CN116496653A - Preparation method of ultraviolet absorbent grafted nano silicon dioxide antifogging liquid - Google Patents

Preparation method of ultraviolet absorbent grafted nano silicon dioxide antifogging liquid Download PDF

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Publication number
CN116496653A
CN116496653A CN202310455389.8A CN202310455389A CN116496653A CN 116496653 A CN116496653 A CN 116496653A CN 202310455389 A CN202310455389 A CN 202310455389A CN 116496653 A CN116496653 A CN 116496653A
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Prior art keywords
silicon dioxide
nano silicon
ultraviolet absorbent
ultraviolet
grafted
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Pending
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CN202310455389.8A
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Chinese (zh)
Inventor
薛涵与
徐忠生
刘新香
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Xiamen Yaoming Technology Co ltd
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Xiamen Yaoming Technology Co ltd
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Priority to CN202310455389.8A priority Critical patent/CN116496653A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/18Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/25Greenhouse technology, e.g. cooling systems therefor

Abstract

The invention provides a preparation method of an ultraviolet absorbent grafted nano silicon dioxide antifogging liquid, and relates to outdoor protection of ultraviolet aging-resistant materials such as color films. The preparation method of the antifogging liquid comprises the following steps: firstly, modifying nano silicon dioxide by using a silane coupling agent in a ball mill; then the dried modified nano silicon dioxide and an ultraviolet absorbent are mixed according to the mass ratio of 1-3: 10, adding 1% of Lewis acid, and grafting an ultraviolet absorbent on the nano silicon dioxide in a ball mill; and finally, matching the ultraviolet absorbent grafted nano silicon dioxide with methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate and a defoaming agent according to a certain mass ratio to obtain the ultraviolet absorbent grafted nano silicon dioxide antifogging liquid. By introducing an ultraviolet absorber, the anti-fog liquid is endowed with ultraviolet resistance, the contact angle of the anti-fog liquid with water is smaller than 25.0 degrees, the contact angle of the anti-fog liquid with diiodomethane is smaller than 35.0 degrees, and the anti-fog ultraviolet resistance is excellent.

