CN106589668A - Titanium dioxide-doped self-cleaning plastic plate and preparation method thereof - Google Patents
Titanium dioxide-doped self-cleaning plastic plate and preparation method thereof Download PDFInfo
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- CN106589668A CN106589668A CN201611010202.XA CN201611010202A CN106589668A CN 106589668 A CN106589668 A CN 106589668A CN 201611010202 A CN201611010202 A CN 201611010202A CN 106589668 A CN106589668 A CN 106589668A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a titanium dioxide-doped self-cleaning plastic plate which is composed of the following raw materials in parts by weight: 3-4 parts of trifluoroethyl methacrylate, 0.6-1 part of dimethyl imidazole, 0.1-0.2 part of dimethyl formamide, 10-14 parts of titanium tetrachloride, 3.7-4 parts of ferric chloride, 6-8 parts of a 25-30% hydrogen peroxide, 7-9 parts of methyl methacrylate, 0.1-0.2 part of azodiisobutyronitrile, 100-130 parts of polyvinyl chloride, 0.7-1 part of a silane coupling agent kh560, 0.5-1 part of stannic oxide, 2-3 parts of ammonium metaborate, 0.7-1 part of ethoxylated alkyl ammonium sulfate, 1-2 parts of ricinoleic acid, and 1-2 parts of sorbitan mono-oleic acid ester. The added iron-doped titanium dioxide has the advantages of good photocatalytic ability, and can degrade and remove pollutants attached on the surface of the plate, so as to realize the self-cleaning performance.
Description
Technical field
The present invention relates to board technology field, more particularly to a kind of titania additive self-clean type plastic plate and its preparation
Method.
Background technology
Titanium dioxide is a kind of transition metal oxide while being also a kind of semi-conducting material, as which has preferable life
The thing compatibility, can resist chemical attack, the advantages of harmless, meanwhile, the material abundance of titanium source content makes titanium dioxide thing
Produce abundant and cheap, therefore obtained people and widely pay close attention to, the application of titanium dioxide is embodied in each of people's life
Aspect, current titanium dioxide have reached world lead level without mechanical goods usage amount.Due to the characteristic of titanium dioxide, Ke Yizuo
For very important inorganic chemical industry material, therefore which has huge in various fields such as national defence aviation industry, commercial production, hard-core technologies
Big power of influence and application.Titanium dioxide can possess color using titanium white production coating out as Chinese white again
Bright-coloured, colorability is strong, and the advantages of covering power is high, and its service life is longer compared with other pigment, therefore its usage amount accounts for institute
Have the 80% of Chinese white.Rather than the other titanium dioxide of pigment-level still possesses the field of being widely applied, be concentrated mainly on metallurgy,
The fields such as ceramics, glass, sheet material；As titanium dioxide has the ability and higher photocatalytic activity that absorb ultraviolet, therefore can
Catalyst, adsorbent, antibacterial etc. are prepared with using this characteristic, in the 70's of eighties of last century, people are found that to water
Middle addition titanium dioxide, under the irradiation of visible ray, water can resolve into oxygen and hydrogen.Subsequently, it is and special because of titanium dioxide
Some physicochemical properties and every excellent properties, so be widely used in numerous fields, including environment, the energy, information,
Material, health, building, medical treatment etc., especially in fields such as photocatalysis, solaode, gas sensor, sterilizations, embody very
Big researching value；
Nano titanium oxide has excellent photocatalytic activity, has quite varied application prospect, however, there is also some
Weak point, nano titanium oxide just must can play a part of catalyst under the promotion of ultraviolet light, and solar energy is produced
Great waste, which greatly limits the use of nano titanium oxide.So we are needed by modified this
Method improves utilization of the nano titanium oxide to solar energy, allows it to make full use of the light of visible region.Research shows, when subtracting
During the size of little titanium dioxide nanoparticle, its surface area, surface tension can be strengthened therewith with surface energy.Little chi is provided with accordingly
The characteristics such as very little effect, quantum size effect, skin effect, it is widely used various that these speciality also cause titanium dioxide to become
Inorganic material product；
Catalysis material improves the living environment of people, and we are can be not only used for using the photoelectric characteristic of catalysis material
Solaode is prepared, can be with degradation of contaminant, maintaining ecological balance.But the problem that needs are solved is, catalysis material
Solar energy can't be efficiently utilized more, and this causes energy transition rate low or the shortcomings of poor photocatalytic degradation efficiency；On the one hand
Shortage of resources, is on the one hand unable to effectively utilizes effective energy（Visible light part）, will all cause the extreme loss of resource.Cause
This, for how to improve titanium dioxide as the problem of photocatalysis efficiency, still needs to further study and improve；
Polyacrylate has pollution-free, low cost and other advantages, has obtained more wide in fields such as building, automobile, packaging, printings
General application, but there is also thermostability, hardness etc. it is poor the problems such as, limit to a certain extent its application, using inorganic nano
Titania modified polyacrylate, can significantly improve the performances such as the hardness of polyacrylate, thermostability, impact strength, from
And further expand its use range；
However, as the specific surface area of nano titanium oxide is big, surface energy is high, in non-thermodynamics stable state, prepared answers
The shortcomings of easily there is nanoparticle reunion, composite poor storage stability, complicated process of preparation in condensation material.
