CN101250278B - Method for preparing modified polymethyl methyl acrylate material and the material - Google Patents
Method for preparing modified polymethyl methyl acrylate material and the material Download PDFInfo
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- CN101250278B CN101250278B CN2007101864330A CN200710186433A CN101250278B CN 101250278 B CN101250278 B CN 101250278B CN 2007101864330 A CN2007101864330 A CN 2007101864330A CN 200710186433 A CN200710186433 A CN 200710186433A CN 101250278 B CN101250278 B CN 101250278B
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- titanium dioxide
- methyl acrylate
- tio
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- pmma
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Abstract
The invention relates to a preparation process of modified polymethyl methyl acrylate material, which comprises firstly washing PMMA in NaOH and acetone solution in turn for 2-3 times through an ultrasonic cleaner, removing grease and dirt on the surface, drying with a vacuum drying box for backup, and then directly depositing titanium dioxide precursor solution on the surface of polymethyl methyl acrylate material through the bionic film-forming technology. The technology aims to prepare self-cleaning polymethyl methyl acrylate material which has anti-aging, wear resistance surface and anti-fog and sterilization through combining with the characteristics of polymethyl methyl acrylate and titanium dioxide, and utilizing the titanium dioxide characteristics of wear resistance, absorbing ultraviolet light, and sterilization and antibiosis and dirt-preventing and self-cleaning on the surface under the irradiation of lights, thereby expanding application ranges.
Description
This invention patent application is on 04 14th, 2006 applying date, application number 200610018801.6, title: the dividing an application of polymethyl methacrylate materials of modification and preparation method thereof.
Technical field
The present invention relates to polymethylmethacrylate (PMMA) material of a kind of modification and preparation method thereof, specifically by at PMMA surface-coated layer of titanium dioxide nano thin-film to improve some performance, expand the technology of its Application Areas.
Background technology
Polymethylmethacrylate (PMMA) is very important a kind of in the transparent polymer material, is commonly called as synthetic glass.It has a lot of good performances, good as chemical stability, physical and mechanical properties is balanced, processing characteristics, weathering resistance, electrical insulating property are good, excellent in optical properties, transmittance is higher more than 10% than common unorganic glass, and light weight is tough or the like, so it is widely used in many fields such as aviation, building, vehicular traffic, health care, optical element.As at building field, synthetic glass is rather well received building and ornament materials, be widely used in buildings layer top, compartment, back, door, top ceiling, pendent lamp, lamp box billboard etc., the sanitary ware made from its moulding such as bathtub just more and more are subjected to liking of people.Yet the use temperature of PMMA low (65 ℃), poor heat resistance (heat decomposition temperature≤200 ℃), surface hardness is little, in use be subject to the influence of sunlight middle-ultraviolet lamp and drawbacks limit such as aging its range of application.For this reason, people are carrying out various trials to improve some performance always, expand its Application Areas.
Titanium dioxide (TiO
2) be a kind of have high refractive index, high transmission rate, very wear-resisting and extraordinary again material of chemical stability, so it has been widely used in fields such as optical coating, microelectronic device, solar cell and supercoat.Utilize TiO
2Visible light permeability and ultraviolet shielded characteristic, can use it for coating, strengthen that it is protected look, protects light, characteristic such as anti-aging; In addition, TiO
2Under ultraviolet light irradiation, can decomposing organic matter and reduction water and TiO
2Contact angle between the surface, thereby it has sterilization, deodorizing, automatically cleaning and function such as antifog.
Summary of the invention
The object of the invention is exactly in conjunction with synthetic glass PMMA and photocatalyst TiO
2Characteristics, apply one deck TiO at the PMMA material surface
2Based nano film utilizes TiO
2Wear resistance, absorb UV-light and have under illumination that sterilization is antibiotic, the self-cleaning characteristics of surface soiling, prepare anti-aging, surface abrasion resistance, antifog germ-resistant automatically cleaning PMMA material, thus the range of application of expansion PMMA material.
