CN115819816B

CN115819816B - Preparation method of autocrine type silicon rubber membrane super-smooth material

Info

Publication number: CN115819816B
Application number: CN202211527973.1A
Authority: CN
Inventors: 姜彦�; 刘一凡; 王勃东; 张洪文
Original assignee: Changzhou University
Current assignee: Changzhou University
Priority date: 2022-12-01
Filing date: 2022-12-01
Publication date: 2023-09-26
Anticipated expiration: 2042-12-01
Also published as: CN115819816A

Abstract

The invention belongs to the field of super-smooth surface materials, and particularly relates to a preparation method of an auto-secretion type silicon rubber film super-smooth material. Firstly, uniformly mixing vinyl-terminated polydimethylsiloxane, a cross-linking agent, a catalyst, an inhibitor and self-made microcapsules, and then curing to prepare the silicone rubber membrane material. And (3) pouring dimethyl silicone oil into the membrane material, so that the material prepared after oil pouring has super-slip performance, and water drops can slide on the surface of the material. The invention successfully prepares the self-secretion type silicon rubber membrane super-smooth material.

Description

Preparation method of autocrine type silicon rubber membrane super-smooth material

Technical Field

The invention belongs to the field of super-smooth surface materials, and particularly relates to a preparation method of an auto-secretion type silicon rubber film super-smooth material.

Background

The open edge of nepenthes is composed of hydrophilic components with regular microstructures, secreted mucus substances and rainwater can be stored in the microstructures, a stable and uniform lubricating film is formed, and insects cannot adhere to the open edge and slide into digestive juice at the bottom when falling on the open edge. In light of this, aizenberg et al propose the concept of (slide liquid-infused porous surface, SLIPS). The ultra-smooth surface has the performances of self cleaning, self repairing and the like, is widely focused by researchers, and has wide application prospects in the fields of anti-icing, anti-fog, anti-corrosion, antibacterial and antifouling and the like. The ultra-slip surface consists of a solid phase substrate with micro/nano asperities and a lubricating liquid locked into the microstructure. Among these, the structure of the solid phase substrate of the coarse structure is particularly important. The silicone rubber is an ideal choice for preparing the ultra-smooth material matrix due to the advantages of excellent heat resistance, cold resistance, weather resistance, chemical stability, physiological inertia and the like. The silicon rubber does not generate byproducts in the curing process, has small shrinkage rate, can be deeply vulcanized, and can be prepared into a high-purity and high-transparency product. Silicone rubber plays an increasingly important role in modern life. The ultra-slip material is mainly composed of a porous matrix and poured oil, but the oil is gradually consumed during use so that the ultra-slip performance is reduced.

Disclosure of Invention

In order to solve the problem of reduced super-slip performance caused by oil consumption, the invention provides a preparation method of an autocrine type silicon rubber membrane super-slip material, which ensures the long-acting performance of super-slip performance by using titanium dioxide coated slow-release alkane (such as octadecane) as a slow-release oil source.

In order to achieve the purpose of the invention, the technical scheme adopted is as follows: the preparation method of the autocrine type silicon rubber membrane super-smooth material comprises the following steps:

(1) Uniformly mixing vinyl-terminated Polydimethylsiloxane (PDMS), a cross-linking agent, a catalyst, an inhibitor and self-made microcapsules, then curing to prepare a silicone rubber membrane material,

furthermore, the cross-linking agent adopts hydrogen-containing silicone oil, and the molar ratio of the silicon hydride group in the hydrogen-containing silicone oil to the vinyl group in the PDMS is 2.5:1;

and/or the catalyst is a platinum catalyst diluted with low-viscosity vinyl silicone oil; further, the mass ratio of the vinyl-terminated polydimethylsiloxane to the vinyl-terminated polydimethylsiloxane is 0.1:100;

the inhibitor is tetramethyl tetravinyl cyclotetrasiloxane, and further, the mass ratio of the inhibitor to vinyl-terminated polydimethylsiloxane is 0.4:100;

further, the mass ratio of the self-made microcapsule to the vinyl-terminated polydimethylsiloxane is 1:20-1:5;

the curing temperature is 25 ℃, and the reaction time is 72 hours;

(2) And (3) pouring the silicone rubber film prepared in the step (1) into dimethyl silicone oil, and vertically placing the sample for at least 12 hours to obtain the ultra-smooth surface.

The invention has the beneficial effects that: the vinyl-terminated Polydimethylsiloxane (PDMS), the cross-linking agent, the catalyst, the inhibitor and the self-made microcapsule are uniformly mixed, and then cured to prepare the silicone rubber membrane material, so that the unique self-secretion type silicone rubber membrane ultra-smooth surface is prepared. Compared with the common structure, the structure has more special surface morphology and has an auto-secretion type super-smooth surface.

Drawings

Fig. 1 is an infrared spectrum of the cured silicone rubber film in example 1.

Fig. 2 is a comparison and SEM image of the prepared silicone rubber film in example 1 after being left at room temperature for several days.

FIG. 3 is a sliding angle diagram of the silicone rubber film in example 1 without and after oiling.

Fig. 4 is a comparison graph and SEM graph of the prepared silicone rubber film in comparative example 1, which was left at room temperature for several days.

FIG. 5 is a sliding angle diagram of the silicone rubber film of comparative example 1 without oil.

