CN107383595B - A kind of anti-ultraviolet polypropene composition and its polypropylene and polypropylene film of preparation - Google Patents
A kind of anti-ultraviolet polypropene composition and its polypropylene and polypropylene film of preparation 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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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- 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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a kind of preparation methods of surface-modified nano cerium oxide, and its surface-modified nano cerium oxide and purposes being prepared, the present invention also provides polypropylene and polypropylene film prepared by a kind of polypropene composition including the surface-modified nano cerium oxide and the composition.The surface-modified nano cerium oxide is that large-particle cerium oxide and surface modifier react in the high-temperature high-pressure microdmain that laser bombardment generates, cerium oxide is set to be reduced in size to nanoscale surface grafting upper surface modifying agent simultaneously, on the one hand the surface-modified nano cerium oxide being prepared using such method can be more effectively surface-treated to cerium oxide；On the other hand nanoscale cerium can be prepared from micron order cerium oxide, saved material cost；Furthermore during the preparation process, since columned cerium oxide solid target can constantly be lowered into Flowing liquid, this preparation method has the advantages that be carried out continuously.
Description
Technical field
The present invention relates to technical field of plastic, and in particular to a kind of anti-ultraviolet polypropene composition and its preparation
Polypropylene and polypropylene film.
Background technique
Ultraviolet light in sunlight is the main reason for causing high molecular material that aging occurs, and high molecular material can absorb purple
Outside line and cause self oxidation, cause polymer to be degraded, this process is known as photoredox or light aging.Although ultraviolet light is only
5% or so of sunlight is accounted for, but energy is huge, energy is enough to destroy the chemical bond of polymer, be broken the generation of its strand,
Crosslinking causes its mechanical property that canceration occurs, meanwhile, color can also change.
Ultraviolet light can be divided into shortwave area (i.e. UVC:200nm-290nm), medium wave area (i.e. UVB:290nm-320nm) by wavelength
With long-wavelength region (i.e. UVA:320nm-400nm).
The ultraviolet light that wavelength is shorter than 290nm when sunlight penetrates atmosphere is fallen by the Ozone Absorption in atmosphere, so, make
The ultraviolet wavelength that aging occurs for high molecular material is concentrated mainly within the scope of 290nm-400nm.
Polypropylene (PP) is a kind of superior thermoplastic of comprehensive performance, has very extensive answer in industrial application
With, such as household electrical appliance, building element, house decorative material, automobile component, flexible packing material.But due to polypropylene molecule
The characteristic of structure so that its sunlight irradiation under weather resistance it is bad, it is particularly sensitive to ultraviolet light, thus limit its
Outdoor use.Polyacrylic anti-ultraviolet aging is the important research direction of numerous technical staff at this stage.
The method that tradition improves polypropylene (PP) anti-ultraviolet property, is mainly added in polyacrylic preparation process
The components such as machine stabilizer such as organic uv absorbers (UVA) and hindered amine light stabilizer (HALS), but all due to UVA and HALS
It is the organic synthesis object lower than acrylic resin molecular weight, either still has to the capture of free radical to the absorption of ultraviolet light
Certain limitation, and can occur to migrate and degrade with the extension of use time, cause the UV Aging Resistance meeting of material
It is gradually reduced, ultimate failure.
Compared with traditional technology, the inorganic material of nanoscale has stronger function of shielding ultraviolet radiation, and has nothing
Poison such as stablizes, does not migrate at the good characteristics, can preferably overcome the shortcomings of above-mentioned organic stabilizer.Studies have shown that specific surface area
Size decides that nano material improves the degree of photostability.The method of usual increasing specific surface area is to reduce particle ruler as far as possible
It is very little, but particle is smaller, dispersion is more difficult, and it is easy to reunite at bulky grain, the screening ability of ultraviolet light can be declined instead.Currently, specially
There is the report for relatively mostly using inorganic nanoparticles to improve PP anti-ultraviolet property in benefit, but improvement is limited, it is steady for PP light
It qualitatively improves and need to be further improved.
