CN114292485B - Antibacterial adhesion-resistant hydrophobic anti-reflection material, and preparation method and application thereof - Google Patents
Antibacterial adhesion-resistant hydrophobic anti-reflection material, and preparation method and application thereof Download PDFInfo
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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
Technical Field
The invention belongs to the field of high molecular functional materials, and particularly relates to a hydrophobic anti-reflection material for resisting bacterial adhesion, a preparation method and application thereof.
Background
Optical antireflection films are widely used in optical devices such as automobile windows, laser systems and solar photovoltaic devices, and are one of the hot spots for research of optical materials. The existing optical transparent film is mainly made of polyethylene terephthalate (Polyethylene terephthalate, PET) film, and the PET molecule main chain has a rigid benzene ring structure, so that the PET has good mechanical property and heat resistance. Although PET has excellent optical properties, PET film has poor hydrophobicity, is easy to adhere to pollutants, and has poor self-cleaning performance, so that the application range of the PET film is limited. Therefore, the surface of the PET film needs to be modified, the surface property of the PET film is improved, the service life of the PET film is prolonged, and the application range of the PET film is widened. Nano SiO 2 Has the characteristics of chemical inertness, optical transparency and the like, and the modified nano SiO 2 Has certain hydrophobicity and is one of important materials of the optical antireflection film. Polydimethylsiloxane (PDMS) is widely used in solar cells due to its high transmittance, low refractive index (1.43) and good adhesive properties, and is a low-cost environment-friendly material. The acrylic resin is used as a material with relatively comprehensive functions, often used as a coating, has relatively good transparency, and obtains corresponding performance by coating on the surface of a matrix material. Compared with acrylic resin and purely inorganic anti-reflection materials, the preparation of the organic-inorganic hybrid anti-reflection material has important significance.
Disclosure of Invention
The invention aims to provide a hydrophobic anti-reflection material for resisting bacterial adhesion, and a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted is as follows:
a method for preparing a hydrophobic anti-reflection material for resisting bacterial adhesion, which comprises the following steps:
(1) Preparation of functionalized nano-silica:
dropwise adding tetraethoxysilane into a mixed solution of ethanol, distilled water and ammonia water, vigorously stirring until the system is light blue to obtain nano silica gel, and adding a silane coupling agent for functional modification, wherein the particle size of the silica is 100+/-20 nm;
specifically, distilled water, absolute ethyl alcohol and ammonia water are sequentially added into a reaction vessel, after uniform stirring, tetraethoxysilane is added, and stirring reaction is carried out for 24 hours at room temperature, thus obtaining nano SiO 2 Colloidal solution. Adding methyltrimethoxysilane (MTMS) into the colloid solution, continuously stirring at room temperature for reaction for 24h, adding gamma-methacryloxytrimethoxysilane (KH-570) into a reaction bottle, and continuously reacting for 24h to obtain functionalized SiO 2 Colloidal solution.
(2) Preparation of vinyl-terminated polysiloxane (V-PDMS):
by octamethyltetrasiloxane (D) in the presence of the catalyst trifluoromethanesulfonic acid 4 ) And a ring opening reaction of 1, 3-divinyl-1, 3-tetramethyldisiloxane (DVMS) to synthesize a vinyl terminated polysiloxane.
Specifically, octamethyl cyclotetrasiloxane (D 4 ) Adding 1, 3-divinyl-1, 3-tetramethyl Disiloxane (DVMS) into a reaction bottle, uniformly stirring, adding a catalyst trifluoromethyl sulfonic acid, and continuously stirring at 70 ℃ for reaction for 6 hours to obtain a product.
(3) Preparation of an anti-reflection material:
uniformly mixing the functionalized nano silicon dioxide prepared in the step (1) with the vinyl-terminated polysiloxane prepared in the step (2), methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) in a solvent N, N-Dimethylformamide (DMF), and carrying out free radical polymerization reaction by taking AIBN as an initiator to obtain the antibacterial adhesion-resistant hydrophobic anti-reflection material.
Specifically, N-Dimethylformamide (DMF) and a molar ratio of 1 were added to a three-necked flask equipped with a condenser tube: 1 Methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA), adding functional nano silicon dioxide and vinyl end-capped polysiloxane after uniformly mixing, taking AIBN as an initiator, and stirring and reacting for 6 hours at 70 ℃ in a nitrogen atmosphere to obtain the product.