The content of the invention
The object of the invention is exactly for the defect for making up prior art, there is provided a kind of titania additive self-clean type plastic plate
Material and preparation method thereof.
The present invention is achieved by the following technical solutions：
A kind of titania additive self-clean type plastic plate, it is made up of the raw material of following weight parts：
Trifluoroethyl methacrylate 3-4, methylimidazole 0.6-1, dimethylformamide 0.1-0.2, titanium tetrachloride 10-14,
The hydrogen peroxide 6-8 of iron chloride 3.7-4,25-30%, methyl methacrylate 7-9, azodiisobutyronitrile 0.1-0.2, polychlorostyrene second
Alkene 100-130, silane coupler kh5600.7-1, tin ash 0.5-1, ammonium metaborate 2-3, ethoxylated alkyl ammonium sulfate
0.7-1, castor oil acid 1-2, sorbic alcohol acid anhydride list olein 1-2.
A kind of preparation method of described titania additive self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned ammonium metaborate is added in the deionized water of its weight 10-13 times, is stirred, liter high-temperature is 60-67
DEG C, insulated and stirred 5-10 minute, sulphuric acid of the Deca concentration for 70-75%, regulation pH is 2-3, stirs to room temperature, adds above-mentioned two
Methylformamide, 100-200 rev/min of stirring 10-17 minute, filter cake at 47-50 DEG C is vacuum dried 1-2 hours, is obtained by sucking filtration
Modified filler；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of its weight 60-70 times, is stirred, add above-mentioned iron chloride,
Ammonia spirit of the Deca concentration for 5.4-6%, regulations pH is 8-9, and sucking filtration will be precipitated and be added to the deionization of its weight 40-50 times
In water, ethoxylated alkyl ammonium sulfate is added, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30%, magnetic agitation 20- is added
30 minutes, above-mentioned tin ash, the insulated and stirred 4-5 hour at 100-105 DEG C is added to send in 57-60 DEG C of baking oven, dry
Dry, discharging obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned silane coupler kh560 is taken, is added in the acetone of its weight 50-60 times, Deca acetic acid, regulation pH are 5-
6, stir, add above-mentioned Fe2O3 doping titanium dioxide, modified filler, ultrasonic 20-30 minutes, sucking filtration to obtain Silane Grafted doping
Titanium dioxide；
（4）Above-mentioned methylimidazole is added in the dehydrated alcohol of its weight 7-10 times, is stirred, liter high-temperature is 70-
75 DEG C, insulated and stirred 10-16 minute, above-mentioned sorbic alcohol acid anhydride list olein is added, is stirred to room temperature, is obtained alcohol dispersion liquid；
（5）Take above-mentioned Silane Grafted titania-doped, be added in the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, the above-mentioned methyl methacrylate of addition, azodiisobutyronitrile, the insulated and stirred 4-6 hour at 57-60 DEG C, centrifugation will
Precipitation absolute ethanol washing 3-4 time, at 50-60 DEG C, vacuum drying 1-2 hours, obtain titania-doped graft polymers；
（6）Above-mentioned titania-doped graft polymers are mixed with alcohol dispersion liquid, is stirred, sucking filtration, by precipitation washing 3-4
Secondary, normal temperature drying is mixed with remaining each raw material, the insulated and stirred 1-2 hour at 70-80 DEG C, sends into double screw extruder, is squeezed
Go out, mould molding, cut off, overlay film, obtain final product the plastic plate.
