130rpm, 140rpm, 150rpm, 160rpm, 180rpm, 200rpm, 250rpm or 300rpm; after extrusion, it is preferably cooled and pelletized to obtain polypropylene-fluorocarbon resin masterbatch.
在本发明提供的制备方法中,制备所述聚丙烯疏水材料所使用的螺杆挤出机优选沿物料挤出方向顺序设置有主加料口、第一支加料口和第二支加料口;制备过程中,所述聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂和疏水接枝增容剂优选通过所述主加料口加入螺杆挤出机中,所述疏水接枝改性剂优选通过所述第一支加料口加入,所述疏水稳定剂优选通过所述第二支加料口加入。其中,所述聚丙烯树脂基料、聚丙烯-氟碳树脂、扩散剂和疏水接枝增容剂在加入到螺杆挤出机中之前,优选先预混均匀。In the preparation method provided by the present invention, the screw extruder used to prepare the polypropylene hydrophobic material is preferably sequentially provided with a main feeding port, a first feeding port and a second feeding port along the extrusion direction of the material; the preparation process Among them, the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent and hydrophobic graft compatibilizer are preferably added to the screw extruder through the main feeding port, and the hydrophobic graft modifier is preferably passed through The first feeding port is added, and the hydrophobic stabilizer is preferably added through the second feeding port. Wherein, the polypropylene resin base material, polypropylene-fluorocarbon resin, diffusing agent and hydrophobic graft compatibilizer are preferably pre-mixed uniformly before being added to the screw extruder.
在本发明提供的制备方法中,制备聚丙烯疏水材料的过程中,所述螺杆挤出机的挤出温度(即,加料斗至模口的温度)优选为150~250℃,更优选为150~230℃;所述螺杆挤出机的螺杆转速优选为80~200rpm,具体可为80rpm、100rpm、120rpm、130rpm、140rpm、160rpm、180rpm或200rpm;挤出后,优选进行冷却和切粒,得到聚丙烯疏水粒料。In the preparation method provided by the present invention, during the preparation of the polypropylene hydrophobic material, the extrusion temperature of the screw extruder (that is, the temperature from the feeding hopper to the die opening) is preferably 150-250° C., more preferably 150° C. ~230°C; the screw speed of the screw extruder is preferably 80~200rpm, specifically 80rpm, 100rpm, 120rpm, 130rpm, 140rpm, 160rpm, 180rpm or 200rpm; after extrusion, it is preferably cooled and pelletized to obtain Polypropylene hydrophobic pellets.
本发明还提供了一种疏水制件,所述疏水制件的材料为上述技术方案所述的聚丙烯疏水材料。本发明提供的疏水制件由所述聚丙烯疏水材料经过成型工艺制成,所述成型工艺包括但不限于挤出成型、注塑成型、中空成型、吹塑成型、模压成型、压延成型等。在本发明中,为进一步提高制件的疏水性能,所述疏水制件的表面优选经过等离子体溅射处理和/或静电负电荷溅射处理;其中,所述等离子体溅射处理的溅射气体温度优选为15~35℃,具体可为25℃(室温),溅射施加的直流电压优选为500~1000V;所述静电负电荷溅射处理的溅射气体温度优选为15~35℃,具体可为25℃(室温),溅射施加的直流电压优选为500~1000V。The present invention also provides a hydrophobic product, the material of which is the polypropylene hydrophobic material described in the above technical solution. The hydrophobic article provided by the present invention is made of the polypropylene hydrophobic material through a molding process, which includes but not limited to extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering molding and the like. In the present invention, in order to further improve the hydrophobic performance of the workpiece, the surface of the hydrophobic workpiece is preferably treated by plasma sputtering and/or electrostatic negative charge sputtering; wherein, the sputtering of the plasma sputtering treatment The gas temperature is preferably 15-35°C, specifically 25°C (room temperature), and the DC voltage applied by sputtering is preferably 500-1000V; the sputtering gas temperature for the electrostatic negative charge sputtering treatment is preferably 15-35°C, Specifically, it may be 25°C (room temperature), and the DC voltage applied to sputtering is preferably 500-1000V.
