CN115972725A - Multi-layer co-extrusion super-hydrophobic polyethylene film and preparation method thereof - Google Patents

Multi-layer co-extrusion super-hydrophobic polyethylene film and preparation method thereof Download PDF

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CN115972725A
CN115972725A CN202211732818.3A CN202211732818A CN115972725A CN 115972725 A CN115972725 A CN 115972725A CN 202211732818 A CN202211732818 A CN 202211732818A CN 115972725 A CN115972725 A CN 115972725A
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film
density polyethylene
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super
hydrophobic
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袁志庆
阳康丽
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Hunan University of Technology
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Hunan University of Technology
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Abstract

The invention discloses a multilayer co-extruded super-hydrophobic polyethylene film and a preparation method thereof, the film is formed by two surface layers sandwiching an intermediate layer, the contact angle of the film surface and water is 153-158 degrees, the rolling angle is less than 9 degrees, the adhesion rate with liquid is less than 0.1 percent, and the surface contact angle still reaches 153-156 degrees after the film surface is rubbed by an eraser loaded with 10N force for 100-200 times. The preparation method comprises (1) mixing low density polyethylene particles and nanometer material particles uniformly and granulating; (2) Carrying out three-layer co-extrusion on the low-density polyethylene master batch, the high-density polyethylene particles and the low-density polyethylene master batch to obtain a three-layer co-extruded thick film; (3) And stretching the three-layer co-extruded thick film into a thin film to obtain the product. The multilayer co-extruded super-hydrophobic polyethylene film has stronger liquid adhesion resistance, better surface wear resistance and better super-hydrophobic stability, and the preparation method is suitable for large-area preparation and has excellent industrialization prospect.

Description

Multi-layer co-extrusion super-hydrophobic polyethylene film and preparation method thereof
Technical Field
The invention belongs to the field of super-hydrophobic films, and particularly relates to a multi-layer co-extrusion super-hydrophobic polyethylene film and a preparation method thereof.
Background
In recent years, inspired by the leaf effect of the load, the super-hydrophobic film with the contact angle of more than 150 degrees with water becomes a hot point of research at home and abroad. The super-hydrophobic film is characterized in that water drops or water-containing liquid (spray, saliva, blood, sewage and the like) is generally spherical on the surface of the super-hydrophobic film, the liquid is difficult to stably stay on the surface of the super-hydrophobic film, the liquid can quickly roll off from the surface of the super-hydrophobic film only by inclining a small angle or under the action of breeze or slight external force, and the dust and other pollutants on the surface of the film are taken away while the liquid rolls off, so that the self-cleaning effect is achieved. The super-hydrophobic film can not be penetrated by any liquid after being soaked in water or aqueous liquid for a long time, and liquid drops can not be adhered to the surface of the super-hydrophobic film after the super-hydrophobic film is taken out, so that the super-hydrophobic film has extremely strong waterproof, water-blocking, bacteriostatic, mildew-proof and liquid adhesion-resistant performances, and the unique properties enable the super-hydrophobic film to have very wide application prospects in agriculture and industry and daily life.
The polyethylene film has the advantages of no toxicity, no odor, low price and the like, is widely applied to packaging and industry and agriculture, but the common polyethylene film in the market has a contact angle with water of less than 110 degrees, has no self-cleaning property, and is easy to be adhered by substances such as dust, thick liquid and the like. If the polyethylene film surface is endowed with super-hydrophobicity, the adhesion of thick liquid on the film surface is greatly reduced, the surface is easier to clean, and the market demand is huge. At present, methods for preparing the super-hydrophobic polyethylene film mainly comprise a template method, an etching method, a micro-phase separation method and the like, however, the reported methods for preparing the super-hydrophobic polyethylene film are limited in a laboratory at present, and the main reason is that the method is difficult to prepare the super-hydrophobic polyethylene film in a large area due to 2 bottlenecks, (1) the reported methods are difficult to prepare the super-hydrophobic polyethylene film in a large area, so that the method is difficult to be practically applied; (2) the super-hydrophobic polyethylene film prepared by the reported method has poor surface wear resistance and poor super-hydrophobic stability.
