CN106589666A - Heat-resistant and self-cleaned plastic sheet material and preparation method therefor - Google Patents
Heat-resistant and self-cleaned plastic sheet material and preparation method therefor Download PDFInfo
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- 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
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- 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
- C08K9/04—Ingredients treated with organic substances
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- 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
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- 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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- 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
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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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
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a heat-resistant and self-cleaned plastic sheet material. The heat-resistant and self-cleaned plastic sheet material is prepared from the following raw materials in parts by weight: 3-4 parts of trisnonyl phenyl phosphite, 0.7-1 part of dialkyl p-diphenol, 0.8-1 part of manganese iso-octoate, 2-3 parts of aluminum-magnesium silicate, 0.7-1 part of alkylphenol polyoxyethylene ether, 10-14 parts of titanium tetrachloride, 3.7-4 parts of ferric chloride, 6-8 parts of 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 silane coupling agent kh560, 2-3 parts of diacetone alcohol, 1-2 parts of oxidized polyethylene wax, 2-3 parts of antimony trioxide and 0.1-0.2 part of hexabromocyclododecane. According to the plastic sheet material, added ferrum-doped titanium dioxide has very good photocatalytic capability, and contaminants attached to the surface of the sheet material can be degraded and removed, so that self-cleaning performance is achieved.
Description
Technical field
The present invention relates to board technology field, more particularly to a kind of heat-resisting self-clean type plastic plate and preparation method thereof.
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 heat-resisting self-clean type plastic plate and its system
Preparation Method.
The present invention is achieved by the following technical solutions：
A kind of heat-resisting self-clean type plastic plate, it is made up of the raw material of following weight parts：
Trisnonyl phenyl phosphite 3-4, dialkyl group are to biphenol 0.7-1, manganese iso-octoate 0.8-1, aluminium-magnesium silicate 2-3, alkyl phenol
Polyoxyethylene ether 0.7-1, 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, polrvinyl chloride 100-130, silane coupler kh5600.7-1, DAA 2-3, oxidation
Tissuemat E 1-2, antimony oxide 2-3, HBCD 0.1-0.2.
A kind of preparation method of described heat-resisting self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned dialkyl group is added to biphenol in the dehydrated alcohol of its weight 10-19 times, it is 54-60 DEG C to rise high-temperature,
Insulated and stirred 10-14 minute, above-mentioned OPE is added, sent in 120-130 DEG C of oil bath, insulated and stirred 5-10 point
Clock, discharging, is mixed with above-mentioned manganese iso-octoate, is stirred to room temperature, obtain alcohol dispersion liquid；
（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, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30% is added, magnetic agitation 20-30 minute, is protected at 100-105 DEG C
Temperature stirring 4-5 hours, send in 57-60 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 its weight 50-60 times, Deca acetic acid, regulation pH are 5-
6, stir, add above-mentioned antimony oxide, Fe2O3 doping titanium dioxide, ultrasonic 20-30 minutes, sucking filtration to obtain Silane Grafted and mix
Miscellaneous titanium dioxide；
（4）Above-mentioned aluminium-magnesium silicate is taken, is added in the deionized water of its weight 64-70 times, ultrasonic 3-4 minutes, add alkyl phenol
Polyoxyethylene ether, the insulated and stirred 10-14 minute at 60-65 DEG C, the above-mentioned Silane Grafted of addition is titania-doped, alcohol dispersion
Liquid, continues insulated and stirred 20-30 minute, filters, and by precipitation washing 3-4 time, is vacuum dried 30-40 minutes, obtains at 50-60 DEG C
Compound grafting is titania-doped；
（5）Take above-mentioned compound grafting titania-doped, be added in the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, adds HBCD, the insulated and stirred 10-14 minute at 70-80 DEG C, adds above-mentioned methyl methacrylate, azo
Bis-isobutyronitrile, it is 57-60 DEG C to reduce temperature, and insulated and stirred 4-6 hour adds above-mentioned DAA, stirs, centrifugation point
From by precipitation absolute ethanol washing 3-4 time, 1-2 hours being vacuum dried at 50-60 DEG C, obtain titania-doped grafting poly-
Compound；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, at 70-80 DEG C, insulated and stirred 1-2 is little
When, double screw extruder is sent into, extrusion, mould molding, is 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 plastic plate of the present invention is with heat-resisting steady well
It is qualitative, it is particularly well-suited to torrid areas, good weatherability, long service life.