Technical scheme of the present invention is as follows:
(1) polymethyl methacrylate materials of modification: on the surface of polymethyl methacrylate materials, be coated with the titanium dioxide base nano thin film layer.
(2) preparation method of the polymethyl methacrylate materials of modification is characterised in that, comprises following preparation process:
(1) preparation TiO 2 sol;
(2) adopt and to lift or flood or spray or other technology is dried after TiO 2 sol being coated in the surface of polymethyl methacrylate materials;
(3) with plasma technique the TiO 2 sol film that is coated in the polymethyl methacrylate materials surface is carried out surperficial aftertreatment and obtains transparent titanium dioxide base nano film.
(3) the another kind of preparation method of the polymethyl methacrylate materials of modification is characterised in that: the preparation of described titanium dioxide base nano film is to adopt bionical film technique directly the titanium dioxide precursor solution to be deposited on the surface of polymethyl methacrylate materials, be deposit fluid promptly with titanium isopropoxide solution or other organic titanium alkoxide solution, with polyvinyl alcohol, or polyoxyethylene glycol, or other water-soluble, film-forming thing conduct and the interactional bionical organic interface of mineral ion, be lower than under 90 ℃ the temperature, with the pH value is 1～5, and the titanium isopropoxide solution or other organic titanium alkoxide that contain 2～8wt%, and the polyvinyl alcohol of 0.5～5w%, or polyoxyethylene glycol, or the ethanolic soln of other water-soluble, film-forming thing, directly by lifting, or dipping, the spraying or other method prepare the titanium dioxide active membrane at material surface.
Effect of the present invention and superiority are: the TiO of (1) wear-resisting UV resistant
2Film has improved PMMA material surface hardness and wear resistance behind the plated film, form the wear-resistant coating of high-clarity, UV resistant; (2) TiO
2Film has good hydrophilic weather resistance and easily and biocompatible, and the PMMA material is had by natural light carry out automatically cleaning, antifog characteristics; (3) TiO under the illumination
2The photocatalytic oxidation properties that film has, the natural light that makes PMMA material use behind the plated film absorb has the performance of antibiotic and sterilizing.
Embodiment
The concrete technical scheme that the present invention adopts is as follows:
One. the preparation of TiO 2 sol and chemically modified thereof
(1) preparation of TiO 2 sol: under the condition of acid pH＜5,, obtain the colloidal sol of homogeneous transparent, regulate pH value to 2～5 of colloidal sol afterwards by dialysis, TiO in the colloidal sol with the alkoxide of titanium (for example titanium isopropylate or tetrabutyl titanate or other) hydrolysis
2Solids content be 0.1～5.0wt% (percent weight in volume).
Two. the pre-treatment on polymethyl methacrylate materials surface
The pre-treatment on polymethyl methacrylate materials surface has two kinds of methods:
(1) sulfonation method: the vitriol oil and distilled water mixed postcooling in 5: 1 by volume～1: 1, and polymethyl methacrylate materials is immersed in 1s～10s in this solution, took out rapidly then, cleaned surperficial debris with distilled water, and dry back is standby.
(2) Cement Composite Treated by Plasma: polymethyl methacrylate materials is put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio-frequency plasma, radio frequency power are 20～80W, and vacuum tightness is 20～60Pa, through O
2Cement Composite Treated by Plasma 0.5～3min is standby.