Therefore, it is of great significance to develop a method which can not only prepare in large area, but also keep the surface of the super-hydrophobic polyethylene film with higher wear resistance and super-hydrophobic stability.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a multilayer co-extruded super-hydrophobic polyethylene film which can be prepared in a large area and can keep higher wear resistance and super-hydrophobic stability on the surface of the super-hydrophobic polyethylene film and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
A multi-layer co-extrusion super-hydrophobic polyethylene film is composed of two surface layers and a middle layer, wherein the surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nano material particles, and the middle layer is a high-density polyethylene film layer; the contact angle of the surface of the multilayer coextruded super-hydrophobic polyethylene film and water is 153-158 degrees, the rolling angle of water drops on the surface of the film is less than 9 degrees, the adhesion rate of the multilayer coextruded super-hydrophobic polyethylene film after being contacted with liquid is less than 0.1 percent, and the contact angle of the surface of the film still reaches 153-156 degrees after the surface of the film is rubbed by rubber loaded with 10N force for 100-200 times.
Preferably, the nano material particles comprise one or more of nano silica particles, nano calcium carbonate particles and nano zinc oxide particles.
Preferably, the average particle size of the nano material particles in the multilayer co-extruded super-hydrophobic polyethylene film is between 1nm and 100 nm.
As a general technical concept, the invention also provides a preparation method of the multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing and granulating low-density polyethylene particles and nano material particles to obtain low-density polyethylene master batches; wherein the mass ratio of the low-density polyethylene particles to the nano material particles is 5-10: 2-1;
(2) Respectively putting the low-density polyethylene master batch, the high-density polyethylene particles and the low-density polyethylene master batch into three hoppers, and performing three-layer co-extrusion to obtain a three-layer co-extruded thick film; wherein the mass ratio of the low-density polyethylene master batch to the high-density polyethylene particles to the low-density polyethylene master batch is 1: 5-50: 1, and the thickness of the three-layer co-extruded thick film is 0.2 mm-1 mm;
(3) And stretching the three-layer co-extruded thick film to a film with the thickness of 0.005-0.1 mm to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
Preferably, in the step (3), the three-layer co-extruded thick film is placed on a longitudinal and transverse stretching frame for stretching.
In the present invention, the low density polyethylene pellets mean a raw material of commercial low density polyethylene pellets having a density of 0.91 to 0.93g/cm without special treatment 3
In the present invention, the high density polyethylene pellets refer to a commercial high density polyethylene pellet material without special treatment, and the density is 0.941 to 0.960g/cm 3
In the invention, the low-density polyethylene master batch refers to low-density polyethylene particles formed by mixing and granulating low-density polyethylene and nano particles.
Compared with the prior art, the invention has the advantages that:
1. compared with the existing super-hydrophobic film, the multilayer co-extruded super-hydrophobic polyethylene film has stronger liquid adhesion resistance, better surface wear resistance and better super-hydrophobic stability. The contact angle of the surface of the multilayer coextruded super-hydrophobic polyethylene film and water is 153-158 degrees, the rolling angle of water drops on the surface of the film is less than 9 degrees, the multilayer coextruded super-hydrophobic polyethylene film has excellent liquid adhesion resistance, the adhesion rate of liquids such as milk, tomato sauce and the like after contacting the multilayer coextruded super-hydrophobic polyethylene film is less than 0.1 percent, and the contact angle of the surface of the film is still more than 153 percent after the surface of the film is rubbed for 100-200 times by using an eraser loaded with 10N force. The multilayer co-extruded super-hydrophobic polyethylene film can greatly reduce the adhesion of thick liquid on the surface of the film, is easier to clean, can keep the surface of the film dry for a long time, and has wider application prospect in the fields of packaging of thick products (liquid milk, tomato sauce and the like), glass, film pasting, paper-plastic composite films and the like, and has huge market demand.
2. The preparation method of the invention has low cost, is suitable for large-area preparation and has excellent industrialization prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the surface of a multilayer co-extruded super-hydrophobic polyethylene film obtained in example 1 of the present invention.
FIG. 2 is a contact angle test chart of the surface of the multilayer co-extruded super-hydrophobic polyethylene film obtained in example 1 of the present invention.
