CN106674568B - It is a kind of with visible light-responded automatically cleaning ABS sheet material and preparation method thereof - Google Patents

It is a kind of with visible light-responded automatically cleaning ABS sheet material and preparation method thereof Download PDF

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CN106674568B
CN106674568B CN201611108824.6A CN201611108824A CN106674568B CN 106674568 B CN106674568 B CN 106674568B CN 201611108824 A CN201611108824 A CN 201611108824A CN 106674568 B CN106674568 B CN 106674568B
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abs
sheet material
automatically cleaning
visible light
abs sheet
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CN106674568A (en
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李赵波
刘星
罗明华
辛敏琦
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Shanghai Kumho Sunny Plastics Co Ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
    • C09D155/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2355/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2323/00 - C08J2353/00
    • C08J2355/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
    • C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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Abstract

The present invention relates to a kind of with visible light-responded automatically cleaning ABS sheet material and preparation method thereof, and automatically cleaning ABS sheet material is formed by ABS substrate and coated in the automatically cleaning film in ABS substrate；Wherein ABS substrate is the ABS sheet material with a thickness of 0.5~2.5cm, and automatically cleaning film is by ABS resin and g-C3N4/TiO2It is prepared.The preparation method comprises the following steps: the predecessor of carbon containing rich nitrogen is obtained g-C in 520~600 DEG C of 4~6h of calcining with the heating rate of 10~20 DEG C/min3N4Powder；Titanium source is added in acetic acid, g-C is added3N4Suspension, the hydro-thermal reaction 12~for 24 hours at 120~180 DEG C, obtains g-C3N4/TiO2；By ABS and g-C3N4/TiO2Polymer mother liquor is made, ABS sheet material is obtained using coating method.The advantages that ABS sheet material provided by the invention has to visible absorption compared with prior art, and photocatalytic activity is high, and automatically cleaning is efficiently quick, can reduce organic pollution, can be applied to the appearances product such as decoration of exterior wall, outdoor equipment.

