CN106633495A - Silane modified self-cleaning plastic sheet and preparation method thereof - Google Patents
Silane modified self-cleaning plastic sheet and preparation method thereof Download PDFInfo
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- CN106633495A CN106633495A CN201611010164.8A CN201611010164A CN106633495A CN 106633495 A CN106633495 A CN 106633495A CN 201611010164 A CN201611010164 A CN 201611010164A CN 106633495 A CN106633495 A CN 106633495A
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a silane modified self-cleaning plastic sheet. The silane modified self-cleaning plastic sheet is prepared from the following raw materials in parts by weight: 0.8-2 parts of maleic anhydride, 0.3-1 part of triallyl isocyanurate, 10-14 parts of titanium tetrachloride, 6-8 parts of 25%-30% hydrogen peroxide, 7-9 parts of methyl methacrylate, 0.1-0.2 parts of azobisisobutyronitrile, 0.7-1 part of a silane coupling agent kh5600, 0.4-1 part of butyl tin tris-2-ethylexanoate, 0.7-1 part of calcium ricinoleate, 0.8-1 part of diacetone acrylamide, 1-2 parts of 8-hydroxyquinoline copper, 1-2 parts of magnesium stearate, 3.7-4 parts of ferric chloride, 100-130 parts of polyvinyl chloride and 1-2 parts of calcium stearate. The added iron doped titanium dioxide has good photocatalytic capacity, pollutants attached to the surface of the sheet can be removed by degradation, and accordingly, the self-cleaning performance is achieved.
Description
Technical field
The present invention relates to board technology field, more particularly to a kind of silane-modified self-clean type plastic plate and its preparation side
Method.
Background technology
Titanium dioxide is a kind of transition metal oxide while being also a kind of semi-conducting material, because it 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 without mechanical goods usage amount has reached world lead level.Due to the characteristic of titanium dioxide, Ke Yizuo
For very important inorganic chemical industry material, therefore it 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 as Chinese white using titanium white production coating out 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；Because titanium dioxide has the ability and higher photocatalytic activity that absorb ultraviolet, therefore can
To prepare catalyst, adsorbent, antibacterial etc. 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, there is 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 strengthen therewith with surface energy.Accordingly it is provided with little chi
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 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 more can't be efficiently utilized, 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 improving titanium dioxide as the problem of photocatalysis efficiency, still needing to further research and improving；
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 hardness, thermostability, the impact strength of polyacrylate, from
And further expand its use range；
However, because 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 to make up the defect of prior art, there is provided a kind of silane-modified self-clean type plastic plate and
Its preparation method.
The present invention is achieved by the following technical solutions：
A kind of silane-modified self-clean type plastic plate, it is made up of the raw material of following weight parts：
Maleic anhydride 0.8-2, Triallyl isocyanurate 0.3-1, the hydrogen peroxide 6-8 of titanium tetrachloride 10-14,25-30%,
Methyl methacrylate 7-9, azodiisobutyronitrile 0.1-0.2, silane coupler kh5600.7-1, three sad butyl tins 0.4-1,
It is calcium ricinoleate 0.7-1, N-[2-(2-methyl-4-oxopentyl) 0.8-1, copper 8-quinolinolate 1-2, magnesium stearate 1-2, iron chloride 3.7-4, poly-
Vinyl chloride 100-130, calcium stearate 1-2.