Three. prepare titanium dioxide base nano film (comprising two kinds of preparation methods) at the PMMA material surface
Method one: the PMMA material of surface preparation is immersed in the TiO 2 sol, then lift the PMMA material, be seated in the radio-frequency (RF) plasma generator after afterwards it being dried, use O with certain speed
2(O
2Purity be 99.999%) radio-frequency plasma carries out surperficial aftertreatment, radio frequency power is 20～80W, vacuum tightness is 20～60Pa, treatment time is that 5～120min is (in this process, by the plasma oxidation effect, and utilize the energy of its generation or localized hyperthermia can obtain suitable titanium dioxide crystal phase structure); After Cement Composite Treated by Plasma finishes, sample is soaked 24～72h with deionized water, then at 80 ℃ or be lower than 80 ℃ of oven dry 2～48 hours down, drying time and bake out temperature are inversely proportional to.Also can adopt dipping or spraying or other technology at the PMMA surface coating, the PMMA material behind the plated film utilizes plasma technique to carry out surperficial aftertreatment equally.
Method two: adopt bionical film technique directly the titanium dioxide precursor solution to be deposited on the surface of polymethyl methacrylate materials, be deposit fluid promptly with titanium isopropoxide solution or other organic titanium alkoxide solution, with polyvinyl alcohol (PVA), or polyoxyethylene glycol, or other water-soluble, film-forming thing conduct and the interactional bionical organic interface of mineral ion, be lower than under 90 ℃ the temperature, with the pH value is 1～5, and the titanium isopropoxide solution or other organic titanium alkoxide that contain 2～8wt% (percent weight in volume), and the polyvinyl alcohol of 0.5～5w% (weight percent), or polyoxyethylene glycol, or the ethanolic soln of other water-soluble, film-forming thing, directly by lifting, or dipping, the spraying or other method prepare the titanium dioxide active membrane at material surface.
The invention will be further described below in conjunction with embodiment.
Embodiment 1: the preparation of TiO 2 sol
Be made into homogeneous solution in the deionized water with 150 milliliters of 1.1 milliliters of concentrated nitric acids (68%) addings, under violent stirring 12.5 milliliters of titanium isopropylates are slowly splashed in the acidic aqueous solution, the suspension that contains white precipitate that hydrolysis obtains continues to stir the colloidal sol that forms homogeneous transparent until the white precipitate dissolving down at 40 ℃.Colloidal sol packed into carry out dialysis with 2 liters of deionized waters in the dialyzer bag and handle, changing water to a dialysis water final pH value every 12 hours is 3.0.Colloidal sol is taken out from dialysis bag, make the TiO 2 sol that concentration is about 2.5% (percent weight in volume).
Embodiment 2:PMMA material surface TiO
2The preparation of based nano film
Earlier the PMMA material is carried out pre-treatment by sulfonation method, promptly earlier the vitriol oil and distilled water were mixed postcooling in 2: 1 by volume, then PMMA is immersed in 2s in this solution, take out then, with the debris on the clean surface of distilled water, drying.
Above-mentioned pretreated PMMA is put into a silk screen, silk screen is put into the TiO that embodiment 1 makes
2In the colloidal sol, lift out, after drying it is seated in the radio-frequency (RF) plasma generator, use O with the speed of 1cm/min
2(O
2Purity be 99.999%) radio-frequency plasma carries out surperficial aftertreatment, radio frequency power is 60W, vacuum tightness is 25Pa, the treatment time is 20min.After Cement Composite Treated by Plasma finishes, sample is soaked 36h with deionized water,, make and be coated with TiO then at 80 ℃ or be lower than 80 ℃ of down oven dry 4h
2The synthetic glass PMMA of photocatalyst film.
According to the preparation process of the foregoing description 1 and embodiment 2, adopt different condition can obtain several groups and be coated with TiO
2The sample of film is shown in Table 1.
Table 1: several groups of samples (adopting sulfonation method that the PMMA material surface is carried out pre-treatment) that adopt the different condition preparation
Changing pretreatment process, be about to polymethyl methacrylate materials and put into radio-frequency (RF) plasma generator, is 99.999% O with purity
2Radio-frequency plasma, radio frequency power are 20～80W, and vacuum tightness is 20～60Pa, and be standby behind processing 0.5～3min, adopts different condition can obtain other several groups and be coated with TiO
2The sample of film is shown in Table 2.