本发明通过构建双连续相结构,可以避免共混过程中低表面能物质形成海岛结构、核壳结构等非连续相,提高共混体系中低表面能物质在微观界面层的分散浓度;通过利用双连续相结构中微流体通道,进行熔融共混接枝反应,不仅可以提高共混体系中的两相在热力学上的相容性,还可以进一步提高共混体系中低表面能物质在微观界面层的分散浓度,从而使材料达到疏水、超疏水的应用要求。另外,本发明提供的聚丙烯疏水材料可以直接通过挤出成型、注塑成型、中空成型、吹塑成型、模压成型、压延成型等工艺制备成制件,特别适用于需要疏水性能的精细结构件的连续化生产。此外,在本发明提供的优选技术方案中,还可以对制件表面进行等离子体溅射处理和/或静电负电荷溅射处理,以进一步提高制件的疏水性能。实验结果表明:本发明提供的聚丙烯疏水材料的水接触角≥118°,经表面处理的制件的水接触角最高可达135°。The present invention can avoid discontinuous phases such as sea-island structure and core-shell structure formed by low surface energy substances in the blending process by constructing a double continuous phase structure, and improve the dispersion concentration of low surface energy substances in the microscopic interface layer in the blending system; by using The microfluidic channel in the bicontinuous phase structure, and the melt blending grafting reaction can not only improve the thermodynamic compatibility of the two phases in the blend system, but also further improve the low surface energy substances in the blend system at the micro interface. The dispersion concentration of the layer can make the material meet the application requirements of hydrophobic and superhydrophobic. In addition, the polypropylene hydrophobic material provided by the present invention can be directly prepared into finished parts by processes such as extrusion molding, injection molding, hollow molding, blow molding, compression molding, calendering, etc., and is especially suitable for fine structural parts that require hydrophobic properties Continuous production. In addition, in the preferred technical solution provided by the present invention, plasma sputtering treatment and/or electrostatic negative charge sputtering treatment can also be performed on the surface of the workpiece, so as to further improve the hydrophobic performance of the workpiece. Experimental results show that: the water contact angle of the polypropylene hydrophobic material provided by the present invention is more than or equal to 118°, and the water contact angle of the surface-treated workpiece can reach up to 135°.
为更清楚起见,下面通过以下实施例和对比例进行详细说明。For more clarity, the following examples and comparative examples are described in detail below.
实施例1Example 1
一种聚丙烯疏水材料的制备,包括以下步骤:A kind of preparation of polypropylene hydrophobic material, comprises the following steps:
1)称取100质量份的聚丙烯树脂(牌号:M800E,产地:中国石化上海石油化工股份有限公司,下同)、50质量份的偏氟乙烯树脂(牌号:710,产地:法国阿科玛,下同)、50质量份的四氟乙烯-六氟丙烯共聚物(牌号:6100,产地:美国杜邦,下同),置于高速混合机(型号:SHR-5,生产厂家:张家港市桓丰机械厂,下同)中,混合5min后取出,置于双螺杆挤出机(型号:CTE-20,生产厂家:南京科倍隆有限公司,下同)的加料斗中;1) Weigh 100 parts by mass of polypropylene resin (brand: M800E, place of origin: Sinopec Shanghai Petrochemical Co., Ltd., the same below), 50 parts by mass of vinylidene fluoride resin (brand: 710, place of origin: Arkema, France , the same below), 50 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer (brand: 6100, place of origin: DuPont, the United States, the same below), placed in a high-speed mixer (model: SHR-5, manufacturer: Zhangjiagang City Huan Feng Machinery Factory, the same below), take it out after mixing for 5min, and place it in the hopper of a twin-screw extruder (model: CTE-20, manufacturer: Nanjing Coperion Co., Ltd., the same below);
2)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为180~330℃;设置螺杆挤出机的螺杆转速为140rpm;2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;
3)将经螺杆挤出机挤出的树脂融体混合物冷确、切粒、干燥后,制得具有双连续相结构的聚丙烯-氟碳树脂母料,备用;3) After cooling, pelletizing and drying the resin melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for use;