Summary of the invention
In order to overcome the drawbacks of the prior art, an object of the present invention is to provide a kind of surface-modified nano cerium oxide
Preparation method and its surface-modified nano cerium oxide and purposes being prepared.
The second object of the present invention is to provide a kind of polypropene composition and preparation method thereof that anti-ultraviolet property is excellent；
It include above-mentioned surface-modified nano cerium oxide in the composition.
The third object of the present invention is to provide a kind of polypropylene, and the polypropylene is prepared by above-mentioned polypropene composition
It obtains.
The fourth object of the present invention is to provide a kind of polypropylene film, and the polypropylene film is by above-mentioned polypropylene system
For what is obtained.
Object of the present invention is to what is be achieved through the following technical solutions:
A kind of preparation method of surface-modified nano cerium oxide, described method includes following steps:
(a) Flowing liquid is prepared, the Flowing liquid includes surface modifier and ethyl alcohol；
(b) cerium oxide is impregnated in the Flowing liquid of step (a), is immersed in the stream continuously flowed with high energy laser beam bombardment
The cerium oxide of surface grafting surface modifier is prepared in the surface of cerium oxide in hydrodynamic phase.
According to the present invention, in step (a), the mass ratio of surface modifier and ethyl alcohol is 1:(5- in the Flowing liquid
20), for example, 1:(10-15), be specifically as follows 1:10.
According to the present invention, the surface modifier be selected from amino silane, epoxy radicals silicone hydride, methacryloxypropyl silane,
At least one of vinyl silanes, isocyanato silanes.
According to the present invention, in step (b), the cerium oxide being impregnated in the Flowing liquid of step (a) is oxidation cerium tablet
Form.For example, the cerium oxide tabletting that partial size is 1~3 μm is prepared into columned oxidation cerium tablet, used as solid target.
In the present invention, the size of the oxidation cerium tablet is not limited, it will be understood by those skilled in the art that the cerium oxide
As long as the size of piece matches with the device space.
According to the present invention, the height that the oxidation cerium tablet is impregnated in the part in Flowing liquid is 0.2mm~1mm.
According to the present invention, the flow of the Flowing liquid is 0.01~0.04mL/s.
According to the present invention, the high energy laser beam is CO2Pulse gas-laser beam or nd yag doubled-frequency laser beam.
According to the present invention, the laser beam is bombarded under the protection of nitrogen and is immersed in the Flowing liquid continuously flowed
The cerium oxide surface.
In the present invention, the cerium oxide is impregnated in the Flowing liquid of step (a), without additional heating, is swashed by high energy
Light bombardment oxidation cerium tablet can generate high temperature moment, and then be reacted on oxidation cerium tablet surface, and surface modification is prepared and receives
Rice cerium oxide.
In the present invention, flow control of reaction time of the oxidation cerium tablet in Flowing liquid by Flowing liquid, height
Can the position of laser beam bombardment oxidation cerium tablet always exist high-temperature area, Flowing liquid by when this oxidation cerium tablet surface therewith
Reaction, then again by subsequent liquid substitution.
In the present invention, the oxidation cerium tablet is impregnated in the height of the part in Flowing liquid and constantly regulate, it is specific and
Speech, by control oxidation cerium tablet be impregnated in the height in Flowing liquid, such as make aoxidize cerium tablet constantly into Flowing liquid under
It visits, guarantees that reaction can continue to carry out；By being added continuously oxidation cerium tablet, being carried out continuously for reaction is realized.