Description

Preparation method of ultraviolet absorbent grafted nano silicon dioxide antifogging liquid
Technical Field
The invention relates to the technical field of anti-ultraviolet aging of anti-fog spray, in particular to a preparation method of an anti-fog liquid containing ultraviolet absorbent grafted nano silicon dioxide.
Background
With the development of technology and the improvement of living standard of people, more and more materials are required to be endowed with functionalization. The anti-fog and anti-ultraviolet functionalization of the material are one of important requirements of human beings. The internal antifogging agent and the ultraviolet absorber are added into the material during the material proportioning, and are characterized by difficult loss and lasting efficacy, but high requirements on the material. For example, it is difficult to obtain good antifogging properties for materials having high crystallinity (e.g., polystyrene).
Different from the internal addition type auxiliary agent, the antifogging/anti-ultraviolet spray is used as an external spray, has the advantages of convenient use, no limitation of the shape of an object and the like, and can be widely applied to various fields of construction, automobiles and the like on the surfaces of various materials such as plastics, rubber, fibers and the like. The anti-fog spray product has low cost, but has poor durability, is easy to wash off or wipe off, has single function, cannot have multiple effects of ultraviolet resistance and the like, and limits the application field.
Disclosure of Invention
(one) solving the technical problems
The invention aims to provide a preparation method of an anti-fog liquid containing ultraviolet absorbent grafted nano silicon dioxide, aiming at the functional deficiency of the existing anti-fog spray product. The modified antifogging agent has an ultraviolet-proof effect compared with the commercially available nanometer antifogging agent, and the antifogging performance is improved.
(II) technical scheme
In order to achieve the above purpose, the invention is realized by the following technical scheme: the nanometer silicon dioxide has high reflectivity to ultraviolet rays with the wavelength of 490nm or less, and can achieve the purposes of long-acting ultraviolet aging resistance and heat aging resistance when being added into the antifogging liquid; the ultraviolet absorber is grafted on the surface of the nano silicon dioxide, so that the ultraviolet resistance mechanism is further enhanced. Specifically, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and nano silicon dioxide are mixed according to the mass ratio of 1:10, mixing, adding deionized water accounting for 20% of the total mass of the two, and carrying out silane coupling agent modified nano silicon dioxide in a ball mill; then the dried silane coupling agent modified nano silicon dioxide and ultraviolet absorbent are mixed according to the mass ratio of 1-3: 10, adding 1% of Lewis acid, and grafting an ultraviolet absorbent onto the nano silicon dioxide in a ball mill (the time is 60 min) according to an epoxy ring opening mechanism to obtain the ultraviolet absorbent grafted nano silicon dioxide; finally, the nanometer silicon dioxide grafted by the ultraviolet absorbent is matched with methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate and defoamer according to a certain mass ratio, and the nanometer silicon dioxide antifogging liquid grafted by the ultraviolet absorbent is prepared by high-speed stirring. The antifogging liquid contains an ultraviolet absorbent, has a contact angle with water of less than 25.0 degrees and a contact angle with diiodomethane of less than 35.0 degrees, and has excellent antifogging and ultraviolet resistance. Can be used for outdoor protection of polyvinyl chloride (PVC) color films and the like.
Preferably, the ultraviolet absorber is 2-hydroxy-4-n-octoxybenzophenone.
Preferably, the ultraviolet absorber grafting method is a ball milling grafting method.
Preferably, the nano silicon dioxide is nano silicon dioxide with the particle size of 8-20 nanometers and the surface containing epoxy groups.
Preferably, the other components of the antifogging agent are methyl methacrylate (10% -20%), n-butyl acrylate (15% -20%), butyl methacrylate (15% -20%), isooctyl acrylate (30% -40%), and defoamer (5%).
Working principle: the invention adopts a ball milling grafting method to graft an ultraviolet absorbent on the surface of the nano silicon dioxide modified by the epoxy silane coupling agent. The method utilizes the high temperature generated in the ball milling process to prepare the material with the characteristic of one-step method, does not need post-treatment, and has quick and simple production. Then, the ultraviolet aging resistance and the anti-fog performance of the anti-fog spray are improved by utilizing the nano silicon dioxide grafted by the ultraviolet absorbent. The mechanism is that the ultraviolet absorbent is grafted with nano silicon dioxide to improve the anti-fog performance and the ultraviolet resistance of the anti-fog spray. The mechanism is that the nano silicon dioxide has high reflectivity to ultraviolet rays with the wavelength of 490nm or less, and the long-acting ultraviolet aging resistance and heat aging resistance can be achieved when the nano silicon dioxide is added into the antifogging liquid; the ultraviolet absorber is grafted on the surface of the nano silicon dioxide, so that the ultraviolet resistance mechanism is further enhanced; the grafted ultraviolet absorbent 2-hydroxy-4-n-octoxybenzophenone is a hydrophilic molecule, so that the hydrophilic performance of the antifogging liquid can be further improved, and the antifogging effect is optimized.