4)称取100质量份的聚丙烯树脂,20质量份的聚丙烯-氟碳树脂母料,1.5质量份的聚氯乙烯(牌号:SG-5,产地:新疆天业集团有限公司,下同),1.5质量份的氯化聚乙烯(牌号:CPE 135A,产地:山东诚顺化工科技有限公司,下同),0.75质量份的马来酸酐接枝聚丙烯树脂(牌号:50E803,产地:美国杜邦,下同),置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;4) Weigh 100 parts by mass of polypropylene resin, 20 parts by mass of polypropylene-fluorocarbon resin masterbatch, 1.5 parts by mass of polyvinyl chloride (brand: SG-5, place of origin: Xinjiang Tianye Group Co., Ltd., the same below ), 1.5 parts by mass of chlorinated polyethylene (brand: CPE 135A, place of origin: Shandong Chengshun Chemical Technology Co., Ltd., the same below), 0.75 parts by mass of maleic anhydride grafted polypropylene resin (brand: 50E803, place of origin: U.S. DuPont, the same below), placed in a high-speed mixer, took out after mixing for 5min, and placed in the hopper of a twin-screw extruder;
5)将全氟烷基乙基甲基丙烯酸(产地:郑州阿尔法化工有限公司,下同)置于一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第一支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,全氟烷基乙基甲基丙烯酸的滴加量为10质量份;5) Put perfluoroalkyl ethyl methacrylic acid (place of origin: Zhengzhou Alpha Chemical Co., Ltd., the same below) in a drip feeding device, through the first feeding port above the barrel of the screw extruder Carry out dropwise, with the consumption of polypropylene resin being 100 mass parts, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 10 mass parts;
6)将聚二甲基硅氧烷(分子量:800,产地:山东瑞鸿德化工科技有限公司,下同)置于另外一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第二支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,聚二甲基硅氧烷的滴加量为5质量份;在本实施例中,加料斗、第一支加料口、第二支加料口、螺杆挤出机模口在螺杆挤出机上的排列顺序为:加料斗→第一支加料口→第二支加料口→螺杆挤出机模口(下同);6) Put polydimethylsiloxane (molecular weight: 800, place of origin: Shandong Ruihongde Chemical Technology Co., Ltd., the same below) in another drop feeding device, and set it above the barrel of the screw extruder The second feed port of the feeder is added dropwise, and the amount of polydimethylsiloxane added dropwise is 5 parts by mass based on 100 parts by mass of the polypropylene resin; in the present embodiment, the feed hopper, the first branch The arrangement order of the feeding port, the second feeding port, and the die opening of the screw extruder on the screw extruder is: feeding hopper → the first feeding port → the second feeding port → the screw extruder die opening (the same below) ;
7)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为150~230℃;设置螺杆挤出机的螺杆转速为120rpm;7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;
8)将经螺杆挤出机挤出的融体混合物冷确切粒后,干燥,即可制得聚丙烯疏水材料。8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.
将本实施例中制备得到的聚丙烯疏水材料,利用注塑成型机(型号:Babyplast 6/10P,产地:西班牙Cronop last公司,下同)工艺,制备得到注塑制品,其表面微观形貌如图1所示,在室温条件对水的接触角为120度;对该注塑制品单独进行等离子体进行表面溅射处理(溅射气体温度为室温,溅射施加直流电压为500V,下同)后,在室温条件对水的接触角为128度;对该注塑制品单独进行表面静电负电荷溅射处理(溅射气体温度为室温,溅射施加直流电压为500V,下同)后,在室温条件对水的接触角为125度;对该注塑制品依次进行表面溅射处理和表面静电负电荷溅射处理后,在室温条件对水的接触角为135度。The polypropylene hydrophobic material prepared in this example was prepared by using an injection molding machine (model: Babyplast 6/10P, place of origin: Cronop last company in Spain, the same below) to prepare an injection molded product, and its surface microscopic appearance is shown in Figure 1 As shown, the contact angle to water at room temperature is 120 degrees; after the surface sputtering treatment (sputtering gas temperature is room temperature, and sputtering applied DC voltage is 500V, the same below) is performed on the injection molded product separately, the The contact angle of water at room temperature is 128 degrees; after the surface electrostatic negative charge sputtering treatment is performed on the injection molded product (the temperature of the sputtering gas is room temperature, and the DC voltage applied to sputtering is 500V, the same below), the water is treated at room temperature. The contact angle of the injection molded product is 125 degrees; after the surface sputtering treatment and the surface electrostatic negative charge sputtering treatment are carried out on the injection molded product in sequence, the contact angle to water at room temperature is 135 degrees.