Specifically, the preparation method of the modified cerium oxide in the surface specifically comprises the following steps:
(a ') by the oxidation cerium tablet that partial size is that 1~3 μm of cerium oxide is pressed into tablet press machine cylindrical pellets structure, as solid
Body target；Surface modifier and ethyl alcohol are mixed according to the mass fraction ratio of 1:10, as Flowing liquid；
The solid target of step (a ') is impregnated in the Flowing liquid by (b '), and the solid target is impregnated in Flowing liquid
The height of part be 0.2mm~1mm, the flow of Flowing liquid is 0.01~0.04mL/s；It is bombarded and is impregnated with high energy laser beam
The surface of the solid target in the Flowing liquid continuously flowed obtains cerium oxide surface grafting upper surface modifying agent
Suspension；The suspension of acquisition is washed, is filtered, it is dry, obtain surface-modified nano cerium oxide.
The present invention also provides a kind of surface-modified nano cerium oxide, and the above method is used to be prepared；The surface changes
Property nano-cerium oxide be surface grafting surface modifier nano-cerium oxide；The particle diameter distribution of the surface-modified nano cerium oxide
For D50=80nm~150nm, meanwhile, D97=D50+ 20nm, D5=D50-20nm。
In the present invention, the D50The index for indicating particle diameter distribution indicates that 50% particle size is less than some numerical value,
Such as D50=80nm indicates that 50% particle size is less than 80nm；D97And D5Definition similarly.
According to the present invention, the pattern of the surface-modified nano cerium oxide is hollow ball shape or cubic.
According to the present invention, since the surface-modified nano cerium oxide uses completely new preparation method, specifically, using
Superlaser continuously bombards solid target and prepares nanometer surface modification cerium oxide, and it is modified that continuous one-step preparation surface may be implemented in this
It is more efficient to reach Nano grade for nano-powder, and without being surface-treated again after material reaches Nano grade, therefore
The surface-modified nano cerium oxide being prepared does not allow easy to reunite, more conducively its dispersion in polypropylene；Moreover, it prepares
The particle diameter distribution of obtained surface-modified nano cerium oxide is narrow, partial size is small.
The present invention also provides the purposes of above-mentioned surface-modified nano cerium oxide, are used to prepare uvioresistant product；It is preferred that
Ground is used to prepare anti-ultraviolet polypropene composition.
The present invention also provides a kind of polypropene composition, the composition includes following components according to mass percent meter:
(1) above-mentioned surface-modified nano cerium oxide, 0.05%~2%；(2) acrylic resin, 90%~99.75%；
(3) antioxidant, 0.1~2%；(4) lubricant, 0.1%~2%.
Preferably, the composition includes following components according to mass percent meter:
(1) above-mentioned surface-modified nano cerium oxide, 0.1%~1.5%；(2) acrylic resin, 96.5%~
99.2%；(3) antioxidant, 0.2~1.0%；(4) lubricant, 0.5%~1.0%.
According to the present invention, the acrylic resin is selected from least one of homopolypropylene, copolymer polypropylene；
According to the present invention, the molecular weight of the acrylic resin is 200000~600000g/mol；
According to the present invention, the antioxidant is selected from tetrapentaerythritol ester, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl
Phenyl) butane, β-(4- hydroxyl -3,5- di-tert-butyl-phenyl) propionic acid n-octadecyl alcohol ester, 1,3,5- tri- (4- tert-butyl -3- hydroxyl
Base -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 triketones, thiodipropionic acid dilauryl cinnamic acid, triphenyl phosphite, season penta
Tetrol bis-phosphite, one of misery diphenyl ester of phosphorous or combinations thereof.
According to the present invention, the lubricant is selected from the sub- second of stearic amide, erucyl amide, oleamide, paraffin, N-N '-
Base bis-stearamides, three hydroxy stearic acid ester of glycerol, polyethylene wax, oxidized polyethylene wax, methyl-silicone oil, one in polymethylphenyl siloxane fluid
Kind or combinations thereof.
The present invention also provides a kind of polypropylene, the polypropylene is prepared by above-mentioned composition.
According to the present invention, the polypropylene has anti-ultraviolet property.
According to the present invention, the polyacrylic melt index is 12.5~35.5g/10min.
