CN109504192A - A kind of carbon nanotube composite stone material protective agent and preparation method thereof - Google Patents

A kind of carbon nanotube composite stone material protective agent and preparation method thereof Download PDF

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Publication number
CN109504192A
CN109504192A CN201811348422.2A CN201811348422A CN109504192A CN 109504192 A CN109504192 A CN 109504192A CN 201811348422 A CN201811348422 A CN 201811348422A CN 109504192 A CN109504192 A CN 109504192A
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China
Prior art keywords
carbon nanotube
resin
protective agent
solution
30min
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CN201811348422.2A
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Chinese (zh)
Inventor
文中流
余宇
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Yunfu Huayun Creative Design Co Ltd
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Yunfu Huayun Creative Design Co Ltd
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Priority to CN201811348422.2A priority Critical patent/CN109504192A/en
Publication of CN109504192A publication Critical patent/CN109504192A/en
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    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • 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
    • C08K2003/2286—Oxides; Hydroxides of metals of silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Catalysts (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention discloses a kind of carbon nanotube composite stone material protective agents, have the carbon nanotube loaded Ag of photocatalytic activity by adding2O composite photocatalyst material, not only greatly improve wearability, weatherability and the barrier performance for improving carbon nanotube composite stone material protective agent, to have excellent protection effect and service life, while also there is excellent purification, antibacterial effect to pollutant, fungi etc., indoor air quality can be optimized.