The preparation method of the antibacterial adhesion-resistant hydrophobic anti-reflection material is used for coating optical plastic products and forming an anti-reflection coating.
Specifically, the diluted copolymer is coated on the surface of an optical plastic product according to the requirement of a lifting impregnation method, and then the optical plastic product is put into an oven for heat treatment at 60 ℃ for 0.5h to be cured into a film, so that the anti-reflection coating is obtained.
Specifically, the optical plastic product is an organic substrate, and can be specifically any one of polycarbonate, polymethyl methacrylate and PET.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the hydrophobic property and antibacterial property of the matrix material are effectively improved by utilizing the reaction of the functionalized nano silicon dioxide and vinyl-terminated polysiloxane with acrylic monomers; the double bond on the functionalized nano silicon dioxide and vinyl terminated polysiloxane is copolymerized with acrylic ester through a free radical reaction, the preparation method is simple, the product is stable, the anti-reflection effect is good, the light transmittance can reach 94.3% at the highest, the contact angle reaches 105 degrees, and the optical material has certain hydrophobicity and is an ideal optical material.
Drawings
FIG. 1 is an infrared view of a nano-silica before and after modification, where a corresponds to SiO 2 B corresponds to MTMS-SiO 2 C corresponds to MTMS/KH570-SiO 2 ；
FIG. 2 is a nuclear magnetic spectrum of vinyl-terminated polysiloxanes;
FIG. 3 shows the prepared nano SiO after different modifications 2 A light transmittance/haze curve of the antireflection film at mass fraction;
FIG. 4 shows the prepared nano SiO after different modifications 2 Contact angle diagram of antireflection film in mass fraction;
FIG. 5 is a graph showing the adhesion amount of bacteria, a is the adhesion amount of E.coli of the antireflective material prepared in comparative example 3, and b is the adhesion amount of E.coli of the antireflective material prepared in example 2.
Detailed Description
The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
The invention is further described in detail below in connection with the examples:
example 1:
(1) Preparation of functionalized nanosilicon dioxide
According to 4:1:45 mol ratio, adding 2g distilled water, 1g ammonia water and 59g absolute ethanol into a 250ml three-neck flask, then adding 18g TEOS into the three-neck flask, magnetically stirring the mixture at room temperature for reaction for 24 hours, and obtaining nano SiO after the reaction is finished 2 Colloidal solution. Then, 1.3g of methyltrimethoxysilane (MTMS) was added to the above colloidal solution, and the reaction was continued with stirring at room temperature for 24 hours. Adding 1.8g KH-570 into a reaction flask to obtain modified functional SiO 2 Colloidal solution (MTMS/KH 570-SiO) 2 )。
FIG. 1 is a nano SiO 2 Infrared spectrogram before and after modification by MTMS and KH570, unmodified nano SiO 2 (a in FIG. 1) at 3480cm -1 The stretching vibration peak of-OH is 1636cm -1 Bending vibration peak of-OH at 1100cm -1 The strong and wide absorption band is an antisymmetric telescopic vibration absorption peak of Si-O-Si, 804cm -1 The symmetrical telescopic vibration absorption peak of Si-O-Si bond is 471cm -1 Is the bending vibration peak of Si-O bond. After being modified by a silane coupling agent MTMS, the modified polymer is modified at 1273cm -1 Appearance of Si-CH 3 Is 2952cm -1 Of (C) CH 3 The appearance of the telescopic vibration absorption peak of (b) indicates that MTMS modification was successful (b in FIG. 1). Nano SiO modified by silane coupling agent KH570 2 Except for nano SiO with the above 2 Outside the characteristic peak of 1723cm -1 A new absorption peak appears at this point, which is the stretching vibration absorption peak of the c=o group in the silane coupling agent KH570 (C in fig. 1). Description of modified nano SiO 2 The surface is provided with organic matters, namely silane coupling agents KH570 and MTMS which are hydrolyzed and then are reacted with nano SiO 2 the-OH on the surface of the particles is dehydrated to generate covalent bonds,nano SiO 2 Chemical grafting bonding occurs with silane coupling agents KH570 and MTMS.