Detailed Description

The invention will now be explained in further detail with reference to the accompanying drawings:

example 1

(1) Uniformly mixing vinyl-terminated Polydimethylsiloxane (PDMS), cross-linking agent hydrogen-containing silicone oil, platinum catalyst diluted by low-viscosity vinyl silicone oil, inhibitor tetramethyl tetravinyl cyclotetrasiloxane and self-made microcapsule at normal temperature (25 ℃), then curing to prepare the silicone rubber membrane material,

the mol ratio of the silicon hydrogen group in the hydrogen-containing silicone oil to the vinyl in the PDMS is 2.5:1, the mass ratio of the PDMS, the self-made microcapsule, the platinum and the tetramethyl tetravinyl cyclotetrasiloxane is 100:5:0.1:0.4,

mixing octadecane, formamide and Sodium Dodecyl Sulfate (SDS) uniformly, adding tetrabutyl titanate, stirring to form stable emulsion, slowly adding aqueous solution of formamide for reaction to obtain self-made microcapsule,

the curing temperature is 25 ℃, and the reaction time is 72 hours;

FIG. 1 is an infrared spectrum of a cured silicone rubber film of 2168cm in the present embodiment ^-1 The Si-H bond at the site is substantially disappeared, 1629cm ^-1 Where Si-ch=ch ₂ The characteristic absorption peak is basically disappeared, which indicates that the silicon rubber film is completely solidified;

fig. 2 is a photograph of a room temperature standing of the silicone rubber film prepared in this example for several days and an SEM image, illustrating that the silicone rubber film has autocrine properties.

Fig. 3 is a sliding angle diagram of the silicone rubber prepared in the example without oiling and after oiling, the sliding angle of the silicone rubber film without oiling is 4 degrees, the sliding angle of the silicone rubber film after oiling is 2 degrees, and the silicone rubber has good self-cleaning property.

Example 2

the mol ratio of the silicon hydrogen group in the hydrogen-containing silicone oil to the vinyl in the PDMS is 2.5:1, the mass ratio of the PDMS, the self-made microcapsule, the platinum and the tetramethyl tetravinyl cyclotetrasiloxane is 100:10:0.1:0.4,

the curing temperature is 25 ℃, and the reaction time is 72 hours;

Example 3

the mol ratio of the silicon hydrogen group in the hydrogen-containing silicone oil to the vinyl in the PDMS is 2.5:1, the mass ratio of the PDMS, the self-made microcapsule, the platinum and the tetramethyl tetravinyl cyclotetrasiloxane is 100:20:0.1:0.4,

the curing temperature is 25 ℃, and the reaction time is 72 hours;

Comparative example 1

In contrast to example 1, no homemade microcapsules were added in step (1):

(1) Uniformly mixing vinyl-terminated Polydimethylsiloxane (PDMS), cross-linking agent hydrogen-containing silicone oil, platinum catalyst diluted by low-viscosity vinyl silicone oil and inhibitor tetramethyl tetravinyl cyclotetrasiloxane at normal temperature (25 ℃), then curing to prepare a silicone rubber membrane material,

the mol ratio of the silicon hydrogen group in the hydrogen-containing silicone oil to the vinyl in the PDMS is 2.5:1, the mass ratio of the PDMS, the platinum and the tetramethyl tetravinyl cyclotetrasiloxane is 100:0.1:0.4,

the curing temperature is 25 ℃, and the reaction time is 72 hours;

(2) And (3) pouring oil on the silicone rubber film prepared in the step (1), and vertically placing a sample for at least 12 hours to prepare the ultra-smooth surface.

The silicone rubber film prepared in this comparative example had no porous structure and no autocrine property as compared with example 1, and the water droplets did not have slidability on the surface thereof when the silicone rubber film was not impregnated with oil, as shown in fig. 4 and 5.

Claims

1. A preparation method of an autocrine type silicon rubber membrane super-smooth material is characterized by comprising the following steps: the method comprises the following steps:

(1) Preparation of a silicone rubber film: uniformly mixing vinyl-terminated polydimethylsiloxane, a cross-linking agent, a catalyst, an inhibitor and titanium dioxide coated slow-release alkane microcapsules, and then curing to prepare a silicone rubber membrane material;

(2) Preparation of the ultra-smooth surface: pouring the silicone rubber membrane material prepared in the step (1) into dimethyl silicone oil, and vertically placing a sample for at least 12 hours to obtain an ultra-smooth surface;

the preparation method of the titanium dioxide coated slow-release alkane microcapsule comprises the following steps: mixing octadecane, formamide and sodium dodecyl sulfate uniformly, adding tetrabutyl titanate, stirring to form stable emulsion, and slowly adding aqueous solution of formamide for reaction.

2. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the vinyl-terminated polydimethylsiloxane in the step (1) is one or a combination of a plurality of VS5000, VS500 and VS 200.

3. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the cross-linking agent in the step (1) is hydrogen-containing silicone oil, and the molar ratio of the hydrosilyl in the hydrogen-containing silicone oil to the vinyl in the PDMS is 2.5:1.

4. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the catalyst in the step (1) is a platinum catalyst diluted with low-viscosity vinyl silicone oil.

5. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 4, which is characterized in that: the mass ratio of the catalyst to the vinyl-terminated polydimethylsiloxane was 0.1:100.

6. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the inhibitor in the step (1) is tetramethyl tetravinyl cyclotetrasiloxane.

7. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 6, which is characterized in that: the mass ratio of inhibitor to vinyl-terminated polydimethylsiloxane was 0.4:100.

8. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the slow release alkane in the step (1) is octadecane.

9. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the curing temperature in the step (1) is 25 ℃ and the reaction time is 72 hours.

10. The method for preparing the autocrine type silicon rubber membrane super-smooth material according to claim 1, which is characterized in that: the mass ratio of the titanium dioxide coated slow-release alkane microcapsule to the vinyl-terminated polydimethylsiloxane is 1:20-1:5.