It is an advantage of the invention that：Silane coupler is anchored in less aggregate surface by the present invention, reduces doping two
The surface energy and surface activity of Titanium particles, prevents doping particle itself that soft-agglomerated phenomenon occurs, due to the particle diameter that adulterates
Very little, enhance be covered in doping particle surface coupling agent molecule between active force and due to coupling agent adsorb and produce
Sterically hindered repulsive force, secondly, after polymethyl methacrylate is grafted on silane treatment by original position emulsion graft polymerization
Particle surface, realizes organising completely for particle surface, causes the carbochain of inorganic nano doping particle surface to be extended, especially
After the linear long-chain molecule of polymethyl methacrylate is by emulsion graft polymerization introducing, hence it is evident that improve inorganic/organic biphase interface
Structure, increased the compatibility, improve the stability of composite；The titania-doped graft polymers meeting that the present invention is added
Increase the crosslink density between matrix resin molecule segment, cause organic matrix macromolecular chain certain distance from shortening, intermolecular work
Firmly strengthen, secondly, anchoring grafting and the realization of emulsion graft polymerization so that the two-phase interface compatibility is enhanced, bonding interface effect
Further it is reinforced, the final result of these effects results in organic molecule chain movement ability in system to be reduced, and improves compound
The heat resistance of material, in addition, the Fe2O3 doping titanium dioxide that the present invention is added has good photo-catalysis capability, can be by sheet material
The contaminant degradation of surface attachment is removed, and so as to realize self-cleaning performance, the sheet material of the present invention has good self-cleaning property, special
Based plate Shi Yongyu not be decorated, surface gloss is good, intensity is high, good toughness.
Specific embodiment
A kind of titania additive self-clean type plastic plate, it is made up of the raw material of following weight parts：
Trifluoroethyl methacrylate 3, methylimidazole 0.6, dimethylformamide 0.1, titanium tetrachloride 10, iron chloride 3.7,
25% hydrogen peroxide 6, methyl methacrylate 7, azodiisobutyronitrile 0.1, polrvinyl chloride 100, silane coupler
Kh5600.7, tin ash 0.5, ammonium metaborate 2, ethoxylated alkyl ammonium sulfate 0.7, castor oil acid 1, sorbic alcohol acid anhydride list Oleic acid
Fat 1.
A kind of preparation method of described titania additive self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned ammonium metaborate is added in the deionized water of 10 times of its weight, is stirred, it is 60 DEG C to rise high-temperature, is protected
Temperature stirring 5 minutes, Deca concentration is 70% sulphuric acid, and it is 2 to adjust pH, is stirred to room temperature, adds above-mentioned dimethylformamide, 100
Rev/min stirring 10 minutes, filter cake is vacuum dried 1 hour at 47 DEG C, obtains modified filler by sucking filtration；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of 60 times of its weight, is stirred, add above-mentioned iron chloride, drop
Plus the ammonia spirit that concentration is 5.4%, it is 8 to adjust pH, and sucking filtration is added to precipitation in the deionized water of 40 times of its weight, adds
Ethoxylated alkyl ammonium sulfate, ultrasound 6 minutes add above-mentioned 25% hydrogen peroxide, magnetic agitation 20 minutes to add above-mentioned two
Stannum oxide, insulated and stirred 4 hours at 100 DEG C are sent in 57 DEG C of baking oven, drying, and discharging obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned silane coupler kh560 is taken, is added in the acetone of 50 times of its weight, Deca acetic acid, it is 5 to adjust pH, stirring
Uniformly, above-mentioned Fe2O3 doping titanium dioxide, modified filler are added, ultrasonic 20 minutes, sucking filtration obtains Silane Grafted titania-doped；
（4）Above-mentioned methylimidazole is added in the dehydrated alcohol of 7 times of its weight, is stirred, it is 70 DEG C to rise high-temperature, is protected
Temperature stirring 10 minutes, adds above-mentioned sorbic alcohol acid anhydride list olein, stirs to room temperature, obtain alcohol dispersion liquid；
（5）Take that above-mentioned Silane Grafted is titania-doped, be added in the dimethyl sulfoxide of 37 times of its weight, ultrasound 5 minutes, plus
Enter above-mentioned methyl methacrylate, azodiisobutyronitrile, insulated and stirred 4 hours at 57 DEG C, centrifugation, will precipitation with anhydrous
Washing with alcohol 3 times, is vacuum dried 1 hour at 50 DEG C, obtains titania-doped graft polymers；
（6）Above-mentioned titania-doped graft polymers are mixed with alcohol dispersion liquid, is stirred, sucking filtration, by precipitation washing 3
Secondary, normal temperature drying is mixed with remaining each raw material, insulated and stirred 1 hour at 70 DEG C, sends into double screw extruder, extrusion, mould
Molding, cut off, overlay film, obtain final product the plastic plate.
Performance test：
Tensile strength： 47.2MPa；
Bending strength： 77MPa；
Anti-flammability：Put out from fire, no black smoke.