(2) Preparation of vinyl-terminated polysiloxanes
9g DVMS and 75g D 4 Into a 250ml three-neck flask, 0.13g of catalyst trifluoromethanesulfonic acid was added thereto while stirring and heating to 70℃and reacted at 70℃for 6 hours with heat preservation to give vinyl-terminated polysiloxane (V-PDMS).
FIG. 2 is a nuclear magnetic spectrum of vinyl-terminated polysiloxane (V-PDMS), wherein a (delta=0.1) is Si-CH 3 Proton hydrogen on b (δ=5.74), c (δ=5.86) and d (δ=6.13) are ch=ch 2 These peaks indicate that the synthetic product molecule contains not only backbone polysiloxane segments but also vinyl groups and the like, and can be used to determine that the experimentally designed vinyl-terminated polysiloxane has been successfully prepared.
(3) Preparation of anti-reflection material
2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF which account for 0.5 percent of the total acrylic monomer modified nano SiO are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Fig. 3 shows the transmittance and haze curves of the antireflection film at different silica mass fractions, and it can be seen that the transmittance of the antireflection film in this experiment is 93.9% and the haze is 3.70%.
Fig. 4 shows contact angles of antireflection films with different silica mass fractions, a is a contact angle of pure PET, 72 °, and b is a contact angle of the antireflection film in this experiment, 92 °.
Example 2:
(1) The preparation method of the functionalized nano-silica is the same as in example 1.
(2) The vinyl-terminated polysiloxane was prepared as in example 1.
(3) Preparation of anti-reflection material
2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF which account for 1% of the total acrylic monomer are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Fig. 3 shows the transmittance and haze curves of the antireflection film at different silica mass fractions, and it can be seen that the transmittance of the antireflection film in this experiment is 94.5% and the haze is 1.42%.
Fig. 4 shows contact angles of antireflection films with different silica mass fractions, c is the contact angle of the antireflection film in this experiment, and is 93 °.
Example 3:
(1) The preparation method of the functionalized nano-silica is the same as in example 1.
(2) The vinyl-terminated polysiloxane was prepared as in example 1.
(3) Preparation of an anti-reflection material:
2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF which account for 1.5 percent of the total acrylic monomer modified nano SiO are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Fig. 3 shows the transmittance and haze curves of the anti-reflection film at different mass fractions, and it can be seen that the transmittance of the anti-reflection film in this experiment is 93.5% and the haze is 3.57%.
Fig. 4 shows contact angles of antireflection films with different silica mass fractions, and d is the contact angle of the antireflection film in this experiment, which is 98 °.
Example 4:
(1) The preparation method of the functionalized nano-silica is the same as in example 1.
(2) The vinyl-terminated polysiloxane was prepared as in example 1.
(3) Preparation of anti-reflection material
2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF which account for 2 percent of the total acrylic monomer modified nano SiO are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Fig. 3 shows the transmittance and haze curves of the antireflection film at different mass fractions, and it can be seen that the transmittance of the antireflection film in this experiment is 92.8% and the haze is 8.18%.
Fig. 4 shows contact angles of antireflection films with different silica mass fractions, e is the contact angle of the antireflection film in this experiment, and is 100 °.
Example 5:
(1) The preparation method of the functionalized nano-silica is the same as in example 1.
(2) The vinyl-terminated polysiloxane was prepared as in example 1.
(3) Preparation of anti-reflection material
2.3g MMA, 3.25g HEMA, 2.3g V-PDMS and 15g DMF which account for 3 percent of the total acrylic monomer modified nano SiO are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Fig. 3 shows the transmittance and haze curves of the antireflection film at different mass fractions, and it can be seen that the transmittance of the antireflection film in this experiment is 92.7% and the haze is 8.83%.
Fig. 4 shows contact angles of the antireflection film at different silica mass fractions, and f is the contact angle of the antireflection film in this experiment, which is 105 °.
Comparative example 1
(1) Preparation of anti-reflection material
2.3g of MMA, 3.25g of HEMA and 15g of DMF are added into a 100ml three-necked flask equipped with a condenser, AIBN is taken as an initiator, and the reaction is completed after the reaction is carried out for 6 hours at 70 ℃ in a nitrogen atmosphere. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Comparative example 1 is mainly different from example 1 in that: no nanosilica and vinyl terminated polysiloxane were added. The transmittance was 92.8% and the haze was 5.38% as determined by the transmittance/haze test; the contact angle was 60 ° as measured by the contact angle test.