Description

A kind of carbon nanotube composite stone material protective agent and preparation method thereof
Technical field:
The present invention relates to stone protectants, and in particular to a kind of carbon nanotube composite stone material protective agent and preparation method thereof
Background technique:
Photocatalysis technology is, using the excitation of nature solar source, to make catalyst using semiconductor material as photochemical catalyst Surface generates effective active specy, and reaches harmful organic substances in degradation environment under multiple transformation and interface interaction Purpose.Because the final mineralising of photodissociation forms CO2、H2O and other inorganic molecules substances are a kind of without the formation for adding secondary pollution Environmentally protective technology.
Stone material application occupies biggish ratio in finishing indoors, as fluorine carbon stone protectant is widely used in interior The protective coating of stone countertops, stone material hand basin etc. is one of the coating that indoor high-grade stone protection has important application.Stone material Water-repellent paint is one of stone protector technology, is had a wide range of applications in modern stone industries.Water-repellent paint is by making Synthetic resin is evenly distributed on stone surface or slowly penetrates into the film of the protective formed inside stone material, has stone material The functions such as waterproof, antifouling, grease proofing, acid and alkali-resistance, weather resistance, anti-aging, freeze thawing resistance, antibiont erosion, to improve stone material use The effect in service life and decorative performance.Fluorocarbon resin class water-repellent paint belongs to stone material waterproofing agent of new generation, compared with traditional coating There are many excellent characteristic, such as extremely low surface can be resistance to extremely strong hydrophobicity, great stain resistance, weatherability and overlength Long property (its weatherability was up to 15 years or more) etc..But when Bartlit protective coating for stone floor brick, stone furniture, Table top etc. in application, not being able to satisfy the requirement that the quality of stone protectant product is continuously improved in user.
Summary of the invention:
The purpose of the present invention overcomes the defect of the above-mentioned prior art, provides a kind of carbon nanotube composite stone material protective agent, leads to Cross the carbon nanotube loaded Ag that addition has photocatalytic activity2O composite photocatalyst material, not only with excellent protection effect and Service life, while also there is excellent purification, antibacterial effect to pollutant, fungi etc., indoor air quality can be optimized.
The present invention is achieved by the following technical programs:
A kind of carbon nanotube composite stone material protective agent, which includes following component: by pvdf resin (VDF) and acrylic resin composition resin raw material, carbon nanotube loaded Ag2O composite photocatalyst material, silane coupling agent, two Chlorine dibutyl tin, solvent；Wherein, resin raw material, carbon nanotube loaded Ag2O composite photocatalyst material, silane coupling agent, solvent Mass ratio are as follows: 2~4.5:1~3:0.02~0.04:90~95, the dichloro dibutyl tin catalyst in every liter of protective agent raw material Additive amount be 0.5~1mg, the relative mass percentage of pvdf resin and acrylic resin is respectively in resin raw material 70%~90% and 10%~30%, the solvent is 10~20:50~65:15~40 solvent naphtha D30, D40 by mass ratio It is mixed with D65, carbon nanotube loaded Ag2O composite photocatalyst material the preparation method is as follows: carbon nanotube is put into deionization The AgNO that concentration is 0.5~1.0mol/L is added in ultrasound 20-30min in water3Solution controls AgNO3Solution and carbon nanotube Mass ratio is 5~10:1, continues ultrasound 20-30min；Then, under magnetic stirring, the adjustment of 2mol/LNaOH solution is added dropwise The pH value of solution is further continued for magnetic agitation 20-30min close to 14；Filter residue is collected in filtering, and filter residue is by deionized water and anhydrous Ethanol washing is then placed in 60 DEG C of air dry ovens dry 12h, obtains carbon nanotube loaded Ag2O composite photocatalyst material, It is denoted as Ag2O/ carbon nanometer pipe catalytic material.
The pvdf resin is preferably polyvinylidene fluroide homopolymer resin, is main water-proof function ingredient；It is described Acrylic resin is preferably polymethyl methacrylate resin, plays a part of to increase to substrate adhesion and coating phase stability；Institute State Ag2O/ carbon nanometer pipe catalytic material plays a dual role of toughening modifying and photocatalysis；The silane coupling agent is preferably silane Coupling agent KH550 mainly plays a part of to increase interface bond strength between nano modifier and resin；The dichloro dibutyl tin is urged Agent mainly plays promotion resin polymerization, improves the effect of filming performance.
The preparation method of the protective agent the following steps are included:
1) carbon nanotube is put into ultrasound 20-30min in deionized water, and the AgNO that concentration is 0.5~1.0mol/L is added3It is molten Liquid controls AgNO3Solution and the mass ratio of carbon nanotube are 5~10:1, continue ultrasound 20-30min；Then, in magnetic agitation Under, the pH value of 2mol/LNaOH solution adjustment solution is added dropwise close to 14, is further continued for magnetic agitation 20-30min；Filtering is received Collect filter residue, washed by deionized water and dehydrated alcohol, is then placed in 60 DEG C of air dry ovens dry 12h, obtains carbon nanometer Pipe loaded Ag2O composite photocatalyst material, is denoted as Ag2O/ carbon nanometer pipe catalytic material；
2) using pvdf resin (VDF) and acrylic resin as resin raw material, silane coupling agent is crosslinking agent, dichloro two Butyl tin is catalyst, and Ag obtained in step 1) is added2O/ carbon nanometer pipe catalytic material, above-mentioned material is dissolved in solvent Afterwards, disperse to obtain within 5~15 minutes carbon nanotube composite stone material protective agent at room temperature using high speed disperser.
The present invention also protects the carbon nanotube composite stone material protective agent in the application of stone surface.
Beneficial effects of the present invention are as follows:
1)Ag2O/ carbon nanometer pipe catalytic material uses the light-sensitive material nanometer Ag of low energy gap width2O is a kind of with preferable Visible light responsible photocatalytic active material, it is with higher activity and stability, can effectively improve the photocatalysis of coating Kill/anti-microbial property.The silver ion on its surface is easy to be reduced into silver atoms and forms cluster, since the plasma resonance of silver is inhaled Produce effects and answer, silver-based semiconductor material is made to show good visible absorption performance, by excitation generate light induced electron wait from Can effectively be shifted under the action of daughter resonance system, separate achieve the purpose that promote photocatalytic activity.
2)Ag2O/ carbon nanometer pipe catalytic material, as catalyst carrier, on the one hand can be improved compound by carbon nanotube The photocatalysis efficiency of photochemical catalyst, another aspect carbon nanotube can be improved carbon nanotube composite stone material protective agent wearability, Weatherability and barrier performance.
In short, the present invention has the carbon nanotube loaded Ag of photocatalytic activity by addition2O composite photocatalyst material, no Wearability, weatherability and the barrier performance for improving carbon nanotube composite stone material protective agent are only greatly improved, to have excellent Protection effect and service life, while also there is excellent purification, antibacterial effect to pollutant, fungi etc., Interior Space can be optimized Makings amount.
Specific embodiment:
It is to further explanation of the invention, rather than limiting the invention below.
Embodiment 1:
(1) that 20g carbon nanotube is put into ultrasound 30min, the 1mol/LAgNO3 that 100g is added dropwise in 2L deionized water is molten Liquid continues ultrasound 20min；Then, under magnetic stirring, the pH value that 2mol/LNaOH solution adjustment solution is added dropwise is close 14, it is further continued for magnetic agitation 30min；Filtering, collects filter residue, and filter residue is washed by deionized water and dehydrated alcohol, is then placed in Dry 12h, obtains Ag in 60 DEG C of air dry ovens2O/ carbon nanometer pipe catalytic material.
(2) 93.5gD30 solvent naphtha, 608gD40 solvent naphtha and 234gD65 solvent naphtha are obtained into 935.5g after mixing Solvent.By 21g polyvinylidene fluroide homopolymer resin, 9g polymethyl methacrylate resin, 1.5gAg2O/ carbon nanometer pipe catalytic material Material, 0.20g Silane coupling agent KH550,935.5g solvent and 0.5mg dichloro dibutyl tin catalyst are placed in Scattered Kettle, are used High speed disperser disperses that the carbon nanotube composite stone material protective agent can be obtained within 10 minutes at room temperature.
After the carbon nanotube composite stone material protective agent is coated on marble sample, carries out fungi and inhibit growth comparison Ag is added in experiment, display2After O/ carbon nanometer pipe catalytic material, the sterilizing ability of stone protectant is significantly improved.
Embodiment 2
(1) that 50g carbon nanotube is put into ultrasound 30min, the 1mol/LAgNO3 that 300g is added dropwise in 5L deionized water is molten Liquid continues ultrasound 20min；Then, under magnetic stirring, the pH value that 2mol/LNaOH solution adjustment solution is added dropwise is close 14, it is further continued for magnetic agitation 30min；Filtering, collects filter residue, and filter residue is washed by deionized water and dehydrated alcohol, is then placed in Dry 12h, obtains Ag in 60 DEG C of air dry ovens2O/ carbon nanometer pipe catalytic material.
(2) that 362gD30 solvent naphtha, 905gD40 solvent naphtha and 542gD65 solvent naphtha are obtained 1809g after mixing is molten Agent.
By 72g polyvinylidene fluroide homopolymer resin, 18g polymethyl methacrylate resin, 25gAg2O/ carbon nanotube is urged Change material, 0.40g Silane coupling agent KH550 and 1809g solvent and 1.2mg dichloro dibutyl tin catalyst be placed in Scattered Kettle, Disperse that the carbon nanotube composite stone material protective agent can be obtained within 15 minutes at room temperature using high speed disperser.