Claims (2)
1. a kind of titania additive self-clean type plastic plate, it is characterised in that it is made up of the raw material of following weight parts：
Trifluoroethyl methacrylate 3-4, methylimidazole 0.6-1, dimethylformamide 0.1-0.2, titanium tetrachloride 10-14,
The hydrogen peroxide 6-8 of iron chloride 3.7-4,25-30%, methyl methacrylate 7-9, azodiisobutyronitrile 0.1-0.2, polychlorostyrene second
Alkene 100-130, silane coupler kh5600.7-1, tin ash 0.5-1, ammonium metaborate 2-3, ethoxylated alkyl ammonium sulfate
0.7-1, castor oil acid 1-2, sorbic alcohol acid anhydride list olein 1-2.
2. a kind of preparation method of titania additive self-clean type plastic plate as claimed in claim 1, it is characterised in that bag
Include following steps：
（1）Above-mentioned ammonium metaborate is added in the deionized water of its weight 10-13 times, is stirred, liter high-temperature is 60-67
DEG C, insulated and stirred 5-10 minute, sulphuric acid of the Deca concentration for 70-75%, regulation pH is 2-3, stirs to room temperature, adds above-mentioned two
Methylformamide, 100-200 rev/min of stirring 10-17 minute, filter cake at 47-50 DEG C is vacuum dried 1-2 hours, is obtained by sucking filtration
Modified filler；
（2）Above-mentioned titanium tetrachloride is added in the deionized water of its weight 60-70 times, is stirred, add above-mentioned iron chloride,
Ammonia spirit of the Deca concentration for 5.4-6%, regulations pH is 8-9, and sucking filtration will be precipitated and be added to the deionization of its weight 40-50 times
In water, ethoxylated alkyl ammonium sulfate is added, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30%, magnetic agitation 20- is added
30 minutes, above-mentioned tin ash, the insulated and stirred 4-5 hour at 100-105 DEG C is added to send in 57-60 DEG C of baking oven, dry
Dry, discharging obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned silane coupler kh560 is taken, is added in the acetone of its weight 50-60 times, Deca acetic acid, regulation pH are 5-
6, stir, add above-mentioned Fe2O3 doping titanium dioxide, modified filler, ultrasonic 20-30 minutes, sucking filtration to obtain Silane Grafted doping
Titanium dioxide；
（4）Above-mentioned methylimidazole is added in the dehydrated alcohol of its weight 7-10 times, is stirred, liter high-temperature is 70-
75 DEG C, insulated and stirred 10-16 minute, above-mentioned sorbic alcohol acid anhydride list olein is added, is stirred to room temperature, is obtained alcohol dispersion liquid；
（5）Take above-mentioned Silane Grafted titania-doped, be added in the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, the above-mentioned methyl methacrylate of addition, azodiisobutyronitrile, the insulated and stirred 4-6 hour at 57-60 DEG C, centrifugation will
Precipitation absolute ethanol washing 3-4 time, at 50-60 DEG C, vacuum drying 1-2 hours, obtain titania-doped graft polymers；
（6）Above-mentioned titania-doped graft polymers are mixed with alcohol dispersion liquid, is stirred, sucking filtration, by precipitation washing 3-4
Secondary, normal temperature drying is mixed with remaining each raw material, the insulated and stirred 1-2 hour at 70-80 DEG C, sends into double screw extruder, is squeezed
Go out, mould molding, cut off, overlay film, obtain final product the plastic plate.
Priority Applications (1)
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| CN201611010202.XA CN106589668A (en) | 2016-11-17 | 2016-11-17 | Titanium dioxide-doped self-cleaning plastic plate and preparation method thereof |
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| CN201611010202.XA CN106589668A (en) | 2016-11-17 | 2016-11-17 | Titanium dioxide-doped self-cleaning plastic plate and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108587047A (en) * | 2018-03-22 | 2018-09-28 | 长沙小新新能源科技有限公司 | A kind of fluorinated plastic and preparation method thereof |
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2016
- 2016-11-17 CN CN201611010202.XA patent/CN106589668A/en active Pending
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| CN101215397A (en) * | 2007-12-26 | 2008-07-09 | 华东理工大学 | Light degradation of polyvinyl chloride resin |
| CN105038010A (en) * | 2015-07-22 | 2015-11-11 | 滁州远方车船装备工程有限公司 | Antibacterial PVC wood plastic plate and preparation method thereof |
| CN105086265A (en) * | 2015-08-26 | 2015-11-25 | 安徽北马科技有限公司 | Photocatalytic antibacterial biomass wood-plastic composite material |
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| CN108587047A (en) * | 2018-03-22 | 2018-09-28 | 长沙小新新能源科技有限公司 | A kind of fluorinated plastic and preparation method thereof |
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