In comparative example 1, the effect of increasing the transparency after coating without the copolymer coating of nanosilica and vinyl-terminated polysiloxane was inferior to that of the antireflection film in example 1, and the contact angle in comparative example 1 was low and the hydrophobicity was poor.
Comparative example 2
(1) The vinyl-terminated polysiloxane was prepared as in example 1.
(2) Preparation of anti-reflection material
In a 100ml three-necked flask equipped with a condenser, 2.3g of MMA, 3.25g of HEMA, 2.3. 2.3g V-PDMS and 15g of DMF were charged, and the reaction was completed after heat-preserving reaction at 70℃for 6 hours in a nitrogen atmosphere with AIBN as an initiator. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Comparative example 2 is mainly different from example 1 in that: no nanosilica was added. The transmittance was 93.8% and the haze was 4.37% as determined by the transmittance/haze test; the contact angle was 98 ° as measured by the contact angle test.
In comparative example 1, the effect of increasing the transmittance after the copolymer coating without nano silica was coated was inferior to that of the antireflection film in example 1, and at the same time, as is clear from the above-mentioned example data, the amount of nano silica introduced was increased, and the transmittance of the antireflection film showed a tendency of increasing first and then decreasing.
Comparative example 3
(1) The preparation method of the functionalized nano-silica is the same as in example 1.
(2) Preparation of an anti-reflection material:
2.3g MMA, 3.25g HEMA, 15g DMF and nano SiO which is 1 percent of the total acrylic monomer after modification are added into a 100ml three-neck flask with a condenser tube 2 And (3) carrying out heat preservation reaction for 6 hours at 70 ℃ in a nitrogen atmosphere by taking AIBN as an initiator to finish the reaction. Cutting the PET film into small square pieces with the length of 4 multiplied by 4cm, coating the diluted anti-reflection material on the surface of the PET film according to the requirement of a dipping and pulling method, and putting the PET film into a 60 ℃ oven for heat treatment for 0.5h to be solidified into a film to obtain the anti-reflection coating.
Comparative example 3 is mainly different from example 1 in that: no vinyl-terminated polysiloxane was added. The transmittance was 92.1% and the haze was 6.42% as determined by the transmittance/haze test; the contact angle was 78 ° as measured by the contact angle test. As shown in FIG. 5, a is the E.coli adhesion without the vinyl-terminated polysiloxane added, and b is the E.coli adhesion of example 2, it can be seen that the addition of the vinyl-terminated polysiloxane can reduce the bacterial adhesion much less than the pure PET bacterial adhesion.
In comparative example 1, the effect of increasing the transparency of the copolymer coating without the vinyl-terminated polysiloxane after coating was inferior to that of the antireflection film of example 1, and at the same time, as is clear from the above-mentioned example data, the introduction of the vinyl-terminated polysiloxane can not only increase the transmittance of the antireflection coating, but also increase the contact angle and hydrophobicity thereof.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme and the concept of the present invention, and should be covered by the scope of the present invention.
Claims (9)
1. A preparation method of a hydrophobic anti-reflection material for resisting bacterial adhesion is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of functionalized nano-silica: dropwise adding tetraethoxysilane into a mixed solution of ethanol, distilled water and ammonia water, vigorously stirring until the system is light blue to obtain nano silica gel, and adding a silane coupling agent for functional modification, wherein the particle size of the silica is 100+/-20 nm;
(2) Preparation of vinyl-terminated polysiloxane (V-PDMS): by octamethyltetrasiloxane (D) in the presence of the catalyst trifluoromethanesulfonic acid 4 ) And a ring-opening reaction of 1, 3-divinyl-1, 3-tetramethyldisiloxane (DVMS) to synthesize a vinyl terminated polysiloxane;
(3) Preparation of an anti-reflection material: uniformly mixing the functionalized nano silicon dioxide prepared in the step (1) with vinyl-terminated polysiloxane prepared in the step (2), methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA) in a solvent N, N-Dimethylformamide (DMF), and carrying out free radical polymerization reaction by taking AIBN as an initiator to obtain the antibacterial adhesion-resistant hydrophobic anti-reflection material;
the specific preparation steps of the functionalized nano silicon dioxide in the step (1) are as follows:
adding distilled water, absolute ethyl alcohol and ammonia water in turn into a reaction vessel, stirring uniformly, adding tetraethoxysilane, stirring at room temperature for reaction to obtain nano SiO 2 Colloid solution, methyl trimethoxy silane (MTMS) is added into the colloid solution, stirring reaction is continued at room temperature, and gamma-methacryloxy trimethoxy silane (KH-570) is added into a reaction bottle to obtain functionalized SiO 2 Colloidal solution.