The test of the nano silicon dioxide containing the ultraviolet absorbent adopts an infrared visible absorption spectrum and a scanning electron microscope; an antifogging agent test, which adopts a glass substrate, and measures the contact angle with water under the conditions that the temperature is 25 ℃ and the relative humidity is 50+/-5%; the anti-aging test uses PVC color film containing organic pigment (easy to age and change color) as base material, and spray-coating anti-fog spray-coating agent on the surface of base material, at 65deg.C, relative humidity of 50+ -5%, xenon lamp 30W/cm 2 Weather resistance was tested under the conditions.
(III) beneficial effects
The invention provides a preparation method of an ultraviolet absorbent grafted nano silicon dioxide antifogging liquid. The beneficial effects are as follows:
1. the preparation of the grafted nano silicon dioxide containing the ultraviolet absorbent adopts a ball milling grafting method, and the method does not need post-treatment, and has quick and simple production. .
2. After the ultraviolet absorbent grafted nano silicon dioxide is introduced into the antifogging liquid, the contact angle of the antifogging liquid with water is smaller than 25.0 degrees, the contact angle of the antifogging liquid with diiodomethane is smaller than 35.0 degrees, and the antifogging effect is obvious.
3. Xenon lamp aging experiments after spraying PVC color films on the anti-fog liquid, the novel anti-fog liquid has excellent anti-fog and ultraviolet resistance.
Drawings
FIG. 1 is an infrared-visible absorption spectrum of the nanosilica containing the ultraviolet light absorber of the present invention;
FIG. 2 is a surface scanning electron microscope image of a nanosilica anti-fog layer containing an ultraviolet light absorber of the present invention;
FIG. 3 is a contact angle test of an anti-fog liquid containing an ultraviolet absorbent grafted nano-silica of the present invention (a. Example 1 versus water; b. Example 1 versus diiodomethane; c. Example 2 versus water; d. Example 2 versus diiodomethane; e. Example 3 versus water; f. Example 3 versus diiodomethane);
FIG. 4 shows the results of a xenon lamp aging test of a PVC color film sprayed with an ultraviolet absorbent grafted nano-silica anti-fog liquid.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Embodiment one:
the embodiment of the invention provides a preparation method of an ultraviolet absorbent grafted nano silicon dioxide antifogging liquid, which comprises the following steps of (by mass ratio) gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and nano silicon dioxide: 10, adding deionized water accounting for 20 percent of the total mass of the two materials, and carrying out silane coupling agent modified nano silicon dioxide in a ball mill (an infrared spectrum of a product is shown as figure 1, and an aggregation form of the nano silicon dioxide on the surface of a material is shown as figure 2); then the dried silane coupling agent modified nano silicon dioxide and an ultraviolet absorber are mixed according to the mass ratio of 2:10, adding 1% of Lewis acid, and performing grafting reaction in a ball mill to obtain nano silicon dioxide grafted by an ultraviolet absorbent; finally, the ultraviolet absorbent grafted nano silicon dioxide (2%) is matched with methyl methacrylate (18%), n-butyl acrylate (20%), butyl methacrylate (20%), isooctyl acrylate (35%) and defoamer (5%) according to a certain mass ratio, and the ultraviolet absorbent grafted nano silicon dioxide antifogging liquid is prepared by stirring at a high speed. The antifogging liquid contains an ultraviolet absorber, and has a contact angle with water of 25.0 DEG and a contact angle with diiodomethane of 26.3 DEG (FIGS. 3a, b); the xenon lamp aging test of the ultraviolet absorbent grafted nano silicon dioxide anti-fog liquid spray-coated PVC color film shows that after 336 hours, the yellowing index of the PVC base material containing the organic color material is 1.5, and the PVC base material is slightly discolored (shown in figure 4).
Embodiment two:
the present embodiment is different from the first embodiment in that: the dosage of the grafted ultraviolet absorbent and the dosage of the nano silicon dioxide are improved. Specifically, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and nano silicon dioxide are mixed according to the mass ratio of 3:10, mixing, adding deionized water accounting for 20% of the total mass of the two, and carrying out silane coupling agent modified nano silicon dioxide in a ball mill; then the dried silane coupling agent modified nano silicon dioxide and an ultraviolet absorber are mixed according to the mass ratio of 3:10, adding 1% of Lewis acid, and grafting an ultraviolet absorbent onto the nano silicon dioxide in a ball mill (the time is 60 min) according to an epoxy ring opening mechanism to obtain the ultraviolet absorbent grafted nano silicon dioxide; finally, the ultraviolet absorbent grafted nano silicon dioxide (5%) is matched with methyl methacrylate (15%), n-butyl acrylate (20%), butyl methacrylate (20%), isooctyl acrylate (35%) and defoamer (5%) according to a certain mass ratio, and the ultraviolet absorbent grafted nano silicon dioxide antifogging liquid is prepared by stirring at a high speed. The antifogging liquid contains an ultraviolet absorbent, the contact angle of the antifogging liquid with water is smaller than 5.0 degrees, the contact angle of the antifogging liquid with diiodomethane is smaller than 21.1 degrees, and the antifogging performance is improved (shown in figures 3c and d); the xenon lamp aging test of the ultraviolet absorbent grafted nano silicon dioxide anti-fog liquid spray-coated PVC color film shows that after 336 hours, the yellowing index of the PVC base material containing the organic color material is 1.3, and the PVC base material is slightly discolored (shown in figure 4).
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (8)

