CN114292485B - A hydrophobic anti-bacterial anti-reflection material and its preparation method and application - Google Patents

Abstract

The invention belongs to the field of high molecular functional materials, and in particular relates to an antibacterial adhesion-resistant hydrophobic anti-reflection material, a preparation method and application thereof; secondly, copolymerizing vinyl-terminated polysiloxane and functionalized nano-silica with methyl methacrylate and hydroxyethyl methacrylate by free radical polymerization to form an organic-inorganic hybrid polymer containing nano-silica and polysiloxane segments. The coating is coated on the surface of an optical plastic product by using a lifting dipping method to form an anti-reflection coating, and the light transmittance of the coated product is found to be increased by a light transmittance test. The optical antireflection film coating is successfully prepared, and the transmittance, the hydrophobicity and the antibacterial adhesion performance of the optical plastic product can be increased after the optical antireflection film coating is reasonably coated.

Description

A hydrophobic anti-bacterial anti-reflection material and its preparation method and application

Technical field

The invention belongs to the field of polymer functional materials, and specifically relates to a hydrophobic anti-bacterial anti-reflection material and its preparation method and application.

Background technique

Optical anti-reflection coating has become one of the research hotspots of optical materials due to its wide application in optical equipment such as automobile windows, laser systems and solar photovoltaic devices. The current optically transparent films are mainly polyethylene terephthalate (PET) films. The PET molecule has a rigid benzene ring structure on the main chain, which makes PET have good mechanical properties and good heat resistance. Although PET has excellent optical properties, the PET film has poor hydrophobicity, easily adheres to pollutants, and poor self-cleaning performance, which limits its application scope. For this reason, the surface of PET film needs to be modified to improve its surface properties, extend its service life and broaden its application range. Nano-SiO ₂ has the characteristics of chemical inertness and optical transparency. After modification, nano-SiO ₂ has a certain degree of hydrophobicity and is one of the important materials for optical anti-reflection coatings. Polydimethylsiloxane (PDMS) is widely used in solar cells due to its high transmittance, low refractive index (1.43) and good adhesive properties. It is also an environmentally friendly material with low cost. As a material with relatively comprehensive functions, acrylic resin is often used as a coating. The polymer itself has relatively good transparency. By coating on the surface of the base material, the corresponding properties can be obtained. Compared with acrylic resins and pure inorganic anti-reflective materials, the preparation of organic-inorganic hybrid anti-reflective materials is of great significance.

Contents of the invention

The purpose of the present invention is to provide a hydrophobic anti-bacterial anti-reflection material and its preparation method and application.

In order to achieve the purpose of the present invention, the technical solutions adopted are:

A method for preparing a hydrophobic anti-bacterial anti-reflection material, including the following steps:

(1) Preparation of functionalized nanosilica:

Add ethyl orthosilicate dropwise to the mixed solution of ethanol, distilled water and ammonia, and stir vigorously until the system turns light blue to obtain nanosilica gel, and then add a silane coupling agent for functional modification, where The particle size of silica is 100±20nm;

Specifically, in the reaction vessel, distilled water, absolute ethanol, and ammonia were added in sequence, and after stirring evenly, ethyl orthosilicate was added, and the reaction was stirred at room temperature for 24 hours to obtain a nano-SiO ₂ colloidal solution. Then add methyltrimethoxysilane (MTMS) to the above colloidal solution, continue to stir the reaction at room temperature for 24 hours, and then add γ-methacryloyloxytrimethoxysilane (KH-570) into the reaction bottle. , continue the reaction for 24h to obtain a functionalized SiO ₂ colloidal solution.

(2) Preparation of vinyl-terminated polysiloxane (V-PDMS):

In the presence of the catalyst trifluoromethanesulfonic acid, octamethylcyclotetrasiloxane (D ₄ ) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane ( DVMS) ring-opening reaction to synthesize vinyl-terminated polysiloxane.

Specifically, add octamethylcyclotetrasiloxane (D ₄ ) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVMS) into the reaction bottle and stir evenly. Afterwards, the catalyst trifluoromethanesulfonic acid was added, and the reaction was continued with stirring at 70°C for 6 hours to obtain the product.

(3) Preparation of anti-reflective materials:

The functionalized nanosilica prepared in step (1) and the vinyl-terminated polysiloxane prepared in step (2), as well as methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) Mix evenly in the solvent N,N-dimethylformamide (DMF), use AIBN as the initiator, and perform a free radical polymerization reaction to obtain the anti-bacterial adhesion hydrophobic anti-reflection material.

