阅读说明：本技术 一种聚丙烯无纺布超疏水膜的制备方法 (Preparation method of polypropylene non-woven fabric super-hydrophobic film ) 是由 薛立新 朱瑶瑶 赵雪婷 蒋国军 高从堦 于 2020-06-18 设计创作，主要内容包括：本发明公开了一种聚丙烯无纺布超疏水膜的制备方法,将甲基丙烯酸(3,3,4,4,5,5,6,6,7,7,8,8,8)-十三氟辛酯、乙烯基三乙氧基硅烷(VTES)、无水乙醇混合,三者质量份比例为10～15:2～3:100；通氮气搅拌,添加聚丙烯无纺布膜、2,2-偶氮二异丁腈溶解液(AIBN)、二氧化钛溶胶,60℃反应4h～4.5h；将聚丙烯膜取出,用无水乙醇清洗,放于真空干燥箱中90℃烘干,烘干结束后取出即可得到聚丙烯超疏水膜。本发明不仅可以降低聚丙烯无纺布的表面自由能,还可以利用原位生长与溶胶凝胶相结合的方法在材料表面增加粗糙度。(The invention discloses a preparation method of a polypropylene non-woven fabric super-hydrophobic membrane, which comprises the following steps of mixing methacrylic acid (3,3,4,4,5,5,6,6,7,7,8,8,8) -tridecafluorooctyl ester, Vinyl Triethoxysilane (VTES) and absolute ethyl alcohol in a mass ratio of 10-15: 2-3: 100; introducing nitrogen and stirring, adding a polypropylene non-woven fabric membrane, 2-azobisisobutyronitrile solution (AIBN) and titanium dioxide sol, and reacting for 4-4.5 h at 60 ℃; and taking out the polypropylene film, cleaning the polypropylene film by using absolute ethyl alcohol, drying the polypropylene film in a vacuum drying oven at 90 ℃, and taking out the polypropylene film after drying to obtain the polypropylene super-hydrophobic film. The method can reduce the surface free energy of the polypropylene non-woven fabric, and can increase the roughness of the material surface by utilizing the method of combining in-situ growth and sol-gel.)

1. A preparation method of a polypropylene non-woven fabric super-hydrophobic film is characterized by comprising the following steps: the method comprises the following steps:

(1) mixing 3,3,4,4,5,5,6,6,7,7,8,8,8) -tridecafluorooctyl methacrylate, Vinyltriethoxysilane (VTES) and absolute ethyl alcohol in a mass ratio of 10-15: 2-3: 100; introducing nitrogen and stirring, adding a polypropylene non-woven fabric membrane, 2-azobisisobutyronitrile solution (AIBN) and titanium dioxide sol, and reacting for 4-4.5 h at 60 ℃;

(2) and (2) taking out the polypropylene membrane after the reaction in the step (1), washing with absolute ethyl alcohol, drying in a vacuum drying oven at 90 ℃, and taking out after drying to obtain the polypropylene super-hydrophobic membrane.

2. The method for preparing the polypropylene non-woven fabric super-hydrophobic film as claimed in claim 1, wherein: in the step (1), the operation of adding the 2, 2-azobisisobutyronitrile solution is as follows: adding the polypropylene non-woven fabric for 10-15 min and then adding; the 2, 2-azobisisobutyronitrile solution is prepared by dissolving 0.08-0.16 parts of 2, 2-azobisisobutyronitrile nanoparticles in 5 parts of absolute ethanol.

3. The method for preparing the polypropylene non-woven fabric super-hydrophobic film as claimed in claim 1, wherein: in the step (1), the operation of adding the titanium dioxide sol is as follows: adding AIBN dissolving solution for 5-10 min; the amount of the titanium dioxide sol is 2-4 parts by mass based on the titanium dioxide nanoparticles.

4. The method for preparing the polypropylene non-woven fabric super-hydrophobic film as claimed in claim 3, wherein: the proportion of the titanium dioxide sol is as follows: tetraethyl titanate: anhydrous ethanol: hydrochloric acid: deionized water with the volume ratio of 4-5: 2-3: 1: 50-60, and mixing and stirring the materials.

5. The method for preparing the polypropylene non-woven fabric super-hydrophobic film as claimed in claim 1, wherein: in the step (1), the stirring speed of the reaction is 500-800 r/min.