实施例2Example 2
一种聚丙烯疏水材料的制备,包括以下步骤:A kind of preparation of polypropylene hydrophobic material, comprises the following steps:
1)称取100质量份的聚丙烯树脂、60质量份的偏氟乙烯树脂、40质量份的四氟乙烯-六氟丙烯共聚物,置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;1) Weigh 100 parts by mass of polypropylene resin, 60 parts by mass of vinylidene fluoride resin, and 40 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer, place them in a high-speed mixer, take them out after mixing for 5 minutes, and place them in double In the hopper of the screw extruder;
2)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为180~330℃;设置螺杆挤出机的螺杆转速为140rpm;2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;
3)将经螺杆挤出机挤出的融体混合物冷确、切粒、干燥后,制得具有双连续相结构的聚丙烯-氟碳树脂母料,备用;3) After cooling, pelletizing and drying the melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for subsequent use;
4)称取100质量份的聚丙烯树脂,20质量份的聚丙烯-氟碳树脂母料,2.0质量份的聚氯乙烯,1.0质量份的氯化聚乙烯,1.0质量份的马来酸酐接枝聚丙烯树脂,置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;4) take by weighing the polypropylene resin of 100 mass parts, the polypropylene-fluorocarbon resin masterbatch of 20 mass parts, the polyvinyl chloride of 2.0 mass parts, the chlorinated polyethylene of 1.0 mass parts, the maleic anhydride of 1.0 mass parts A polypropylene resin is placed in a high-speed mixer, taken out after mixing for 5min, and placed in the hopper of a twin-screw extruder;
5)将全氟烷基乙基甲基丙烯酸置于一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第一支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,全氟烷基乙基甲基丙烯酸的滴加量为12质量份;5) Perfluoroalkyl ethyl methacrylic acid is placed in a drop feeding device, and is added dropwise through the first feeding port above the barrel of the screw extruder, with the amount of polypropylene resin being 100 In parts by mass, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 12 parts by mass;
6)将聚二甲基硅氧烷(分子量:600,产地:山东瑞鸿德化工科技有限公司,下同)置于另外一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第二支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,聚二甲基硅氧烷的滴加量为5质量份;6) Put polydimethylsiloxane (molecular weight: 600, place of origin: Shandong Ruihongde Chemical Technology Co., Ltd., the same below) in another drop feeding device, and set it above the barrel of the screw extruder The second feeding port of the second branch is added dropwise, and the consumption of polypropylene resin is 100 mass parts, and the dripping amount of polydimethylsiloxane is 5 mass parts;
7)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为150~230℃;设置螺杆挤出机的螺杆转速为120rpm;7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;
8)将经螺杆挤出机挤出的融体混合物冷确切粒后,干燥,即可制得聚丙烯疏水材料。8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.
将本实施例中制备得到的聚丙烯疏水材料,利用注塑成型机工艺,制备得到的注塑制品,在室温条件对水的接触角为118度;对该注塑制品单独进行等离子体进行表面溅射处理后,在室温条件对水的接触角为128度;对该注塑制品单独进行表面静电负电荷溅射处理后,在室温条件对水的接触角为125度;对该注塑制品依次进行表面溅射处理和表面静电负电荷溅射处理后,在室温条件对水的接触角为133度。Using the polypropylene hydrophobic material prepared in this example, using the injection molding machine process, the injection molded product prepared has a contact angle of 118 degrees to water at room temperature; the injection molded product is subjected to plasma sputtering treatment alone Finally, the contact angle to water at room temperature is 128 degrees; after the surface electrostatic negative charge sputtering treatment is performed on the injection molded product separately, the contact angle to water at room temperature is 125 degrees; the surface sputtering of the injection molded product is carried out in turn After treatment and surface electrostatic negative charge sputtering treatment, the contact angle to water at room temperature is 133 degrees.