A kind of preparation method of described silane-modified self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned maleic anhydride is added in the deionized water of its weight 27-30 times, is stirred, liter high-temperature is 54-60
DEG C, insulated and stirred 3-5 minute, above-mentioned N-[2-(2-methyl-4-oxopentyl) is added, continue insulated and stirred 6-9 minute, add above-mentioned stearic acid
Magnesium, stirs to room temperature, sucking filtration, and filter cake is washed 2-3 time, and 1-2 hours are vacuum dried at 37-40 DEG C, obtains 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,
Deca concentration is the ammonia spirit of 5.4-6%, and regulation pH is 8-9, and sucking filtration will precipitate the deionization for being added to 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, protected at 100-105 DEG C
Temperature stirring 4-5 hours, in sending into 57-60 DEG C of baking oven, drying, discharging obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned calcium ricinoleate is added in the dehydrated alcohol of its weight 10-17 times, is stirred, liter high-temperature is 60-65
DEG C, insulated and stirred 10-13 minute, above-mentioned three sad butyl tins, Fe2O3 doping titanium dioxide are added, stir to room temperature, filter, will be heavy
Form sediment and wash 3-4 time, normal temperature drying obtains Modified Iron titania-doped；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of its weight 50-60 times, Deca acetic acid, regulation pH is 5-
6, stir, add above-mentioned Modified Iron titania-doped, ultrasonic 20-30 minutes, sucking filtration obtains Silane Grafted doping titanium dioxide
Titanium；
（5）By above-mentioned Silane Grafted is titania-doped, the mixing of modified filler, calcium stearate, compound weight 37-40 is added to
In dimethyl sulfoxide again, ultrasonic 5-7 minutes, above-mentioned methyl methacrylate, azodiisobutyronitrile are added, at 57-60 DEG C
Insulated and stirred 4-6 hour, centrifugation, by precipitation absolute ethanol washing 3-4 time, is vacuum dried 1-2 little at 50-60 DEG C
When, obtain titania-doped graft polymers；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1-2 is little at 70-80 DEG C
When, double screw extruder is sent into, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
It is an advantage of the invention that：
The present invention silane coupler is anchored in into less aggregate surface, reduce titania-doped particle surface energy and
Surface activity, prevents doping particle itself that soft-agglomerated phenomenon occurs, and due to particle diameter very little of adulterating, enhances and is covered in doping
Active force between the coupling agent molecule of particle surface and the sterically hindered repulsive force produced because coupling agent adsorbs, its
Secondary, after polymethyl methacrylate is grafted on into silane treatment by emulsion graft polymerization in situ particle surface, realizes particle table
Face organises completely, the carbochain for causing inorganic nano doping particle surface is extended, especially polymethyl methacrylate
After linear long-chain molecule is introduced by emulsion graft polymerization, hence it is evident that improve inorganic/organic biphase interfacial structure, increased the compatibility,
Improve the stability of composite；The titania-doped graft polymers that the present invention is added can increase matrix resin strand
Intersegmental crosslink density, causes organic matrix macromolecular chain certain distance from shortening, and intermolecular active force is strengthened, secondly, anchoring
Grafting and the realization of emulsion graft polymerization so that the two-phase interface compatibility is enhanced, bonding interface effect is further reinforced, these works
Final result results in organic molecule chain movement ability in system and reduces, and improves the heat resistance of composite, in addition,
The Fe2O3 doping titanium dioxide that the present invention is added has good photo-catalysis capability, the contaminant degradation that can adhere to plate surface
Remove, so as to realize self-cleaning performance, the present invention adopts silane-modified process, can effectively improve the hydrophobic of finished product sheet material
Property, improve dispersibility of the filler grain between polymer.
Specific embodiment
A kind of silane-modified self-clean type plastic plate, it is made up of the raw material of following weight parts：
Maleic anhydride 0.8, Triallyl isocyanurate 0.3, the hydrogen peroxide 6, methyl methacrylate of titanium tetrachloride 10,25%
Ester 7, azodiisobutyronitrile 0.1, silane coupler kh5600.7, three sad butyl tins 0.4, calcium ricinoleate 0.7, diacetone acrylamide
Amide 0.8,8 copper quinolinates 1, magnesium stearate 1, iron chloride 3.7, polrvinyl chloride 100, calcium stearate 1.
A kind of preparation method of described silane-modified self-clean type plastic plate, comprises the following steps：
（1）Above-mentioned maleic anhydride is added in the deionized water of 27 times of its weight, is stirred, it is 54 DEG C to rise high-temperature, is protected
Temperature stirring 3 minutes, adds above-mentioned N-[2-(2-methyl-4-oxopentyl), continues insulated and stirred 6 minutes, adds above-mentioned magnesium stearate, stir to
Room temperature, sucking filtration washes filter cake 2 times, is vacuum dried 1 hour at 37 DEG C, obtains modified filler；
（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 obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned calcium ricinoleate is added in the dehydrated alcohol of 10 times of its weight, is stirred, it is 60 DEG C to rise high-temperature, is protected
Temperature stirring 10 minutes, adds above-mentioned three sad butyl tins, Fe2O3 doping titanium dioxide, stirs to room temperature, filters, by precipitation washing 3
Secondary, normal temperature drying obtains Modified Iron titania-doped；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of 50 times of its weight, Deca acetic acid, it is 5 to adjust pH, stirring
Uniformly, add above-mentioned Modified Iron titania-doped, ultrasound 20 minutes, sucking filtration obtains Silane Grafted titania-doped；
（5）By above-mentioned Silane Grafted is titania-doped, the mixing of modified filler, calcium stearate, 37 times of compound weight is added to
Dimethyl sulfoxide in, ultrasound 5 minutes adds above-mentioned methyl methacrylate, azodiisobutyronitrile, the insulated and stirred at 57 DEG C
4 hours, centrifugation, by precipitation absolute ethanol washing 3 times, was vacuum dried 1 hour at 50 DEG C, obtains titania-doped connecing
Branch polymer；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1 hour, send at 70 DEG C
Enter double screw extruder, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
Performance test：
Tensile strength： 45.1MPa；
Bending strength： 79MPa；
Anti-flammability：Put out from fire, without black smoke.