Specifically, add N,N-dimethylformamide (DMF) and methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) with a molar ratio of 1:1 to a three-necked flask equipped with a condenser tube. ), after mixing evenly, add functionalized nanosilica and vinyl-terminated polysiloxane, use AIBN as the initiator, stir and react at 70°C for 6 hours in a nitrogen atmosphere to obtain the product.

The preparation method of the anti-bacterial adhesion hydrophobic anti-reflection material prepared by the present invention is used to coat optical plastic products and form an anti-reflection coating.

Specifically, the diluted copolymer is coated on the surface of the optical plastic product according to the requirements of the pulling and impregnation method, and then placed in an oven for heat treatment at 60°C for 0.5 hours to solidify into a film to obtain an anti-reflective coating.

Specifically, the optical plastic product is an organic substrate, which can be any one of polycarbonate, polymethylmethacrylate, and PET.

Compared with the prior art, the beneficial effects of the present invention are:

The invention utilizes functionalized nanosilica and vinyl-terminated polysiloxane to react with acrylate monomers to effectively improve the hydrophobicity and bacteriostatic properties of the base material; functionalized nanosilica and vinyl-terminated polysiloxane The double bonds on the siloxane are copolymerized with acrylate through free radical reaction. The preparation method is simple, the product is stable, and the anti-reflection effect is good. The light transmittance can reach up to 94.3%, the contact angle reaches 105°, and it has a certain degree of hydrophobicity. It is an ideal optical material.

Description of the drawings

Figure 1 shows the infrared images of nano-silica before and after modification. In the figure, a corresponds to SiO ₂ , b corresponds to MTMS-SiO ₂ , and c corresponds to MTMS/KH570-SiO ₂ ;

Figure 2 is the NMR spectrum of vinyl-terminated polysiloxane;

Figure 3 shows the transmittance/haze curve of the anti-reflection coating prepared with different modified nano-SiO ₂ mass fractions;

Figure 4 shows the contact angle diagram of the anti-reflection coating prepared with different modified nano-SiO ₂ mass fractions;

Figure 5 is a graph showing the bacterial adhesion amount. a is the E. coli adhesion amount of the anti-reflection material prepared in Comparative Example 3, and b is the E. coli adhesion amount of the anti-reflection material prepared in Example 2.

Detailed ways

The present invention is not limited to the following specific embodiments. Based on the disclosure of the present invention, those of ordinary skill in the art can adopt a variety of other specific embodiments to implement the present invention, or simply change or adopt the design structure and ideas of the present invention. Any modifications fall within the protection scope of the present invention. It should be noted that, as long as there is no conflict, the embodiments and features in the embodiments of the present invention can be combined with each other.

The present invention will be further described in detail below in conjunction with the examples:

Example 1:

(1) Preparation of functionalized nanosilica

Add 2g distilled water, 1g ammonia, and 59g absolute ethanol into a 250ml three-necked flask according to the molar ratio of 4:1:45, then add 18g TEOS to it, and magnetically stir the reaction at room temperature for 24h. After the reaction, nano-SiO is obtained. ₂ Colloidal solution. Then, 1.3 g of methyltrimethoxysilane (MTMS) was added to the above colloidal solution, and the reaction was continued to stir at room temperature for 24 h. Finally, 1.8g of KH-570 was added into the reaction bottle to obtain a modified functionalized SiO ₂ colloidal solution (MTMS/KH570-SiO ₂ ).

Figure 1 shows the infrared spectra of nano-SiO ₂ before and after modification by MTMS and KH570. The unmodified nano-SiO ₂ (a in Figure 1) has the stretching vibration peak of -OH at 3480cm ^-1 and - at 1636cm ^-1 The bending vibration peak of OH, the strong and broad absorption band at 1100cm ^-1 is the antisymmetric stretching vibration absorption peak of Si-O-Si, and the 804cm ^-1 is the symmetric stretching vibration absorption peak of Si-O-Si bond, 471cm ^{- 1} is the bending vibration peak of Si-O bond. After modification with the silane coupling agent MTMS, the stretching vibration peak of Si-CH ₃ appeared at 1273 cm ^-1 and the stretching vibration absorption peak of -CH ₃ appeared at 2952 cm ^-1 , indicating that the MTMS modification was successful (b in Figure 1). In addition to the above characteristic peaks of nano-SiO ₂ , nano-SiO ₂ modified by silane coupling agent KH570 also has a new absorption peak at 1723 cm ^-1 , which is the stretching vibration of the C=O group in silane coupling agent KH570 Absorption peak (c in Figure 1). It shows that there are organic substances on the surface of modified nano-SiO ₂ , that is, after hydrolysis of silane coupling agent KH570 and MTMS, it reacts with -OH on the surface of nano-SiO ₂ particles to form a covalent bond. Nano-SiO ₂ and silane coupling agent KH570 and MTMS Chemical graft bonding occurs.