实施例3Example 3
一种聚丙烯疏水材料的制备,包括以下步骤:A kind of preparation of polypropylene hydrophobic material, comprises the following steps:
1)称取100质量份的聚丙烯树脂、50质量份的偏氟乙烯树脂、50质量份的四氟乙烯-六氟丙烯共聚物,置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;1) Weigh 100 parts by mass of polypropylene resin, 50 parts by mass of vinylidene fluoride resin, and 50 parts by mass of tetrafluoroethylene-hexafluoropropylene copolymer, place them in a high-speed mixer, take them out after mixing for 5 minutes, and place them in double In the hopper of the screw extruder;
2)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为180~330℃;设置螺杆挤出机的螺杆转速为140rpm;2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;
3)将经螺杆挤出机挤出的融体混合物冷确、切粒、干燥后,制得具有双连续相结构的聚丙烯-氟碳树脂母料,备用;3) After cooling, pelletizing and drying the melt mixture extruded by the screw extruder, a polypropylene-fluorocarbon resin masterbatch with a dual continuous phase structure is prepared for subsequent use;
4)称取100质量份的聚丙烯树脂,15质量份的聚丙烯-氟碳树脂母料,1.5质量份的聚氯乙烯,4.5质量份的马来酸酐接枝聚丙烯树脂,置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;4) The polypropylene resin of 100 mass parts, the polypropylene-fluorocarbon resin masterbatch of 15 mass parts, the polyvinyl chloride of 1.5 mass parts, the maleic anhydride grafted polypropylene resin of 4.5 mass parts, place high-speed mixing In the machine, take it out after mixing for 5 minutes, and place it in the feeding hopper of the twin-screw extruder;
5)将全氟烷基乙基甲基丙烯酸置于一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第一支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,全氟烷基乙基甲基丙烯酸的滴加量为10质量份;5) Perfluoroalkyl ethyl methacrylic acid is placed in a drop feeding device, and is added dropwise through the first feeding port above the barrel of the screw extruder, with the amount of polypropylene resin being 100 In parts by mass, the dripping amount of perfluoroalkyl ethyl methacrylic acid is 10 parts by mass;
6)将三氟丙基甲基二甲氧基硅烷(产地:湖北东曹化学科技有限公司)置于另外一个滴液加料装置中,通过开设于螺杆挤出机的机筒上方的第二支加料口进行滴加,以聚丙烯树脂的用量为100质量份计,三氟丙基甲基二甲氧基硅烷的滴加量为6质量份;6) Place trifluoropropylmethyldimethoxysilane (Origin: Hubei Dongcao Chemical Technology Co., Ltd.) in another drop feeding device, and pass through the second branch above the barrel of the screw extruder. The feeding port is added dropwise, with the amount of polypropylene resin being 100 parts by mass, the amount of trifluoropropylmethyldimethoxysilane added dropwise is 6 parts by mass;
7)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为150~230℃;设置螺杆挤出机的螺杆转速为120rpm;7) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 150-230°C from the feed hopper to the die opening; set the screw speed of the screw extruder to 120rpm;
8)将经螺杆挤出机挤出的融体混合物冷确切粒后,干燥,即可制得聚丙烯疏水材料。8) The melt mixture extruded by the screw extruder is cooled and pelletized, and then dried to obtain a polypropylene hydrophobic material.
将本实施例中制备得到的聚丙烯疏水材料,利用注塑成型机工艺,制备得到的注塑制品,在室温条件对水的接触角为121度;对该注塑制品单独进行等离子体进行表面溅射处理后,在室温条件对水的接触角为129度;对该注塑制品单独进行表面静电负电荷溅射处理后,在室温条件对水的接触角为127度;对该注塑制品依次进行表面溅射处理和表面静电负电荷溅射处理后,在室温条件对水的接触角为135度。Using the polypropylene hydrophobic material prepared in this example, using the injection molding machine process, the injection molded product prepared has a contact angle of 121 degrees to water at room temperature; the injection molded product is subjected to plasma sputtering treatment alone Finally, the contact angle to water at room temperature is 129 degrees; after the surface electrostatic negative charge sputtering treatment is carried out separately on the injection molded product, the contact angle to water at room temperature is 127 degrees; the injection molded product is subjected to surface sputtering in turn After treatment and surface electrostatic negative charge sputtering treatment, the contact angle to water at room temperature is 135 degrees.