Claims (4)

1. a kind of carbon nanotube composite stone material protective agent, which is characterized in that the protective agent raw material includes following component: by inclined fluorine second Resin raw material, the carbon nanotube loaded Ag of olefine resin and acrylic resin composition2O composite photocatalyst material, silane coupling agent, two Chlorine dibutyl tin, solvent；Wherein, resin raw material, carbon nanotube loaded Ag2O composite photocatalyst material, silane coupling agent, solvent Mass ratio are as follows: 2~4.5:1~3:0.02~0.04:90~95, the dichloro dibutyl tin catalyst in every liter of protective agent raw material Additive amount be 0.5~1mg, the relative mass percentage of pvdf resin and acrylic resin is respectively in resin raw material 70%~90% and 10%~30%, the solvent is 10~20:50~65:15~40 solvent naphtha D30, D40 by mass ratio It is mixed with D65, carbon nanotube loaded Ag2O composite photocatalyst material the preparation method is as follows: carbon nanotube is put into deionization The AgNO that concentration is 0.5~1.0mol/L is added in ultrasound 20-30min in water3Solution controls AgNO3Solution and carbon nanotube Mass ratio is 5~10:1, continues ultrasound 20-30min；Then under magnetic stirring, the adjustment of 2mol/LNaOH solution is added dropwise The pH value of solution is further continued for magnetic agitation 20-30min close to 14；Filter residue is collected in filtering, and filter residue is by deionized water and anhydrous Ethanol washing is then placed in 60 DEG C of air dry ovens dry 12h, obtains carbon nanotube loaded Ag2O composite photocatalyst material, It is denoted as Ag2O/ carbon nanometer pipe catalytic material.
2. carbon nanotube composite stone material protective agent according to claim 1, which is characterized in that the pvdf resin is Polyvinylidene fluroide homopolymer resin；The acrylic resin is polymethyl methacrylate resin；The silane coupling agent is silicon Alkane coupling agent KH550.
3. a kind of preparation method of protective agent described in claim 1, which comprises the following steps:
1) carbon nanotube is put into ultrasound 20-30min in deionized water, and the AgNO that concentration is 0.5~1.0mol/L is added3Solution, control AgNO processed3Solution and the mass ratio of carbon nanotube are 5~10:1, continue ultrasound 20-30min；Then, under magnetic stirring, by The pH value of 2mol/LNaOH solution adjustment solution is added dropwise to close to 14, is further continued for magnetic agitation 20-30min；Filter is collected in filtering Slag is washed by deionized water and dehydrated alcohol, is then placed in 60 DEG C of air dry ovens dry 12h, is obtained Ag2O/ carbon nanometer Pipe catalysis material；
2) using pvdf resin and acrylic resin as resin raw material, silane coupling agent is crosslinking agent, and dichloro dibutyl tin is Ag obtained in step 1) is added in catalyst2O/ carbon nanometer pipe catalytic material after above-mentioned material is dissolved in solvent, utilizes High speed disperser disperses to obtain within 5~15 minutes carbon nanotube composite stone material protective agent at room temperature.
4. application of the carbon nanotube composite stone material protective agent in stone surface described in claim 1.
CN201811348422.2A 2018-11-13 2018-11-13 A kind of carbon nanotube composite stone material protective agent and preparation method thereof Pending CN109504192A (en)

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Citations (5)

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Publication number Priority date Publication date Assignee Title
CN103819222A (en) * 2014-01-27 2014-05-28 厦门诺恩斯科技有限公司 Novel oil contamination-resistant water-resistant stone repellent and preparation method thereof
CN105289685A (en) * 2015-10-10 2016-02-03 浙江工业大学 Surface plasmon resonance enhanced photocatalyst for air purification, preparation method of surface plasmon resonance enhanced photocatalyst and application of surface plasmon resonance enhanced photocatalyst
CN107812520A (en) * 2017-11-08 2018-03-20 扬州大学 A kind of loading type silver catalyst preparation method for purifying formaldehyde
CN108165171A (en) * 2017-12-14 2018-06-15 云浮华云创新设计有限公司 A kind of nano-material modified fluorocarbon resin class stone material water-repellent paint
CN108203559A (en) * 2017-12-29 2018-06-26 云浮华云创新设计有限公司 It is a kind of for aqueous stone protectant of anti-mildew photocuring of stone surface and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103819222A (en) * 2014-01-27 2014-05-28 厦门诺恩斯科技有限公司 Novel oil contamination-resistant water-resistant stone repellent and preparation method thereof
CN105289685A (en) * 2015-10-10 2016-02-03 浙江工业大学 Surface plasmon resonance enhanced photocatalyst for air purification, preparation method of surface plasmon resonance enhanced photocatalyst and application of surface plasmon resonance enhanced photocatalyst
CN107812520A (en) * 2017-11-08 2018-03-20 扬州大学 A kind of loading type silver catalyst preparation method for purifying formaldehyde
CN108165171A (en) * 2017-12-14 2018-06-15 云浮华云创新设计有限公司 A kind of nano-material modified fluorocarbon resin class stone material water-repellent paint
CN108203559A (en) * 2017-12-29 2018-06-26 云浮华云创新设计有限公司 It is a kind of for aqueous stone protectant of anti-mildew photocuring of stone surface and preparation method thereof

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Application publication date: 20190322