(2) Preparation of vinyl-terminated polysiloxane

Add 9g DVMS and 75g D ₄ into a 250ml three-necked flask, then stir and raise the temperature to 70°C, add 0.13g catalyst trifluoromethanesulfonic acid to it, and insulate and react at 70°C for 6 hours to obtain vinyl-terminated polysiloxane. alkane (V-PDMS).

Figure 2 is the NMR spectrum of vinyl-terminated polysiloxane (V-PDMS), where a (δ=0.1) is the proton hydrogen on Si-CH ₃ , b (δ=5.74), c (δ=5.86 ) and d (δ = 6.13) are the proton hydrogen on CH=CH _2. These peaks indicate that the synthesized product molecules not only contain skeleton polysiloxane segments, but also vinyl and other groups, which can be judged to have been successfully prepared for the experiment. Engineered vinyl-terminated polysiloxane.

(3) Preparation of anti-reflective materials

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15gDMF, accounting for 0.5% of the total acrylate monomer, modified nano-SiO ₂ particles, and use AIBN as the trigger agent, and the reaction was completed after incubating the reaction at 70°C for 6 hours in a nitrogen atmosphere. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Figure 3 shows the transmittance and haze curves of the anti-reflection coating under different silica mass fractions. It can be seen that the transmittance of the anti-reflection coating in this experiment is 93.9% and the haze is 3.70%.

Figure 4 shows the contact angle of the antireflection coating under different silica mass fractions. a is the contact angle of pure PET, which is 72°, and b is the contact angle of the antireflection coating in this experiment, which is 92°.

Example 2:

(1) The preparation method of functionalized nanosilica is the same as in Example 1.

(2) The preparation of vinyl-terminated polysiloxane is the same as in Example 1.

(3) Preparation of anti-reflective materials

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15gDMF, accounting for 1% of the total acrylic monomers, modified nano-SiO ₂ particles, with AIBN as the trigger agent, and the reaction was completed after incubating the reaction at 70°C for 6 hours in a nitrogen atmosphere. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Figure 3 shows the transmittance and haze curves of the anti-reflection coating under different silica mass fractions. It can be seen that the transmittance of the anti-reflection coating in this experiment is 94.5% and the haze is 1.42%.

Figure 4 shows the contact angle of the antireflection coating under different silica mass fractions. c is the contact angle of the antireflection coating in this experiment, which is 93°.

Example 3:

(1) The preparation method of functionalized nanosilica is the same as in Example 1.

(2) The preparation of vinyl-terminated polysiloxane is the same as in Example 1.

(3) Preparation of anti-reflective materials:

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15gDMF, accounting for 1.5% of the total acrylic monomers, modified nano-SiO ₂ particles, with AIBN as the trigger agent, and the reaction was completed after incubating the reaction at 70°C for 6 hours in a nitrogen atmosphere. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Figure 3 shows the transmittance and haze curves of the anti-reflection coating at different mass fractions. It can be seen that the transmittance of the anti-reflection coating in this experiment was 93.5% and the haze was 3.57%.

Figure 4 shows the contact angle of the antireflection coating under different silica mass fractions. d is the contact angle of the antireflection coating in this experiment, which is 98°.

Example 4:

(1) The preparation method of functionalized nanosilica is the same as in Example 1.

(2) The preparation of vinyl-terminated polysiloxane is the same as in Example 1.

(3) Preparation of anti-reflective materials

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15gDMF, accounting for 2% of the total acrylate monomer, modified nano-SiO ₂ particles, using AIBN as the trigger agent, and the reaction was completed after incubating the reaction at 70°C for 6 hours in a nitrogen atmosphere. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Figure 3 shows the transmittance and haze curves of the anti-reflection coating at different mass fractions. It can be seen that the transmittance of the anti-reflection coating in this experiment was 92.8% and the haze was 8.18%.