对比例1Comparative example 1
1)称取100质量份的聚丙烯树脂,5质量份的偏氟乙烯树脂,5质量份的四氟乙烯-六氟丙烯共聚物,1.5质量份的聚氯乙烯,1.5质量份的氯化聚乙烯,0.75质量份的马来酸酐接枝聚丙烯树脂,置于高速混合机中,混合5min后取出,置于双螺杆挤出机的加料斗中;1) Weigh the polypropylene resin of 100 mass parts, the vinylidene fluoride resin of 5 mass parts, the tetrafluoroethylene-hexafluoropropylene copolymer of 5 mass parts, the polyvinyl chloride of 1.5 mass parts, the chlorinated polyvinyl chloride of 1.5 mass parts Ethylene, the maleic anhydride grafted polypropylene resin of 0.75 mass parts, place in the high-speed mixer, take out after mixing 5min, place in the hopper of twin-screw extruder;
2)设置双螺杆挤出机的喂料机加料速率200rpm,设置双螺杆挤出机的螺杆温度由加料斗至模口为180~330℃;设置螺杆挤出机的螺杆转速为140rpm;2) Set the feeding rate of the feeder of the twin-screw extruder to 200rpm, set the screw temperature of the twin-screw extruder to 180-330°C from the feeding hopper to the die opening; set the screw speed of the screw extruder to 140rpm;
3)将经螺杆挤出机挤出的融体混合物冷确切粒后,干燥,即可制得本对比例制备的聚丙烯疏水材料。3) After the melt mixture extruded by the screw extruder is cooled and pelletized, and then dried, the polypropylene hydrophobic material prepared in this comparative example can be obtained.
将本对比例中制备得到的聚丙烯疏水材料,利用注塑成型机工艺,制备得到注塑制品,其表面微观形貌如图2所示,在室温条件对水的接触角为95度。The polypropylene hydrophobic material prepared in this comparative example was used to prepare an injection molded product by using an injection molding machine process. The surface microscopic appearance is shown in Figure 2, and the contact angle to water at room temperature is 95 degrees.
对比本发明实施例1和对比例1的测试结果可以看出:对于注塑制品在室温条件下的表面SEM图不难看出,在对比例1中,在注塑制品的表面,低表面能物质在基体PP树脂中是以海岛结构分散存在的,低表面能物质在界面层的分散浓度和分散比表面积较小,因此,在有水浸润到注塑制品的表面时,低表面能物质只能以独立分散的点状位置抵御水的浸润,而在没有低表面能物质存在的其他位置,水仍然能够浸润到注塑制品的表面;而在实施例1中,在注塑制品的表面,低表面能物质和基体PP树脂是以双连续相结构分散存在的,而且低表面能物质在双螺杆共混/注塑成型过程中,在机械剪切作用力下呈树枝状分散结构,该结构的最大有益效果是,低表面能物质能够以连续结构存在于注塑制品的表面,能够进一步提高提注塑制品中低表面能物质在界面层的分散浓度和分散比表面积,因此,在有水浸润到注塑制品的表面时,低表面能物质抵御水的浸润的作用面积会更大;同时,低表面能物质存在的树枝状分散结构,在界面层上还能形成三维空间上的微/纳米结构,可以进一步提高注塑制品的疏水性。同时,如果对注塑制品表面进行进一步的等离子体溅射处理时,可以更加优化注塑制品表面的三维空间上的微/纳米结构;进行进一步的静电负电荷溅射处理时,可以更加优化注塑制品表面静电斥力,在有水浸润到注塑制品的表面时,能够进一步提高抵御水在注塑制品表面浸润的能力,以进一步增强注塑制品的疏水效果。Comparing the test results of Example 1 of the present invention and Comparative Example 1, it can be seen that: for the surface SEM image of the injection molded product at room temperature, it is not difficult to find out that in Comparative Example 1, on the surface of the injection molded product, the low surface energy substance is in the matrix PP resin is dispersed in sea-island structure, and the dispersion concentration and dispersion specific surface area of low surface energy substances in the interface layer are small. Therefore, when water infiltrates the surface of injection molded products, low surface energy substances can only be dispersed independently The dotted position resists the infiltration of water, while in other positions where there is no low surface energy substance, water can still infiltrate the surface of the injection molded product; and in Example 1, on the surface of the injection molded product, the low surface energy substance and matrix The PP resin is dispersed in a dual continuous phase structure, and the low surface energy material exhibits a dendritic dispersion structure under mechanical shear force during the twin-screw blending/injection molding process. The biggest beneficial effect of this structure is that it is low Surface energy substances can exist on the surface of injection molded products in a continuous structure, which can further increase the dispersion concentration and dispersion specific surface area of low surface energy substances in the interface layer of injection molded products. Therefore, when water infiltrates on the surface of injection molded products, low Surface energy substances will have a larger area of action against water infiltration; at the same time, the dendritic dispersed structure of low surface energy substances can also form a three-dimensional micro/nano structure on the interface layer, which can further improve the hydrophobicity of injection molded products. sex. At the same time, if the surface of the injection molded product is further treated by plasma sputtering, the micro/nano structure in the three-dimensional space of the surface of the injection molded product can be further optimized; when further electrostatic negative charge sputtering treatment is performed, the surface of the injection molded product can be further optimized Electrostatic repulsion, when water infiltrates the surface of the injection molded product, can further improve the ability to resist water infiltration on the surface of the injection molded product, so as to further enhance the hydrophobic effect of the injection molded product.