Description

It is a kind of with visible light-responded automatically cleaning ABS sheet material and preparation method thereof
Technical field
The invention belongs to ABS based composites technical fields, are related to a kind of with visible light-responded automatically cleaning ABS sheet material And preparation method thereof.
Background technique
Acrylonitrile, butadiene and styrene copolymer (ABS) are current production rate maximum, most widely used polymer One of, the comprehensive mechanical property of rigidity, toughness and hardness phase equilibrium is shown in performance；Because it is with good mechanical performance With excellent processing and forming characteristic, it is widely used in the fields such as mechanical fitting, household electrical appliance, electronic device and auto industry.
With the development of economy and society, ABS product and its composite material are in modern economic construction using also increasingly wider It is general, especially on outdoor and ornament materials.But along with the exacerbation of environmental pollution, ABS product in use can be because For a large amount of oily matters deposition and cause the color of material surface and gloss to subside, while contaminated material surface is not due to Easy cleaning, it is difficult to the reason of wiping and eventually lead to and be not available.Therefore exploitation photocatalysis class ABS self-cleaning material is for extension ABS products application range meets automatically cleaning demand, promotes value of the product and is of great significance.
Titanium dioxide (TiO2) with the advantages that its chemical property is stable, photocatalytic activity is high, nontoxic and cheap, become The most widely used photochemical catalyst in photocatalytic degradation of organic matter.Current most of TiO2Photochemical catalyst is in the prevalence of reaction It is inefficient；Solar energy utilization ratio is low (can only to absorb the ultraviolet light of accounting deficiency sun spectral range 5%, and to accounting for the sun 47% visible light utilization efficiency is but very low in energy) the problems such as.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind, and there is visible light to ring Automatically cleaning ABS sheet material answered and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions: a kind of with visible light-responded automatically cleaning ABS Sheet material, which is characterized in that automatically cleaning ABS sheet material is formed by ABS substrate and coated in the automatically cleaning film in ABS substrate；Its Middle ABS substrate is the ABS sheet material with a thickness of 0.5~2.5cm, and automatically cleaning film is by ABS resin and g-C3N4/TiO2It is prepared.
As a preferred technical scheme:
The automatically cleaning ABS sheet material have vis-absorbing and anti-ultraviolet ageing, photocatalytic degradation efficiency be 85~ 90%.
The weight average molecular weight of the ABS resin be 80000~200000Da, butadiene rubber content be 10~ 20wt%, butadiene rubber partial size are 0.2~3 μm.
The g-C3N4/TiO2It is using g-C3N4The method of doping is to TiO2It is modified and is prepared.
The present invention also provides a kind of above-mentioned preparation method with visible light-responded automatically cleaning ABS sheet material, features It is, comprising the following steps:
(1) by the predecessor of carbon containing rich nitrogen with the heating rate of 10~20 DEG C/min in 520~600 DEG C of 4~6h of calcining, to After natural cooling, g-C is obtained3N4Powder；
(2) by g-C3N4It is scattered in methanol, 1~2h of ultrasound obtains g-C3N4Suspension takes titanium source to be added dropwise to acetic acid In, and the g-C after ultrasound is added3N4Suspension, stir 0.5h after, obtained solution at 120~180 DEG C hydro-thermal reaction 12~ For 24 hours, it cleans and collects product after dry and obtain g-C3N4/TiO2；
(3) ABS resin and g-C for being 3~6:1 by mass ratio3N4/TiO2It is added into acetone, 0.5~1h is stirred by ultrasonic, Polymer mother liquor is formed, this polymer mother liquor is coated in ABS substrate using coating method then, is volatilized under room temperature molten Agent obtains the automatically cleaning ABS sheet material for having visible light-responded.
As a preferred technical scheme:
The predecessor of the carbon containing rich nitrogen is cyanamide and/or melamine.
The titanium source is isopropyl titanate or tetrabutyl titanate, g-C3N4Molar ratio with titanium source is 1~3:26.
The volume of the methanol and acetic acid is 1~1.5:6.
The concentration of the polymer mother liquor is 10~20wt%.
The coating method is knifing or spin-coating method, wherein scraping in embrane method knifing speed is 50~250cm/min, in spin-coating method Spin speed is 700~3500rpm.
The present invention uses graphite-phase nitrogen carbide (g-C3N4) carried titanium dioxide method to TiO2It is modified, to improve TiO2Catalytic activity is realized and is absorbed to the multiband of sunlight；By preparing automatically cleaning film and being coated onto ABS substrate Method makes ABS material have excellent self-cleaning property, reduces organic pollution, has a extensive future.
Compared with prior art, the invention has the following beneficial effects:
1) automatically cleaning ABS sheet material provided by the present invention has excellent Photocatalytic Degradation Property under visible light, catalysis It is active high；Photocatalytic degradation efficiency is up to 85~90%；
2) automatically cleaning ABS sheet material provided by the present invention utilizes g-C in automatically cleaning film3N4/TiO2Efficient catalytic degradation greasy dirt Equal organic matters (being detailed in Fig. 2) the problems such as so as to effectively solve traditional ABS sheet material vulnerable to pollution, do not bear dirty, has automatically cleaning Property, the wide of market application prospect
3) present invention utilizes g-C3N4/TiO2/ ABS has preferable absorption in visible light region, compared to TiO2The purple of/ABS Outer absorption region, spectral absorption range obviously increase the multiband absorption (being detailed in Fig. 1), it can be achieved that sunlight, make this hair Have the function of that visible light-responded automatically cleaning ABS sheet material also has ageing-resistant, uvioresistant etc. provided by bright；