6. The method for preparing the polypropylene non-woven fabric super-hydrophobic film as claimed in claim 1, wherein: in the step (2), the vacuum drying time is 4-5 h.

Technical Field

The invention belongs to the field of super-hydrophobic membrane materials, and particularly relates to a preparation method of a polypropylene non-woven fabric super-hydrophobic membrane.

Background

In recent years, with the research on wettability, people have gradually recognized that superhydrophobic materials have wide application prospects in self-cleaning, waterproofing, antifogging, anti-pollution and anticorrosion, prevention of current conduction and the like, so that the preparation of superhydrophobic films also becomes a focus of attention. There are two classical evaluation methods for the evaluation of the superhydrophobicity of an object surface

(D,oner,T.J.McCarthy,Langmuir,2000,16,7777；M.Miwa,A.Nakajima,A.Fujishima,

Hashimoto, t.watannabe, Langmuir,2000,16, 5754; onda T, Shibuichi S, Satoh N, Tsujii K.Languuir 1996,12:2125) Contact Angle (CA) and roll angle (SA). The super-hydrophobic surface refers to a surface with a contact angle with water of more than 150 degrees and a rolling angle of less than 10 degrees. As known from the classical Young's equation, the wettability of the surface of a substance is directly determined by the surface energy, the surface energy can be reduced as much as possible to improve the hydrophobicity, but still the surface energy cannot exceed 120 degrees, and on the other hand, the surface roughness is also related to the hydrophobicity of the film. There are thus two main approaches to the preparation of superhydrophobic surfaces: one is to form a suitable roughness on the surface of the hydrophobic material; another is to modify the surface of a material with a suitable roughness with a low surface energy chemical.

Polypropylene (PP), one of the most commonly used plastics at present, has the advantages of high cost performance, excellent mechanical properties, good thermal stability and the like, and is widely applied to pipes, films, plastic products and the like due to the excellent properties; if the surface of polypropylene can be endowed with hydrophobicity on the basis of the above, the application range can be further widened.

Generally, the preparation of a super-hydrophobic surface needs to reduce the surface free energy by surface modification of fluorocarbon or long-chain alkyl (the surface wettability is reduced along with the enrichment of fluorine-containing groups, the growth of fluorine-containing chains and the increase of branches of the high-hydrophobic surface prepared by using a low-surface-energy fluorine-containing material). Also, since the contact angle of a smooth surface is small, wettability can be increased by increasing surface roughness, but increasing the roughness of the surface material is not very uniform and does not have long-term stability. The current methods for constructing a rough surface include: sol gel methods, chemical vapor deposition, dip coating methods, and the like. However, the roughness uniformity of the surface of the substrate prepared by the methods is not good, and most of the surfaces have high manufacturing cost, complicated processes and the like, so that the wide-range manufacturing and application are difficult.

Disclosure of Invention

The invention aims to solve the problems, and provides a modification method of a polypropylene non-woven fabric-based superhydrophobic film, which can reduce the surface free energy of the material, can grow in situ to increase the roughness, and can obtain a superhydrophobic polypropylene film material with a good effect.

The technical scheme of the invention is as follows: a preparation method of a polypropylene non-woven fabric super-hydrophobic film comprises the following steps:

(1) mixing 3,3,4,4,5,5,6,6,7,7,8,8,8) -tridecafluorooctyl methacrylate, Vinyltriethoxysilane (VTES) and absolute ethyl alcohol in a mass ratio of 10-15: 2-3: 100; introducing nitrogen and stirring, adding a polypropylene non-woven fabric membrane, 2-azobisisobutyronitrile solution (AIBN) and titanium dioxide sol, and reacting for 4-4.5 h at 60 ℃;

(2) and (2) taking out the polypropylene membrane after the reaction in the step (1), washing with absolute ethyl alcohol, drying in a vacuum drying oven at 90 ℃, and taking out after drying to obtain the polypropylene super-hydrophobic membrane.

In the step (1), the operation of adding the 2, 2-azobisisobutyronitrile solution is as follows: adding the polypropylene non-woven fabric for 10-15 min and then adding; the 2, 2-azobisisobutyronitrile solution is prepared by dissolving 0.08-0.16 parts of 2, 2-azobisisobutyronitrile nanoparticles in 5 parts of absolute ethanol.