FIG. 3 is a contact angle test chart of the surface of the multilayer co-extruded super-hydrophobic polyethylene film obtained in example 2 of the present invention.
FIG. 4 is a contact angle test chart of the surface of the multi-layer co-extruded super-hydrophobic polyethylene film obtained in example 3 of the present invention.
FIG. 5 is a contact angle test chart of the surface of the multilayer co-extruded super-hydrophobic polyethylene film obtained in example 4 of the present invention.
FIG. 6 is a contact angle test chart of the surface of the multi-layer co-extruded super-hydrophobic polyethylene film obtained in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and instruments used in the following examples are commercially available.
Example 1
The invention relates to a preparation method of a multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing low-density polyethylene particles and nano silicon dioxide particles with the average particle size of 30nm according to the mass ratio of 5: 2, and granulating to form low-density polyethylene master batches;
(2) Weighing low-density polyethylene master batches, high-density polyethylene granules and low-density polyethylene master batches according to the mass ratio of 1: 5: 1, respectively putting the low-density polyethylene master batches, the high-density polyethylene granules and the low-density polyethylene master batches into corresponding hoppers, and extruding a three-layer co-extrusion thick film with the thickness of 0.2mm by a three-layer co-extruder;
(3) And (3) placing the three-layer co-extruded thick film on a longitudinal and transverse stretching frame, and stretching the three-layer co-extruded thick film to a film with the thickness of 0.005mm at a constant speed to obtain the multi-layer co-extruded super-hydrophobic polyethylene film, wherein a scanning electron microscope image of the surface appearance of the film is shown in figure 1.
The multilayer co-extruded super-hydrophobic polyethylene film of the embodiment is formed by two surface layers (outer surface layers) sandwiching an intermediate layer, namely, the surface layer, the intermediate layer and the surface layer, wherein the two surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nano material particles, and the intermediate layer is a high-density polyethylene film layer. As shown in fig. 2, the contact angle test result shows that the contact angle of the water drop on the surface of the multilayer coextruded super-hydrophobic polyethylene film of the embodiment is 153 °, and the rolling angle of the water drop on the surface of the film is 8 °. The adhesion rate of the milk after contacting the surface of the multilayer coextruded super-hydrophobic polyethylene film is less than 0.1%, and after the surface of the film is rubbed for 100 times by an eraser loaded with 10N force, the contact angle of the surface of the film is still kept at 153 degrees, so that excellent liquid adhesion resistance and wear resistance are embodied.
Example 2
The invention relates to a preparation method of a multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing low-density polyethylene particles and nano calcium carbonate particles with the average particle size of 60nm according to the mass ratio of 10: 1, and granulating to form low-density polyethylene master batches;
(2) Weighing low-density polyethylene master batch, high-density polyethylene particles and low-density polyethylene master batch according to the mass ratio of 1: 50: 1, respectively placing the low-density polyethylene master batch, the high-density polyethylene particles and the low-density polyethylene master batch into corresponding hoppers, and extruding a three-layer co-extrusion thick film with the thickness of 1mm by a three-layer co-extruder;
(3) And placing the three-layer co-extruded thick film on a longitudinal and transverse stretching frame to stretch the film with the thickness of 0.1mm at a constant speed, so as to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
The multilayer co-extruded super-hydrophobic polyethylene film of the embodiment is formed by two surface layers sandwiching an intermediate layer, the two surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nano material particles, and the intermediate layer is a high-density polyethylene film layer. As shown in FIG. 3, a contact angle test result shows that the contact angle of a water drop on the surface of the multilayer co-extruded super-hydrophobic polyethylene film is 158 degrees, the rolling angle of the water drop on the surface of the film is 2 degrees, the adhesion rate of the surface of the film after contacting with tomato paste is less than 0.08 percent, the contact angle of the surface of the film is still maintained at 155 degrees after the surface of the film is rubbed for 200 times by an eraser loaded with 10N force, and excellent liquid adhesion resistance and wear resistance are reflected.