Figure 4 shows the contact angle of the antireflection coating under different silica mass fractions. e is the contact angle of the antireflection coating in this experiment, which is 100°.

Example 5:

(1) The preparation method of functionalized nanosilica is the same as in Example 1.

(2) The preparation of vinyl-terminated polysiloxane is the same as in Example 1.

(3) Preparation of anti-reflective materials

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15gDMF, accounting for 3% of the total acrylate monomer, modified nano-SiO ₂ particles, using AIBN as the trigger agent, and the reaction was completed after incubating the reaction at 70°C for 6 hours in a nitrogen atmosphere. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Figure 3 shows the transmittance and haze curves of the antireflection coating at different mass fractions. It can be seen that the transmittance of the antireflection coating in this experiment was 92.7% and the haze was 8.83%.

Figure 4 shows the contact angle of the antireflection coating under different silica mass fractions. f is the contact angle of the antireflection coating in this experiment, which is 105°.

Comparative example 1

(1) Preparation of anti-reflective materials

Add 2.3g MMA, 3.25g HEMA, and 15g DMF to a 100ml three-necked flask equipped with a condenser tube, use AIBN as the initiator, and incubate the reaction at 70°C for 6 hours in a nitrogen atmosphere before ending the reaction. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Compared with Example 1, the main difference between Comparative Example 1 and Example 1 is that nano-silica and vinyl-terminated polysiloxane were not added. Through the light transmittance/haze test, the light transmittance was determined to be 92.8% and the haze was 5.38%; through the contact angle test, the contact angle was 60°.

In Comparative Example 1, the copolymer coating without adding nano-silica and vinyl-terminated polysiloxane has a penetration-increasing effect that is not as good as the anti-reflection coating in Example 1, and the contact angle in Comparative Example 1 Very low, poor hydrophobicity.

Comparative example 2

(1) The preparation of vinyl-terminated polysiloxane is the same as in Example 1.

(2) Preparation of anti-reflective materials

Add 2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF to a 100ml three-necked flask equipped with a condenser tube. Use AIBN as the initiator and incubate the reaction at 70°C for 6 hours in a nitrogen atmosphere before ending the reaction. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Compared with Example 1, the main difference between Comparative Example 2 and Example 1 is that no nano-silica was added. Through the light transmittance/haze test, the light transmittance was determined to be 93.8% and the haze was 4.37%; through the contact angle test, the contact angle was 98°.

In Comparative Example 1, the penetration-increasing effect of the copolymer coating without adding nano-silica is not as good as the anti-reflection coating in Example 1. At the same time, it can be seen from the data of the above examples that the introduction of nano-silica increases. , the light transmittance of the anti-reflection coating shows a trend of increasing first and then decreasing.

Comparative example 3

(1) The preparation method of functionalized nanosilica is the same as in Example 1.

(2) Preparation of anti-reflective materials:

In a 100ml three-necked flask equipped with a condenser tube, add 2.3g MMA, 3.25g HEMA, 15g DMF and modified nano-SiO ₂ particles accounting for 1% of the total acrylate monomer, with AIBN as the initiator, in a nitrogen atmosphere The reaction was completed after incubation at 70°C for 6 hours. Cut the PET film into small square pieces of 4×4cm, apply the diluted antireflection material on the surface of the PET film according to the requirements of the dipping and pulling method, and put it into a 60°C oven for heat treatment for 0.5h to solidify into a film to obtain antireflection. coating.

Compared with Example 1, the main difference between Comparative Example 3 and Example 1 is that no vinyl-terminated polysiloxane was added. Through the light transmittance/haze test, the light transmittance was determined to be 92.1% and the haze was 6.42%; through the contact angle test, the contact angle was 78°. As shown in Figure 5, a is the adhesion amount of E. coli without adding vinyl-terminated polysiloxane, and b is the adhesion amount of E. coli in Example 2. It can be seen that adding vinyl-terminated polysiloxane can Reduce the amount of bacterial adhesion. Compared with pure PET, the amount of bacterial adhesion is much reduced.