In the step (1), the operation of adding the titanium dioxide sol is as follows: adding AIBN dissolving solution for 5-10 min; the amount of the titanium dioxide sol is 2-4 parts by mass based on the titanium dioxide nanoparticles.

The proportion of the titanium dioxide sol is as follows: tetraethyl titanate: anhydrous ethanol: hydrochloric acid: deionized water with the volume ratio of 4-5: 2-3: 1: 50-60, and mixing and stirring the materials.

In the step (1), the stirring speed of the reaction is 500-800 r/min.

In the step (2), the vacuum drying time is 4-5 h.

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

1. the invention provides a modification method based on a polypropylene non-woven fabric super-hydrophobic membrane, which can reduce the surface free energy of the polypropylene non-woven fabric, can increase the roughness on the surface of a material by utilizing a method of combining in-situ growth and sol-gel, and overcomes the problems of carbon chain length, fluorine-containing group enrichment and the like of a fluorine-containing carbon compound for reducing the surface free energy of the material.

2. According to the method, fluorine-containing substances and titanium dioxide sol are added in the step (1), and the fluorine-containing substances and the sol are combined, so that the surface free energy of the material can be reduced, and the surface roughness can be increased. In addition, the prepared super-hydrophobic material has long-lasting effect.

Drawings

FIG. 1 is a scanning electron micrograph of the film prepared in example 1 and example 4; the membrane of example 1 is labeled P-0, the membrane of example 4 is labeled P-1;

FIG. 2 is an energy spectrum of the film prepared in example 1 and example 4; the membrane of example 1 is labeled P-0, the membrane of example 4 is labeled P-1;

FIG. 3 is an infrared image of the film prepared in example 1 and example 4; the membrane of example 1 is labeled P-0, the membrane of example 4 is labeled P-1;

FIG. 4 is a graph of the contact angle of the film prepared in example 1 with example 6; the membrane of example 1 is labeled P-0 and the membrane of example 6 is labeled P-3.

Having the embodiments

The method for modifying a polypropylene nonwoven fabric-based superhydrophobic film according to the present invention is further illustrated by the following examples. It is to be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the present invention, and that various changes and modifications apparent to those skilled in the art in light of the teachings herein are deemed to be within the scope of the present invention.

Example 1:

in this embodiment, a method for modifying a polypropylene nonwoven fabric-based superhydrophobic film includes the following steps:

(1) mixing 2.75g of methacrylic acid (3,3,4,4,5,5,6,6,7,7,8,8,8) -tridecafluorooctyl methacrylate, 0.55g of Vinyltriethoxysilane (VTES) and 25g of absolute ethyl alcohol for reaction, introducing nitrogen for stirring, adding a PP non-woven fabric membrane, 2-azobisisobutyronitrile solution (AIBN) and titanium dioxide sol, and reacting for 4 hours at 60 ℃;

(2) and (2) taking out the PP membrane after the reaction in the step (1), cleaning the PP membrane by using absolute ethyl alcohol, drying the PP membrane in a vacuum drying oven at 90 ℃, and taking out the PP membrane after the drying is finished to obtain the super-hydrophobic polypropylene membrane.

In the step (1), the AIBN is added by the following steps: and adding the PP non-woven fabric for 10-15 min. The AIBN dissolving solution in the step (1) is as follows: 0.0400g of AIBN was dissolved in 1.25g of absolute ethanol.

In the step (1), the operation of adding the titanium dioxide sol is as follows: and adding the AIBN dissolving solution (5-10 min later). The proportion of the titanium dioxide sol is as follows: 4ml of tetraethyl titanate: 2ml of absolute ethanol: 0.7ml) hydrochloric acid: 50ml of deionized water are mixed and stirred at the rotating speed of 500 r/min.

In the step (1), the stirring speed of the reaction is 500 r/min;

in the step (2), the vacuum drying time is 4 h. The film was labeled P-0 and tested accordingly, with the topographical characterization shown in fig. 1, the elemental energy spectrum shown in fig. 2, the infrared test shown in fig. 3, and the contact angle above 150 °, as shown in fig. 4.