本发明所列举的各原料(如:聚丙烯、四氟乙烯、六氟丙烯、四氟乙烯/六氟丙烯的共聚物、偏氟乙烯树脂、四氟乙烯/六氟丙烯共聚物、四氟乙烯-全氟烷氧基乙烯基醚共聚物、聚全氟烷氧基树脂、聚二甲基硅氧烷、三异丙基硅烷、三氟丙基甲基二甲氧基硅烷、聚全氟烷基硅氧烷、氟代烷基硅烷、十七氟癸基三甲氧基硅烷、十七氟癸基三乙氧基硅烷、2-(三氟甲基)丙烯酸、全氟烷基乙基甲基丙烯酸、聚甲基丙烯酸(N-全氟环烷基)酰胺酯、聚丙烯酸全氟辛基甲酯、氟化异氰酸酯、马来酸酐接枝聚乙烯树脂、马来酸酐接枝聚丙烯树脂、马来酸酐接枝氯化聚乙烯树脂、马来酸酐接枝氯化聚丙烯树脂),以及本发明各原料的上下限、区间取值,以及工艺参数(如温度、时间等)的上下限、区间取值都能实现本发明,在此不一一列举实施例。Each raw material listed in the present invention (such as: polypropylene, tetrafluoroethylene, hexafluoropropylene, tetrafluoroethylene/hexafluoropropylene copolymer, vinylidene fluoride resin, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene - Perfluoroalkoxy vinyl ether copolymer, polyperfluoroalkoxy resin, polydimethylsiloxane, triisopropylsilane, trifluoropropylmethyldimethoxysilane, polyperfluoroalkane fluoroalkylsilane, heptadecylfluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, 2-(trifluoromethyl)acrylic acid, perfluoroalkylethylmethyl Acrylic acid, poly(N-perfluorocycloalkyl)amide polymethacrylate, polyperfluorooctylmethyl acrylate, fluorinated isocyanate, maleic anhydride grafted polyethylene resin, maleic anhydride grafted polypropylene resin, maleic anhydride grafted polypropylene resin, chlorinated polyethylene resin grafted with maleic anhydride, chlorinated polypropylene resin grafted with maleic anhydride), and the upper and lower limits and interval values of each raw material of the present invention, and the upper and lower limits and intervals of process parameters (such as temperature, time, etc.) Values can be used to realize the present invention, and the embodiments are not listed one by one here.
本说明书中应用了具体实施例对本发明进行了阐述,只是本发明的优选实施方式,应当指出,对于本领域的一般技术人员,依据本发明的思想在具体实施方式及应用范围上可能在实施过程中会有改变之处。因此,本说明书记载的内容不应理解为对本发明的限制。In this description, the application of specific embodiments has been described to the present invention, which is only the preferred implementation mode of the present invention. It should be pointed out that for those of ordinary skill in the art, the idea of the present invention may be implemented in the specific implementation mode and application scope. There will be changes in . Therefore, the contents described in this specification should not be understood as limiting the present invention.
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