4) it is provided by the present invention have visible light-responded automatically cleaning ABS sheet material in sheet body substrate be by upper layer The ABS substrate of automatically cleaning ABS substrate and lower layer, both ABS substrate, so automatically cleaning film is good with ABS substrate compatibility, surely Qualitative height.
Detailed description of the invention
Fig. 1 is the ABS sheet material Ultraviolet visible absorption spectrum figure of different loads；
Fig. 2 is the ABS sheet material solar radiation photocatalytic degradation methyl orange efficiency chart of different loads.
Specific embodiment
Below by specific embodiment, the present invention is further explained, it is necessary to point out that these embodiments are merely to illustrate this It invents and does not limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Some nonessential modifications and adaptations that member makes the present invention still fall within protection scope of the present invention.
Embodiment 1
A kind of preparation method with visible light-responded automatically cleaning ABS sheet material, 5g melamine is placed in crucible and is put Enter Muffle furnace, with the heating rate of 10 DEG C/min in 520 DEG C of calcining 6h, after natural cooling, light yellow g-C obtained by collecting3N4 Powder；Take 0.1 gram of g-C3N4It is scattered in 10mL methanol, ultrasonic 1h is stand-by.9.6g tetrabutyl titanate is taken to be added dropwise to 60mL In acetic acid (HAc), and the g-C after ultrasound is added3N4Suspension transfers the solution into the water heating kettle of 100mL after stirring 0.5h, 18h is reacted at 150 DEG C.Product deionized water and ethyl alcohol are cleaned in the baking oven for be placed in several times 60 DEG C and are done after completion of the reaction Dry 10h collects product and obtains g-C3N4/TiO2Powder；By 27gABS (weight average molecular weight 100000Da, butadiene rubber content 16%, number average bead diameter is 1.4 μm) and 6 grams of g-C3N4/TiO2It is added into 297g acetone, 0.5h is stirred by ultrasonic, form polymer Then this polymer mother liquor is coated in the ABS substrate of 0.5cm thickness by mother liquor using embrane method (knifing speed 250cm/min) is scraped, Solvent flashing is under room temperature to get to visible light-responded automatically cleaning ABS sheet material.
Obtained ABS sheet material is stood on into 50ml 10-5In the methyl orange solution of M, with 500W xenon source simulated solar irradiation, Light source is 15cm at a distance from sample, irradiation time 6h, and the methyl orange solution concentration under test record difference light application time is adopted It is tested with solar radiation photocatalytic degradation methyl orange efficiency of the ultraviolet-uisible spectrophotometer to ABS sheet material.Test result shows The automatically cleaning ABS sheet material of preparation 6h under xenon lamp irradiation, catalytic degradation methyl orange efficiency are 89%.
Embodiment 2
A kind of preparation method with visible light-responded automatically cleaning ABS sheet material, 8g cyanamide is placed in crucible and is put into Muffle furnace, with the heating rate of 15 DEG C/min in 560 DEG C of calcining 5h, after natural cooling, light yellow g-C obtained by collecting3N4Powder End；Take 0.2 gram of g-C3N4It is scattered in 15mL methanol, ultrasonic 1h is stand-by.9.6g isopropyl titanate is taken to be added dropwise to 60mL acetic acid (HAc) in, and the g-C after ultrasound is added3N4Suspension transfers the solution into the water heating kettle of 100mL, In after stirring 0.5h 12h is reacted at 180 DEG C.Product deionized water and ethyl alcohol clean dry in the baking oven for be placed in several times 60 DEG C after completion of the reaction 10h collects product and obtains g-C3N4/TiO2Powder；By 42gABS (weight average molecular weight 150000Da, butadiene rubber content 13%, number average bead diameter is 0.9 μm) and 7 grams of g-C3N4/TiO2It is added into 278g acetone, 1h is stirred by ultrasonic, it is female to form polymer Then this polymer mother liquor is coated in the ABS substrate of 1.5cm thickness, room by liquid using embrane method (knifing speed 50cm/min) is scraped Solvent flashing is under the conditions of temperature to get to visible light-responded automatically cleaning ABS sheet material.
Obtained ABS sheet material is stood on into 50ml 10-5In the methyl orange solution of M, with 500W xenon source simulated solar irradiation, Light source is 15cm at a distance from sample, irradiation time 6h, and the methyl orange solution concentration under test record difference light application time is adopted It is tested with solar radiation photocatalytic degradation methyl orange efficiency of the ultraviolet-uisible spectrophotometer to ABS sheet material.Test result shows Automatically cleaning ABS sheet material obtained 6h under xenon lamp irradiation, catalytic degradation methyl orange efficiency are 85%.
Embodiment 3
A kind of preparation method with visible light-responded automatically cleaning ABS sheet material, 5g cyanamide and 5g melamine are mixed Conjunction object, which is placed in crucible, is put into Muffle furnace, with the heating rate of 20 DEG C/min in 600 DEG C of calcining 4h, after natural cooling, collects Acquired light yellow g-C3N4Powder；Take 0.3 gram of g-C3N4It is scattered in 15mL methanol, ultrasonic 1h is stand-by.Take 9.6g metatitanic acid four different Butyl ester is added dropwise in 60mL acetic acid (HAc), and the g-C after ultrasound is added3N4Suspension shifts solution after stirring 0.5h Into the water heating kettle of 100mL, reacted for 24 hours at 120 DEG C.Product is cleaned several times with deionized water and ethyl alcohol after completion of the reaction, and It is placed in 60 DEG C of baking oven dry 10h, product is collected and obtains g-C3N4/TiO2Powder；By 24gABS (weight average molecular weight 200000Da, butadiene rubber content 10%, number average bead diameter are 3 μm) and 8 grams of g-C3N4/TiO2It is added into 128g acetone, surpasses Sound stirs 1h, forms polymer mother liquor, is then coated in this polymer mother liquor using spin-coating method (spin speed 1000rpm) In the ABS substrate of 2.5cm thickness, solvent flashing is under room temperature to get to visible light-responded automatically cleaning ABS sheet material.