The present invention also provides above-mentioned polyacrylic preparation methods, and described method includes following steps:
(1) each component in above-mentioned composition is weighed by weight percentage；
(2) each component in composition is uniformly mixed, extruding pelletization, the polypropylene is prepared.
According to the present invention, described to be combined by what high-speed mixer was uniformly mixed.
According to the present invention, the extruding pelletization is by double screw extruder extruding pelletization, and the extrusion temperature is 180-
195 DEG C, for example, 180 DEG C, 195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C.
The present invention also provides a kind of polypropylene film, the polypropylene film is prepared by above-mentioned polypropylene.
According to the present invention, the polypropylene film with a thickness of 10 μm~100 μm.
According to the present invention, uv transmittance≤10% of the polypropylene film.
The present invention also provides the preparation methods of above-mentioned polypropylene film, and described method includes following steps:
After above-mentioned polypropylene fusion is handled, through casting step, the polypropylene film is prepared.
According to the present invention, after casting step, it can also include stretching step, stretched polypropene film is prepared.
The beneficial effects of the present invention are:
The present invention provides a kind of surface-modified nano cerium oxide and its preparation method and application, and the present invention also provides one kind
The polypropylene and polypropylene film of polypropene composition and the composition preparation including the surface-modified nano cerium oxide.Institute
Stating surface-modified nano cerium oxide is large-particle cerium oxide and surface modifier in the high-temperature high-pressure microdmain that laser bombardment generates
It reacts, so that cerium oxide is reduced in size to nanoscale surface grafting upper surface modifying agent simultaneously, prepared using such method
On the one hand obtained surface-modified nano cerium oxide can be more effectively surface-treated to cerium oxide；It on the other hand can be with
Nanoscale cerium is prepared from micron order cerium oxide, has saved material cost；Furthermore it is during the preparation process, described due to piece
The cerium oxide solid target of shape can the constantly test into Flowing liquid, therefore, this preparation method have can be carried out continuously it is excellent
Point.
Simultaneously as good surface modification and lesser powder size, nano-cerium oxide can be better dispersed in poly-
In allyl resin, the effect of shielding ultraviolet rays is played.Therefore, the uvioresistant polypropylene that is prepared and polypropylene film it is anti-
It is ultraviolet to have excellent performance, after carrying out ultraviolet ageing test 9 months according to standard ASTM-D4329-2005, the UV light permeability of film
Still≤10%, mechanical strength still 80% or more of original strength of materials, does not have much affect to the transparency of material rate.
Detailed description of the invention
Fig. 1 is preparation facilities schematic diagram of the present invention；
Wherein, 1 is superlaser generator；2 be laser reflection system；3 be liquid phase fluid reservoir；4 is outstanding for nano-cerium oxide
Supernatant liquid collector；5 be to prepare reaction chamber；6 be fixed target controller；7 be liquid phase flow rate controller.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.Furthermore, it is to be understood that after having read documented content of the invention, this field skill
Art personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within limited range of the present invention.
Instrument and equipment:
In the present embodiment, the ultraviolet ageing is carried out according to standard ASTM-D4329-2005.
In the present embodiment, the ultraviolet permeability be on 950 type UV-Vis spectrophotometry tester of Lambda,
It 23 DEG C, is tested under conditions of 65%RH.
In the present embodiment, the mechanical strength is tested according to standard GB 13022-91 in universal testing machine.
In the present embodiment, the mist degree is produced according to standard GBT 2410-2008 by BYK-Gardner Gmbh company
Reinforced #4725 mist degree instrument tested.
In the present embodiment, the high energy laser beam is CO2Pulse gas-laser beam or nd yag doubled-frequency laser beam.
Wherein, the CO2Pulse gas-laser beam is wavelength 10600nm, pulse duration 0.5ms；The neodymium-doped yttrium-aluminum garnet
Laser beam is wavelength 1064nm, pulse duration 0.5ms.