Table 2: several groups of samples (the using plasma technology is carried out pre-treatment to the PMMA material surface) that adopt the different condition preparation
Embodiment 3: the antibiotic and sterilizing test
12 groups of prints that will make by embodiment 2 and do not apply TiO
2The blank PMMA print surface of film with high-pressure steam sterilization after, apply the colon bacillus of certain dilution, indoor placement 16 hours, then get bacterium and cultivate, carry out enumeration by 4.2 method among the GB4789.2-84 after 48 hours by GB4789.2-84 " microbiological test of food hygiene total number of bacterial colony mensuration " 4.1.6 bar method.To three groups of number calculating mean values of sample and blank sample bacterium number, the data representation mode is pressed the method for 4.3.3 bar among the GB4789.2-84 and is carried out respectively.Wash bacterium colony and cultivate, count, calculate the sterilizing rate of sample.Calculation formula is as follows:
Sample sterilizing rate (%)=(N-S)/N * 100
In the formula: blank group bacterial concentration after the N-illumination, individual/dm
2
Sample sets bacterial concentration after the S-illumination, individual/dm
2
The results are shown in Table shown in 3 of above-mentioned print.
Table 3 print is killed the result of escherichia coli performance
Embodiment 4: wetting ability test and the test of anti-mist
Wetting ability can draw by the height of more static hydrolysis contact angle.For this reason, print that embodiment 2 is made and uncoated TiO
2The blank PMMA print of film is through UVA (predominant wavelength 365nm, intensity of illumination 0.5mW/cm
2) activation is after 5 minutes, goes up at OCA20 type contact angle instrument (German Dataphysics InstrumentsGmbh-data physical apparatus company) and adopts sessile drop method to measure the contact angle of film surface to water, the volume of water droplet is 5 μ L.The several contact angles of METHOD FOR CONTINUOUS DETERMINATION are averaged then during experiment, and measuring error is ± 2 °.The result is:
Be not coated with TiO
2The PMMA group of film: 15.8 ± 2 °;
Be coated with TiO
2The PMMA of film group: contact angle is little can't be measured to instrument.
When further blow in two prints surfaces after process illumination, be coated with TiO
2The print surface of film can not form mist, and is not coated with TiO
2The blank PMMA print surface of film forms one deck mist, and opaque.
The The above results explanation, behind the PMMA print surface coating, its wetting ability is improved, and has anti-mist effect.
Embodiment 5: wearability test
Print and uncoated TiO that embodiment 2 is made
2The blank PMMA print of film carries out the test of wear resisting property by standard GB 1768-79 " Determination of Abrasion Resistance for Coating Film ".This testing method is checked rete adhesion strength and the wear-resistant ability of rete simultaneously with the loading friction mode.Test result shows, applies TiO
212 groups of PMMA material sample surfaces of film are behind loading 750 grams, rotation 750 circles, and the abrasion loss on surface is 0.002 gram～0.005 gram.Uncoated TiO in contrast
2The abrasion loss on the blank PMMA print surface of film is 0.10 gram.This explanation ordinary PMMA coated materials TiO
2Behind the film, its wear resistance is improved.
Embodiment 6:PMMA surface TiO
2Bionical one-tenth membrane prepare and performance test thereof
Earlier PMMA is cleaned 2 times～3 times through ultrasonic cleaner in NaOH and acetone soln successively, remove the grease and the dirt on surface, use the vacuum drying oven dry for standby.Add the 3g titanium isopropylate in the 100ml ethanolic soln, 10mL 3～7% polyvinyl alcohol (PVA) aqueous solution drips the dense HNO of 0.1mL
3, in water-bath, be heated to 80 ℃ in the stirring, keep 4h.Then above-mentioned clean PMMA material speed with 1cm/min in this solution is lifted, make TiO after drying
2Active membrane.