Obtained ABS sheet material is stood on into 50ml 10-5In the methyl orange solution of M, with 500W xenon source simulated solar irradiation, Light source is 15cm at a distance from sample, irradiation time 6h, and the methyl orange solution concentration under test record difference light application time is adopted It is tested with solar radiation photocatalytic degradation methyl orange efficiency of the ultraviolet-uisible spectrophotometer to ABS sheet material.Test result shows Automatically cleaning ABS sheet material obtained 6h under xenon lamp irradiation, catalytic degradation methyl orange efficiency are 90%.
Embodiment 4
A kind of preparation method with visible light-responded automatically cleaning ABS sheet material, 7g cyanamide and 3g melamine are mixed Conjunction object, which is placed in crucible, is put into Muffle furnace, with the heating rate of 18 DEG C/min in 580 DEG C of calcining 4.5h, after natural cooling, receives Light yellow g-C obtained by collecting3N4Powder；Take 0.3 gram of g-C3N4It is scattered in 12mL methanol, ultrasonic 1h is stand-by.Take 9.6g metatitanic acid four Isobutyl ester is added dropwise in 58mL acetic acid (HAc), and the g-C after ultrasound is added3N4After stirring 0.5h, solution is turned for suspension It moves on in the water heating kettle of 100mL, reacts 16h at 160 DEG C.Product deionized water and ethyl alcohol clean several times after completion of the reaction, It is placed in 60 DEG C of baking oven dry 12h, product is collected and obtains g-C3N4/TiO2Powder；By 40gABS (weight average molecular weight 80000Da, butadiene rubber content 20%, number average bead diameter are 0.2 μm) and 8 grams of g-C3N4/TiO2It is added into 352g acetone, surpasses Sound stirs 0.5h, forms polymer mother liquor, is then coated in this polymer mother liquor using spin-coating method (spin speed 3500rpm) In the ABS substrate of 2cm thickness, solvent flashing is under room temperature to get to visible light-responded automatically cleaning ABS sheet material.
Obtained ABS sheet material is stood on into 50ml 10-5In the methyl orange solution of M, with 500W xenon source simulated solar irradiation, Light source is 15cm at a distance from sample, irradiation time 6h, and the methyl orange solution concentration under test record difference light application time is adopted It is tested with solar radiation photocatalytic degradation methyl orange efficiency of the ultraviolet-uisible spectrophotometer to ABS sheet material.Test result shows Automatically cleaning ABS sheet material obtained 6h under xenon lamp irradiation, catalytic degradation methyl orange efficiency are 87%.
Comparative example 1
It is a kind of to load the preparation method for having the ABS sheet material of titanium dioxide, 60ml is added dropwise in 9.6 grams of tetrabutyl titanates In acetic acid, stir evenly, then by this solution at 160 DEG C hydro-thermal reaction 16h.It is clear through deionized water and ethyl alcohol after reaction Product is washed, dry 10h under the conditions of 60 DEG C collects product and obtains TiO2Powder；By 27gABS and 6 gram of TiO2It is added to 297g acetone In, 0.5h is stirred by ultrasonic, forms polymer mother liquor, then this polymer mother liquor is used and scrapes embrane method (knifing speed 100cm/ Min) in the ABS substrate coated in 0.5cm thickness, solvent flashing is under room temperature to get the ABS piece for having titanium dioxide to load Material.
Obtained ABS sheet material ultraviolet-visible absorption is tested using ultraviolet-uisible spectrophotometer.Fig. 1 is to implement Example 1 obtain have visible light-responded automatically cleaning ABS sheet material (load has g-C3N4/TiO2ABS sheet material) be denoted as g-C3N4/ TiO2The load that/ABS and comparative example 1 obtain has the ABS sheet material of titanium dioxide to be denoted as TiO2The Ultraviolet visible absorption spectrum of/ABS Figure.As can be seen from the figure g-C3N4/TiO2/ ABS has preferable absorption in visible light region, compared to TiO2/ ABS's is ultraviolet Absorption region, spectral absorption range obviously increases, it can be achieved that the multiband to sunlight absorbs.
Comparative example 2
A kind of preparation method for the ABS sheet material loading ABS film, by 27gABS (weight average molecular weight 100000Da, butadiene rubber Glue content 16%, number average bead diameter are 1.4 μm) it is added into 297g acetone, 0.5h is stirred by ultrasonic, forms polymer mother liquor, then This polymer mother liquor is coated in the ABS substrate of 0.5cm thickness using embrane method (knifing speed 100cm/min) is scraped, room temperature condition Lower solvent flashing is to get the ABS sheet material for arriving load ABS film.
The obtained sunlight with visible light-responded automatically cleaning ABS sheet material is urged using ultraviolet-uisible spectrophotometer Change degradation methyl orange efficiency to be tested.Fig. 2 for what embodiment 1 obtained there is visible light-responded automatically cleaning ABS sheet material to be denoted as g-C3N4/TiO2The load that/ABS, comparative example 1 obtain has the ABS sheet material of titanium dioxide to be denoted as TiO2/ ABS and comparative example 2 load The solar radiation photocatalytic degradation methyl orange efficiency chart of the ABS sheet material of ABS film, wherein C0 is methyl orange initial concentration, and C is different illumination When the methyl orange concentration inscribed, (C0-C)/C0 indicates photocatalytic degradation efficiency.The g- that embodiment 1 obtains as can be seen from Figure C3N4/TiO2The solar radiation photocatalytic degradation performance of/ABS is compared with TiO2The catalytic degradation of/ABS and single ABS sheet material is had excellent performance, and Catalytic degradation efficiency is high.