Claims (2)
1. a kind of silane-modified self-clean type plastic plate, it is characterised in that it is made up of the raw material of following weight parts：
Maleic anhydride 0.8-2, Triallyl isocyanurate 0.3-1, the hydrogen peroxide 6-8 of titanium tetrachloride 10-14,25-30%,
Methyl methacrylate 7-9, azodiisobutyronitrile 0.1-0.2, silane coupler kh5600.7-1, three sad butyl tins 0.4-1,
It is calcium ricinoleate 0.7-1, N-[2-(2-methyl-4-oxopentyl) 0.8-1, copper 8-quinolinolate 1-2, magnesium stearate 1-2, iron chloride 3.7-4, poly-
Vinyl chloride 100-130, calcium stearate 1-2.
2. a kind of preparation method of silane-modified self-clean type plastic plate as claimed in claim 1, it is characterised in that include with
Lower step：
（1）Above-mentioned maleic anhydride is added in the deionized water of its weight 27-30 times, is stirred, liter high-temperature is 54-60
DEG C, insulated and stirred 3-5 minute, above-mentioned N-[2-(2-methyl-4-oxopentyl) is added, continue insulated and stirred 6-9 minute, add above-mentioned stearic acid
Magnesium, stirs to room temperature, sucking filtration, and filter cake is washed 2-3 time, and 1-2 hours are vacuum dried at 37-40 DEG C, obtains 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,
Deca concentration is the ammonia spirit of 5.4-6%, and regulation pH is 8-9, and sucking filtration will precipitate the deionization for being added to 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, protected at 100-105 DEG C
Temperature stirring 4-5 hours, in sending into 57-60 DEG C of baking oven, drying, discharging obtains Fe2O3 doping titanium dioxide；
（3）Above-mentioned calcium ricinoleate is added in the dehydrated alcohol of its weight 10-17 times, is stirred, liter high-temperature is 60-65
DEG C, insulated and stirred 10-13 minute, above-mentioned three sad butyl tins, Fe2O3 doping titanium dioxide are added, stir to room temperature, filter, will be heavy
Form sediment and wash 3-4 time, normal temperature drying obtains Modified Iron titania-doped；
（4）Above-mentioned silane coupler kh560 is taken, in being added to the acetone of its weight 50-60 times, Deca acetic acid, regulation pH is 5-
6, stir, add above-mentioned Modified Iron titania-doped, ultrasonic 20-30 minutes, sucking filtration obtains Silane Grafted doping titanium dioxide
Titanium；
（5）By above-mentioned Silane Grafted is titania-doped, the mixing of modified filler, calcium stearate, compound weight 37-40 is added to
In dimethyl sulfoxide again, ultrasonic 5-7 minutes, above-mentioned methyl methacrylate, azodiisobutyronitrile are added, at 57-60 DEG C
Insulated and stirred 4-6 hour, centrifugation, by precipitation absolute ethanol washing 3-4 time, is vacuum dried 1-2 little at 50-60 DEG C
When, obtain titania-doped graft polymers；
（6）Above-mentioned titania-doped graft polymers are mixed with remaining each raw material, insulated and stirred 1-2 is little at 70-80 DEG C
When, double screw extruder is sent into, extrusion, mould molding, cut off, overlay film, obtain final product the plastic plate.
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| CN201611010164.8A CN106633495A (en) | 2016-11-17 | 2016-11-17 | Silane modified self-cleaning plastic sheet and preparation method thereof |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602147A (en) * | 2016-01-29 | 2016-05-25 | 宁波远欣石化有限公司 | Anticorrosion stable anti-aging plastic plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602147A (en) * | 2016-01-29 | 2016-05-25 | 宁波远欣石化有限公司 | Anticorrosion stable anti-aging plastic plate |
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Application publication date: 20170510 |