Example 3
The invention relates to a preparation method of a multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing low-density polyethylene particles and nano zinc oxide particles with the average particle size of 80nm according to the mass ratio of 8: 2, and granulating to form low-density polyethylene master batches;
(2) Weighing low-density polyethylene master batches, high-density polyethylene granules and low-density polyethylene master batches according to the mass ratio of 1: 10: 1, respectively putting the low-density polyethylene master batches, the high-density polyethylene granules and the low-density polyethylene master batches into corresponding hoppers, and extruding a three-layer co-extrusion thick film with the thickness of 0.5mm by a three-layer co-extruder;
(3) And placing the three-layer co-extruded thick film on a longitudinal and transverse stretching frame to stretch the film with the thickness of 0.05mm at a constant speed, so as to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
The multilayer co-extruded super-hydrophobic polyethylene film is formed by two surface layers in a clamping mode, the two surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nanometer material particles, and the middle layer is a high-density polyethylene film layer. As shown in fig. 4, the contact angle test result shows that the contact angle of the water drop on the surface of the film is 157 degrees, and the rolling angle of the water drop on the surface of the film is 3 degrees. The adhesion rate of the milk after contacting the surface of the multilayer coextruded super-hydrophobic polyethylene film is less than 0.05%, and after the surface of the film is rubbed for 100 times by an eraser loaded with 10N force, the contact angle of the surface of the film is still maintained at 156 degrees, so that the liquid adhesion resistance and the wear resistance are very good.
Example 4
The invention relates to a preparation method of a multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing low-density polyethylene particles and nano zinc oxide particles with the average particle size of 50nm according to the mass ratio of 9: 2, and granulating to form low-density polyethylene master batches;
(2) Weighing low-density polyethylene master batches, high-density polyethylene granules and low-density polyethylene master batches according to the mass ratio of 1: 20: 1, respectively putting the low-density polyethylene master batches, the high-density polyethylene granules and the low-density polyethylene master batches into corresponding hoppers, and extruding a three-layer co-extrusion thick film with the thickness of 0.6mm by a three-layer co-extruder;
(3) And placing the three-layer co-extruded thick film on a longitudinal and transverse stretching frame to stretch the film with the thickness of 0.08mm at a constant speed, so as to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
The multilayer co-extruded super-hydrophobic polyethylene film of the embodiment is formed by two surface layers sandwiching an intermediate layer, the two surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nano material particles, and the intermediate layer is a high-density polyethylene film layer. As shown in FIG. 5, the contact angle test result shows that the contact angle of the water drop on the surface of the multilayer coextruded super-hydrophobic polyethylene film of the embodiment is 155 degrees, and the rolling angle of the water drop on the surface of the film is 5 degrees. The adhesion rate of the milk after contacting the surface of the multilayer coextruded super-hydrophobic polyethylene film is less than 0.03%, and after the surface of the film is rubbed for 150 times by an eraser loaded with 10N force, the contact angle of the surface of the film is still kept at 153 degrees, so that excellent liquid adhesion resistance and wear resistance are embodied.
Example 5
The invention relates to a preparation method of a multilayer co-extruded super-hydrophobic polyethylene film, which comprises the following steps:
(1) Uniformly mixing low-density polyethylene particles and nano calcium carbonate particles with the average particle size of 50nm according to the mass ratio of 9: 1, and granulating to form low-density polyethylene master batches;
(2) Weighing low-density polyethylene master batches, high-density polyethylene granules and low-density polyethylene master batches according to the mass ratio of 1: 30: 1, respectively putting the low-density polyethylene master batches, the high-density polyethylene granules and the low-density polyethylene master batches into corresponding hoppers, and extruding a three-layer co-extrusion thick film with the thickness of 0.8mm by a three-layer co-extruder;
(3) And placing the three-layer co-extruded thick film on a longitudinal and transverse stretching frame to stretch the film with the thickness of 0.01mm at a constant speed, so as to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
The multilayer co-extruded super-hydrophobic polyethylene film is formed by two surface layers in a clamping mode, the two surface layers are nano porous composite film layers, the nano porous composite film layers are made of low-density polyethylene particles and nanometer material particles, and the middle layer is a high-density polyethylene film layer. As shown in FIG. 6, the contact angle test result shows that the contact angle of the water drop on the surface of the multilayer coextruded super-hydrophobic polyethylene film of the embodiment is 154 degrees, and the rolling angle of the water drop on the surface of the film is 7 degrees. The adhesion rate of the tomato sauce after contacting the surface of the multilayer co-extruded super-hydrophobic polyethylene film is less than 0.08%, and after the surface of the film is rubbed 160 times by an eraser loaded with 10N force, the contact angle of the surface of the film is still kept at 153 degrees, so that excellent liquid adhesion resistance and wear resistance are embodied.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modifications, equivalent substitutions, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention are within the scope of the technical scheme of the present invention.