Claims (9)

1. a kind of with visible light-responded automatically cleaning ABS sheet material, which is characterized in that automatically cleaning ABS sheet material is by ABS substrate With the automatically cleaning film composition being coated in ABS substrate；Wherein ABS substrate is the ABS sheet material with a thickness of 0.5~2.5cm, automatically cleaning Film is by ABS resin and g-C3N4/TiO2It is prepared；
The g-C3N4/TiO2It is using g-C3N4The method of doping is to TiO2Be modified and be prepared, by mass ratio be 3~ The ABS resin and g-C of 6:13N4/TiO2It is added into acetone, 0.5~1h is stirred by ultrasonic, polymer mother liquor is formed, then by this Polymer mother liquor is coated in ABS substrate using coating method, solvent flashing under room temperature, obtain having it is visible light-responded from Clean ABS sheet material.
2. according to claim 1 a kind of with visible light-responded automatically cleaning ABS sheet material, which is characterized in that described Automatically cleaning ABS sheet material has vis-absorbing and anti-ultraviolet ageing, and photocatalytic degradation efficiency is 85~90%.
3. according to claim 1 a kind of with visible light-responded automatically cleaning ABS sheet material, which is characterized in that described The weight average molecular weight of ABS resin is 80000~200000Da, and butadiene rubber content is 10~20wt%, butadiene rubber grain Diameter is 0.2~3 μm.
4. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material as described in claims 1 to 3 is any, It is characterized in that, comprising the following steps:
(1) by the predecessor of carbon containing rich nitrogen with the heating rate of 10~20 DEG C/min in 520~600 DEG C of 4~6h of calcining, to nature After cooling, g-C is obtained3N4Powder；
(2) by g-C3N4It is scattered in methanol, 1~2h of ultrasound obtains g-C3N4Suspension takes titanium source to be added dropwise in acetic acid, and G-C after ultrasound is added3N4Suspension, after stirring 0.5h, obtained solution hydro-thermal reaction 12~for 24 hours at 120~180 DEG C, clearly Product is collected after washing and drying obtains g-C3N4/TiO2；
(3) ABS resin and g-C for being 3~6:1 by mass ratio3N4/TiO2It is added into acetone, 0.5~1h is stirred by ultrasonic, formed Then this polymer mother liquor is coated in ABS substrate by polymer mother liquor using coating method, solvent flashing, obtains under room temperature To with visible light-responded automatically cleaning ABS sheet material.
5. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material according to claim 4, feature exist In the predecessor of the carbon containing rich nitrogen is cyanamide and/or melamine.
6. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material according to claim 4, feature exist In the titanium source is isopropyl titanate or tetrabutyl titanate, g-C3N4Molar ratio with titanium source is 1~3:26.
7. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material according to claim 4, feature exist In the volume of the methanol and acetic acid is 1~1.5:6.
8. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material according to claim 4, feature exist In the concentration of the polymer mother liquor is 10~20wt%.
9. a kind of preparation method with visible light-responded automatically cleaning ABS sheet material according to claim 4, feature exist In the coating method is knifing or spin-coating method, wherein scraping knifing speed in embrane method is 50~250cm/min, spin coating in spin-coating method Speed is 700~3500rpm.
CN201611108824.6A 2016-12-06 2016-12-06 It is a kind of with visible light-responded automatically cleaning ABS sheet material and preparation method thereof Active CN106674568B (en)

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CN104311864A (en) * 2014-10-16 2015-01-28 扬州喜达屋环保科技有限公司 High-efficiency visible light antibacterial fresh-keeping plastic packaging material and preparation method thereof

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