In Comparative Example 1, the penetration increasing effect of the copolymer coating without adding vinyl-terminated polysiloxane is not as good as the anti-reflection coating in Example 1. At the same time, it can be seen from the data of the above examples that the vinyl-terminated polysiloxane The introduction of polysiloxane can not only improve the light transmittance of the anti-reflection coating, but also increase its contact angle and improve hydrophobicity.

The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person familiar with the technical field can, within the technical scope disclosed in the present invention, implement the technical solutions of the present invention. Any equivalent substitutions or changes in the concepts thereof shall be included in the protection scope of the present invention.

Claims (9)

1. A method for preparing a hydrophobic anti-bacterial anti-reflection material, which is characterized in that it includes the following steps: (1) Preparation of functionalized nanosilica: Add ethyl orthosilicate dropwise to the mixed solution of ethanol, distilled water and ammonia, stir vigorously until the system turns light blue, obtain nanosilica gel, and then add The silane coupling agent is functionally modified, in which the silica particle size is 100±20 nm; (2) Preparation of vinyl-terminated polysiloxane (V-PDMS): in the presence of the catalyst trifluoromethanesulfonic acid, through octamethylcyclotetrasiloxane (D ₄ ) and 1,3-bis Ring-opening reaction of vinyl-1,1,3,3-tetramethyldisiloxane (DVMS) to synthesize vinyl-terminated polysiloxane; (3) Preparation of anti-reflection material: Combine the functionalized nanosilica prepared in step (1) and the vinyl-terminated polysiloxane prepared in step (2), methyl methacrylate (MMA), and Mix hydroxyethyl acrylate (HEMA) in the solvent N, N-dimethylformamide (DMF) evenly, and use AIBN as the initiator to perform a free radical polymerization reaction to obtain a hydrophobic anti-bacterial anti-reflection material; Step (1) The specific preparation steps of functionalized nanosilica are: In the reaction vessel, add distilled water, absolute ethanol, and ammonia in sequence, stir evenly, then add ethyl orthosilicate, stir the reaction at room temperature to obtain a nano- _SiO2 colloidal solution, and then add methyltrimethoxysilane (MTMS) into the above colloidal solution, continue to stir the reaction at room temperature, and then add γ-methacryloyloxytrimethoxysilane (KH-570) into the reaction bottle to obtain a functionalized SiO ₂ colloidal solution. 2. The preparation method of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 1, characterized in that: in the preparation step of step (1) functionalized nano-silica (SiO ₂ ), the amount of nano-SiO ₂ colloidal solution is The preparation reaction time is 24 h; And/or, the silane coupling agent modified nanosilica is carried out through a two-step method. After adding methyltrimethoxysilane (MTMS) and reacting for 24 hours, γ-methacryloyloxytrimethoxy is added. silane (KH-570) and continue the reaction for 24 hours. 3. The preparation method of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 1, characterized in that: the specific preparation steps of step (2) vinyl-terminated polysiloxane (V-PDMS) are: Add octamethylcyclotetrasiloxane (D ₄ ) and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (DVMS) into the reaction bottle, stir evenly, and then add Catalyst trifluoromethanesulfonic acid, continue stirring the reaction to obtain the product. 4. The preparation method of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 3, characterized in that: in the preparation step of step (2) vinyl-terminated polysiloxane (V-PDMS): reaction temperature The temperature was 70 °C and the reaction time was 6 h. 5. The preparation method of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 1, characterized in that: the specific preparation step of the anti-reflection material in step (3) is: in a three-necked flask equipped with a condenser tube Add N,N-dimethylformamide (DMF) and methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) with a molar ratio of 1:1. After mixing evenly, add functionalized nanometer dioxide. After mixing silicon and vinyl-terminated polysiloxane, AIBN is used as the initiator and stirred in a nitrogen atmosphere to react to obtain the product. 6. The preparation method of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 5, characterized in that: in the specific preparation steps of the anti-reflection material described in step (3): the reaction temperature is 70 ° C. The time is 6 hours. 7. The anti-bacterial adhesion hydrophobic anti-reflection material prepared according to the preparation method of the anti-bacterial adhesion hydrophobic anti-reflection material according to any one of claims 1 to 6. 8. The application of the anti-bacterial adhesion hydrophobic anti-reflective material according to claim 7, characterized in that it is used to form an anti-reflective coating for optical plastic products. 9. The application of anti-bacterial adhesion hydrophobic anti-reflection material according to claim 8, characterized in that the optical plastic product is any one of polycarbonate, polymethylmethacrylate and PET.