Claims (5)

1. A multi-layer co-extrusion super-hydrophobic polyethylene film is characterized by being formed by two surface layers clamping an intermediate layer, wherein the surface layers are nano porous composite film layers which are made of low-density polyethylene particles and nano material particles as raw materials, and the intermediate layer is a high-density polyethylene film layer; the contact angle of the surface of the multilayer coextruded super-hydrophobic polyethylene film and water is 153-158 degrees, the rolling angle of water drops on the surface of the film is less than 9 degrees, the adhesion rate of the multilayer coextruded super-hydrophobic polyethylene film after contacting with liquid is less than 0.1 percent, and the contact angle of the surface of the film still reaches 153-156 degrees after the film is rubbed on the surface of the film for 100-200 times by an eraser loaded with 10N force.
2. The multilayer coextruded superhydrophobic polyethylene film of claim 1, wherein the nanomaterial particles comprise one or more of nano silica particles, nano calcium carbonate particles, and nano zinc oxide particles.
3. The multilayer co-extruded superhydrophobic polyethylene film according to claim 1 or 2, wherein the average particle size of the nano material particles is between 1nm and 100 nm.
4. A method for preparing a multilayer co-extruded super hydrophobic polyethylene film according to any of claims 1 to 3, comprising the steps of:
(1) Uniformly mixing and granulating low-density polyethylene particles and nano material particles to obtain low-density polyethylene master batches; wherein the mass ratio of the low-density polyethylene particles to the nano material particles is 5-10: 2-1;
(2) Respectively putting the low-density polyethylene master batch, the high-density polyethylene particles and the low-density polyethylene master batch into three hoppers, and performing three-layer co-extrusion to obtain a three-layer co-extruded thick film; wherein the mass ratio of the low-density polyethylene master batch to the high-density polyethylene particles to the low-density polyethylene master batch is 1: 5-50: 1, and the thickness of the three-layer co-extruded thick film is 0.2-1 mm;
(3) And stretching the three-layer co-extruded thick film to a film with the thickness of 0.005-0.1 mm to obtain the multi-layer co-extruded super-hydrophobic polyethylene film.
5. The method for preparing the multilayer co-extruded super-hydrophobic polyethylene film as claimed in claim 4, wherein in the step (3), the three-layer co-extruded thick film is placed on a longitudinal and transverse stretching frame for stretching.
CN202211732818.3A 2022-12-30 2022-12-30 Multi-layer co-extrusion super-hydrophobic polyethylene film and preparation method thereof Pending CN115972725A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201941208U (en) * 2011-02-28 2011-08-24 海宁市粤海彩印有限公司 Low-temperature impact-resistant polyethylene film
CN102627799A (en) * 2012-04-25 2012-08-08 上海长歌包装材料有限公司 Super-hydrophobicity low-density polyethylene thin film material and preparation method thereof
CN110218347A (en) * 2019-06-12 2019-09-10 华东理工大学 A kind of preparation method of hydrophobic polymer membrane material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN201941208U (en) * 2011-02-28 2011-08-24 海宁市粤海彩印有限公司 Low-temperature impact-resistant polyethylene film
CN102627799A (en) * 2012-04-25 2012-08-08 上海长歌包装材料有限公司 Super-hydrophobicity low-density polyethylene thin film material and preparation method thereof
CN110218347A (en) * 2019-06-12 2019-09-10 华东理工大学 A kind of preparation method of hydrophobic polymer membrane material

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