Change titanium isopropylate concentration, pH value, or replace polyvinyl alcohol, make other film forming precursor solution, thereby make other TiO on the PMMA surface with Macrogol 2000
2Anti-produced film.Totally 4 groups in sample is numbered 13～16.
With above-mentioned sample respectively by the method for embodiment 3, embodiment 4 and embodiment 5 sterilize, wetting ability (water droplet contact angle) and wearability test, and contrast with blank sample.Above-mentioned preparation condition and the performance of respectively organizing sample relatively is shown in Table 4.
Table 4: utilize anti-polymethyl methacrylate materials and the performance thereof that embrane method prepares that generate under different condition
| Test group | The pH value of solution value | Titanium isopropylate content (wt%) | Film forming matter and content thereof (wt%) | Treatment temp (℃) | Sterilization rate (%) | The water droplet contact angle (°) | Abrasion loss (g) |
| 13 | 1 | 2.0 | Polyvinyl alcohol 5.0 | 60 | 95 | 2.0 | 0.002 |
| 14 | 3 | 8.0 | Polyvinyl alcohol 2.0 | 20 | 93 | 3.0 | 0.003 |
| 15 | 3 | 4.5 | Polyoxyethylene glycol 0.5 | 80 | 96 | 1.0 | 0.004 |
| 16 | 5 | 3.0 | Polyoxyethylene glycol 2.0 | 60 | 94 | 0 | 0.004 |
Claims (1)
1. the preparation method of the polymethyl methacrylate materials of a modification, it is characterized in that: on the surface of polymethyl methacrylate materials, be coated with the titanium dioxide base nano thin film layer, the preparation of described titanium dioxide base nano thin film layer is to adopt bionical film technique directly the titanium dioxide precursor solution to be deposited on the surface of polymethyl methacrylate materials, be deposit fluid promptly with titanium isopropoxide solution or other organic titanium alkoxide solution, with polyvinyl alcohol, or polyoxyethylene glycol, or other water-soluble, film-forming thing conduct and the interactional bionical organic interface of mineral ion, in the 100ml ethanolic soln, add the 3g titanium isopropylate, 10mL 3～7% polyvinyl alcohol water solutions drip the dense HNO of 0.1mL
3, in water-bath, be heated to 80 ℃ in the stirring, keep 4h, then above-mentioned PMMA material speed with 1cm/min in this solution is lifted, make TiO after drying
2Active membrane.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101864330A CN101250278B (en) | 2006-04-14 | 2006-04-14 | Method for preparing modified polymethyl methyl acrylate material and the material |
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|---|---|---|---|
| CN2007101864330A CN101250278B (en) | 2006-04-14 | 2006-04-14 | Method for preparing modified polymethyl methyl acrylate material and the material |
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|---|---|---|---|
| CN200610018801A Division CN1837270B (en) | 2006-04-14 | 2006-04-14 | Modified polymethyl methacrylate materials and process for preparing same |
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| CN101250278B true CN101250278B (en) | 2010-08-11 |
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| CN101672091B (en) * | 2008-09-09 | 2011-06-15 | 阿波罗（中国）有限公司 | Nano-titanium dioxide modified composite board |
| CN106847516B (en) * | 2017-03-17 | 2018-10-26 | 宁波高新区远创科技有限公司 | A kind of preparation method of dye-sensitized solar cell anode material |
| CN108864463B (en) * | 2017-05-09 | 2021-01-12 | 中国科学院上海硅酸盐研究所 | Self-supporting flexible super-hydrophilic titanium oxide film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224036A (en) * | 1998-10-30 | 1999-07-28 | 中国科学院感光化学研究所 | Titanium sol-gel paint adding nm inorganic compound particles, method for preparing same and use thereof |
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1224036A (en) * | 1998-10-30 | 1999-07-28 | 中国科学院感光化学研究所 | Titanium sol-gel paint adding nm inorganic compound particles, method for preparing same and use thereof |
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
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