1. A preparation method of an ultraviolet absorbent grafted nano silicon dioxide antifogging liquid is characterized by comprising the following steps: gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and nano silicon dioxide are mixed according to the mass ratio of 1:10, mixing, adding deionized water accounting for 20% of the total mass of the two, and carrying out silane coupling agent modified nano silicon dioxide in a ball mill; then the dried silane coupling agent modified nano silicon dioxide and ultraviolet absorbent are mixed according to the mass ratio of 1-3: 10, adding 1% of Lewis acid, and grafting an ultraviolet absorbent onto the nano silicon dioxide in a ball mill (the time is 60 min) according to an epoxy ring opening mechanism to obtain the ultraviolet absorbent grafted nano silicon dioxide; finally, the nanometer silicon dioxide grafted by the ultraviolet absorbent is matched with methyl methacrylate, n-butyl acrylate, butyl methacrylate, isooctyl acrylate and defoamer according to a certain mass ratio, and the nanometer silicon dioxide antifogging liquid grafted by the ultraviolet absorbent is prepared by high-speed stirring.
2. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: adopting a ball milling grafting method, and mixing gamma- (2, 3-glycidoxy) propyl trimethoxy silane and nano silicon dioxide according to the mass ratio of 1:10, mixing, adding deionized water accounting for 20% of the total mass of the two, and carrying out silane coupling agent modified nano silicon dioxide in a ball mill; then the dried silane coupling agent modified nano silicon dioxide and ultraviolet absorbent are mixed according to the mass ratio of 1-3: 10, adding 1% of Lewis acid, and grafting the ultraviolet absorbent on the nano silicon dioxide in a ball mill (the time is 60 min) according to an epoxy ring opening mechanism to obtain the ultraviolet absorbent grafted nano silicon dioxide. The ball milling method is fast, simple and convenient, and is suitable for popularization of enterprises.
3. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the ultraviolet absorbent is 2-hydroxy-4-n-octoxybenzophenone.
4. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the other components are methyl methacrylate (10-20%), n-butyl acrylate (15-20%), butyl methacrylate (15-20%), isooctyl acrylate (30-40%) and defoamer (5%).
5. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the nano silicon dioxide is unmodified nano silicon dioxide with the particle size of 8-20 nanometers.
6. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the contact angle with water is smaller than 25.0 degrees, the contact angle with diiodomethane is smaller than 35.0 degrees, and the anti-fog and ultraviolet-resistant performances are excellent.
7. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the ultraviolet absorbent grafted nano silicon dioxide adopts a ball milling grafting method. The method utilizes the high temperature generated in the ball milling process to quickly volatilize the aqueous solution of the ethanol, and the preparation method has the characteristic of one-step method, does not need post treatment, and is quick and simple.
8. The method for preparing the ultraviolet absorbent grafted nano silica antifogging liquid according to claim 1, which is characterized in that: the ultraviolet absorbent is grafted with the nano silicon dioxide to improve the anti-fog performance and the ultraviolet resistance of the anti-fog spray. The mechanism is that the nano silicon dioxide has high reflectivity to ultraviolet rays with the wavelength of 490nm or less, and the long-acting ultraviolet aging resistance and heat aging resistance can be achieved when the nano silicon dioxide is added into the antifogging liquid; the ultraviolet absorber is grafted on the surface of the nano silicon dioxide, so that the ultraviolet resistance mechanism is further enhanced; the grafted ultraviolet absorbent 2-hydroxy-4-n-octoxybenzophenone is a hydrophilic molecule, so that the hydrophilic performance of the antifogging liquid can be further improved, and the antifogging effect is optimized.
CN202310455389.8A 2023-04-25 2023-04-25 Preparation method of ultraviolet absorbent grafted nano silicon dioxide antifogging liquid Pending CN116496653A (en)

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