Specific embodiment
A kind of heat-resisting self-clean type plastic plate, it is made up of the raw material of following weight parts：
Trisnonyl phenyl phosphite 3, dialkyl group is to biphenol 0.7, manganese iso-octoate 0.8, aluminium-magnesium silicate 2, alkylphenol-polyethenoxy
It is ether 0.7, titanium tetrachloride 10, the hydrogen peroxide 6 of iron chloride 3.7,25%, methyl methacrylate 7, azodiisobutyronitrile 0.1, poly-
Vinyl chloride 100, silane coupler kh5600.7, DAA 2, OPE 1, antimony oxide 2, HBCD
0.1。
A kind of preparation method of described heat-resisting self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned dialkyl group is added to biphenol in the dehydrated alcohol of 10 times of its weight, it is 54 DEG C to rise high-temperature, and insulation is stirred
Mix 10 minutes, add above-mentioned OPE, send in 120 DEG C of oil bath, insulated and stirred 5 minutes, discharging is different pungent with above-mentioned
Sour manganese mixing, stirs to room temperature, obtains alcohol dispersion liquid；
（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, ultrasound
6 minutes, the hydrogen peroxide of addition above-mentioned 25%, magnetic agitation 20 minutes, insulated and stirred 4 hours at 100 DEG C send into 57 DEG C
In baking oven, drying, discharging obtain 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 antimony oxide, Fe2O3 doping titanium dioxide, ultrasound 20 minutes, sucking filtration is added to obtain Silane Grafted doping titanium dioxide
Titanium；
（4）Above-mentioned aluminium-magnesium silicate is taken, is added in the deionized water of 64 times of its weight, ultrasound 3 minutes adds alkyl phenol polyoxy second
Alkene ether, insulated and stirred 10 minutes at 60 DEG C, the above-mentioned Silane Grafted of addition is titania-doped, alcohol dispersion liquid, continues insulation and stirs
Mix 20 minutes, filter, precipitation washing 3 times is vacuum dried 30 minutes at 50 DEG C, grafting must be combined titania-doped；
（5）Take above-mentioned compound grafting titania-doped, be added in the dimethyl sulfoxide of 37 times of its weight, ultrasound 5 minutes, plus
Enter HBCD, insulated and stirred 10 minutes at 70 DEG C add above-mentioned methyl methacrylate, azodiisobutyronitrile, drop
Low temperature is 57 DEG C, and insulated and stirred 4 hours adds above-mentioned DAA, stirs, and precipitation is used anhydrous second by centrifugation
Alcohol is washed 3 times, is vacuum dried 1 hour, obtains titania-doped graft polymers at 50 DEG C；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, at 70 DEG C, insulated and stirred 1 hour, send
Enter double screw extruder, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
Performance test：
Tensile strength： 42.3MPa；
Bending strength： 78MPa；
Anti-flammability：Put out from fire, no black smoke.
Claims (2)
1. a kind of heat-resisting self-clean type plastic plate, it is characterised in that it is made up of the raw material of following weight parts：
Trisnonyl phenyl phosphite 3-4, dialkyl group are to biphenol 0.7-1, manganese iso-octoate 0.8-1, aluminium-magnesium silicate 2-3, alkyl phenol
Polyoxyethylene ether 0.7-1, 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, polrvinyl chloride 100-130, silane coupler kh5600.7-1, DAA 2-3, oxidation
Tissuemat E 1-2, antimony oxide 2-3, HBCD 0.1-0.2.
2. a kind of preparation method of heat-resisting self-clean type plastic plate as claimed in claim 1, it is characterised in that including following step
Suddenly：
（1）Above-mentioned dialkyl group is added to biphenol in the dehydrated alcohol of its weight 10-19 times, it is 54-60 DEG C to rise high-temperature,
Insulated and stirred 10-14 minute, above-mentioned OPE is added, sent in 120-130 DEG C of oil bath, insulated and stirred 5-10 point
Clock, discharging, is mixed with above-mentioned manganese iso-octoate, is stirred to room temperature, obtain alcohol dispersion liquid；
（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, ultrasonic 6-10 minutes, the hydrogen peroxide of above-mentioned 25-30% is added, magnetic agitation 20-30 minute, is protected at 100-105 DEG C
Temperature stirring 4-5 hours, send in 57-60 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 its weight 50-60 times, Deca acetic acid, regulation pH are 5-
6, stir, add above-mentioned antimony oxide, Fe2O3 doping titanium dioxide, ultrasonic 20-30 minutes, sucking filtration to obtain Silane Grafted and mix
Miscellaneous titanium dioxide；
（4）Above-mentioned aluminium-magnesium silicate is taken, is added in the deionized water of its weight 64-70 times, ultrasonic 3-4 minutes, add alkyl phenol
Polyoxyethylene ether, the insulated and stirred 10-14 minute at 60-65 DEG C, the above-mentioned Silane Grafted of addition is titania-doped, alcohol dispersion
Liquid, continues insulated and stirred 20-30 minute, filters, and by precipitation washing 3-4 time, is vacuum dried 30-40 minutes, obtains at 50-60 DEG C
Compound grafting is titania-doped；
（5）Take above-mentioned compound grafting titania-doped, be added in the dimethyl sulfoxide of its weight 37-40 times, ultrasonic 5-7 point
Clock, adds HBCD, the insulated and stirred 10-14 minute at 70-80 DEG C, adds above-mentioned methyl methacrylate, azo
Bis-isobutyronitrile, it is 57-60 DEG C to reduce temperature, and insulated and stirred 4-6 hour adds above-mentioned DAA, stirs, centrifugation point
From by precipitation absolute ethanol washing 3-4 time, 1-2 hours being vacuum dried at 50-60 DEG C, obtain titania-doped grafting poly-
Compound；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, at 70-80 DEG C, insulated and stirred 1-2 is little
When, double screw extruder is sent into, extrusion, mould molding, is cut off, overlay film, obtain final product the plastic plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201611010200.0A CN106589666A (en) | 2016-11-17 | 2016-11-17 | Heat-resistant and self-cleaned plastic sheet material and preparation method therefor |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611010200.0A CN106589666A (en) | 2016-11-17 | 2016-11-17 | Heat-resistant and self-cleaned plastic sheet material and preparation method therefor |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105860816A (en) * | 2016-04-29 | 2016-08-17 | *** | Self-cleaning water-borne polyurethane coating and preparation method thereof |
| CN106117911A (en) * | 2016-08-04 | 2016-11-16 | 安徽嘉木橡塑工业有限公司 | A kind of plastic material and preparation method thereof |
-
2016
- 2016-11-17 CN CN201611010200.0A patent/CN106589666A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105860816A (en) * | 2016-04-29 | 2016-08-17 | *** | Self-cleaning water-borne polyurethane coating and preparation method thereof |
| CN106117911A (en) * | 2016-08-04 | 2016-11-16 | 安徽嘉木橡塑工业有限公司 | A kind of plastic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 罗美芳等: "改性TiO_2在PVC基体中的分散行为研究", 《中国塑料》 * |
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Application publication date: 20170426 |