2. The method for preparing the antibacterial adhesive hydrophobic anti-reflection material according to claim 1, wherein: step (1)Functionalized nano silicon dioxide (SiO) 2 ) Nano SiO in the preparation step of (2) 2 The preparation reaction time of the colloidal solution is 24 h;
and/or the silane coupling agent modified nano silicon dioxide is carried out by a two-step method, and after methyl trimethoxy silane (MTMS) is added for reaction 24h, gamma-methacryloxy trimethoxy silane (KH-570) is added for further reaction 24h.
3. The method for preparing the antibacterial adhesive hydrophobic anti-reflection material according to claim 1, wherein: the specific preparation steps of the vinyl-terminated polysiloxane (V-PDMS) in the step (2) are as follows:
octamethyl cyclotetrasiloxane (D) 4 ) Adding 1, 3-divinyl-1, 3-tetramethyl Disiloxane (DVMS) into a reaction bottle, uniformly stirring, adding a catalyst trifluoromethyl sulfonic acid, and continuously stirring for reaction to obtain a product.
4. A method of preparing an antibacterial adherent hydrophobic antireflective material according to claim 3, wherein: step (2) preparation of vinyl-terminated polysiloxane (V-PDMS): the reaction temperature was 70 ℃ and the reaction time was 6 h.
5. The method for preparing the antibacterial adhesive hydrophobic anti-reflection material according to claim 1, wherein: the preparation method of the anti-reflection material in the step (3) comprises the following steps: n, N-Dimethylformamide (DMF) and a molar ratio of 1 were added to a three-necked flask equipped with a condenser: 1 Methyl Methacrylate (MMA) and hydroxyethyl methacrylate (HEMA), adding functional nano silicon dioxide and vinyl end-capped polysiloxane after uniformly mixing, and stirring and reacting in a nitrogen atmosphere by taking AIBN as an initiator to obtain the product.
6. The method for preparing the antibacterial adhesive hydrophobic anti-reflection material according to claim 5, wherein: in the specific preparation steps of the anti-reflection material in the step (3): the reaction temperature was 70 ℃ and the reaction time was 6 h.
7. An antibacterial-adherent hydrophobic anti-reflection material produced by the method for producing an antibacterial-adherent hydrophobic anti-reflection material according to any one of claims 1 to 6.
8. Use of an antibacterial adherent hydrophobic antireflective material according to claim 7, wherein: an antireflective coating for forming an optical plastic product.
9. Use of an antibacterial adherent hydrophobic antireflective material according to claim 8, wherein: the optical plastic product is any one of polycarbonate, polymethyl methacrylate and PET.
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| CN103102503A (en) * | 2012-04-23 | 2013-05-15 | 常州大学 | Preparation method of optical anti-reflection polyester films |
| CN109666111A (en) * | 2018-12-27 | 2019-04-23 | 浙江东进新材料有限公司 | A kind of Nano-meter SiO_22/ organosilicon-modified acrylate emulsion |
| CN109762289A (en) * | 2019-01-21 | 2019-05-17 | 杨鼎杰 | A kind of heat-insulated polypropylene plastics and preparation method thereof |
| CN112280043A (en) * | 2020-10-30 | 2021-01-29 | 三棵树(上海)新材料研究有限公司 | Silicon dioxide/polyacrylate/polysiloxane composite emulsion, preparation method and application thereof |
| CN112940203A (en) * | 2021-04-01 | 2021-06-11 | 惠州市安品新材料有限公司 | Organosilicon modified acrylic acid secondary dispersion and preparation method thereof |
| CN113817382A (en) * | 2021-09-16 | 2021-12-21 | 常州大学 | Anti-reflection coating for enhancing thermal stability of film and preparation method and application thereof |
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