Embodiment 1
A kind of uvioresistant polypropylene film preparation method, the preparation method of the film include the following steps:
(1) cerium oxide surface is modified: the cerium oxide that initial size is 1 μm is pressed into tablet press machine it is cylindric, as solid
Target；Surface modifier and ethyl alcohol are mixed according to the mass fraction ratio of 1:10, as Flowing liquid；
The solid target is set to be impregnated into the Flowing liquid, the height that solid target is immersed in the part in Flowing liquid is
0.2mm, the flow of Flowing liquid are 0.01ml/s；
With the surface for the solid target that high energy laser beam bombardment is immersed in the Flowing liquid continuously flowed, obtain
The suspension of cerium oxide surface grafting upper surface modifying agent, and cerium oxide is decomposed into nanometer due to being bombarded by superlaser
Size, modified cerium oxide partial size are D50=80nm, while D97=100nm, D5=60nm；
Suspension liquid obtained is washed, is filtered, it is dry, obtain surface-modified nano cerium oxide.
(2) by 0.2% step (1) preparation the modified oxidized cerium in surface, 99.1% acrylic resin, 0.2% antioxidant,
0.5% lubricant is uniformly mixed by high-speed mixer, uses double screw extruder extruding pelletization, extrusion temperature are as follows: 180 DEG C,
195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C, are prepared polypropylene particles；
(3) particle prepared by step (2) is fabricated to film using casting machine, uvioresistant as of the present invention is poly-
Polypropylene film.
Wherein, the high energy laser beam is CO2Pulse gas-laser beam.
Wherein, described in the laser beam is bombarded under the protection of nitrogen and is immersed in the Flowing liquid continuously flowed
The surface of solid target.
Wherein, the surface modifier is amino silane.
Wherein, polypropylene film with a thickness of 50 μm.
Embodiment 2
A kind of uvioresistant polypropylene film preparation method, the preparation method of the film include the following steps:
(1) cerium oxide surface is modified: the cerium oxide that initial size is 2 μm is pressed into tablet press machine it is cylindric, as solid
Target；Surface modifier and ethyl alcohol are mixed according to the mass fraction ratio of 1:10, as Flowing liquid；
The solid target is set to be impregnated into the Flowing liquid, the height that solid target is immersed in the part in Flowing liquid is
0.6mm, the flow of Flowing liquid are 0.02ml/s；
With the surface for the solid target that high energy laser beam bombardment is immersed in the Flowing liquid continuously flowed, obtain
The suspension of cerium oxide surface grafting upper surface modifying agent, and cerium oxide is decomposed into nanometer due to being bombarded by superlaser
Size, modified cerium oxide partial size are D50=100nm, while D97=120nm, D5=80nm；
Suspension liquid obtained is washed, is filtered, it is dry, obtain surface-modified nano cerium oxide.
(2) by 1.0% step (1) preparation the modified oxidized cerium in surface, 97.7% acrylic resin, 0.5% antioxidant,
0.8% lubricant is uniformly mixed by high-speed mixer, uses double screw extruder extruding pelletization, extrusion temperature are as follows: 180 DEG C,
195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C, are prepared polypropylene particles；
(3) particle prepared by step (2) is fabricated to film using casting machine, uvioresistant as of the present invention is poly-
Polypropylene film.
Wherein, the high energy laser beam is nd yag doubled-frequency laser beam.
Wherein, described in the laser beam is bombarded under the protection of nitrogen and is immersed in the Flowing liquid continuously flowed
The surface of solid target.
Wherein, the surface modifier is epoxy radicals silicone hydride.
Wherein, polypropylene film with a thickness of 50 μm.
Embodiment 3
A kind of uvioresistant polypropylene film preparation method, the preparation method of the film include the following steps:
(1) cerium oxide surface is modified: the cerium oxide that initial size is 3 μm is pressed into tablet press machine it is cylindric, as solid
Target；Surface modifier and ethyl alcohol are mixed according to the mass fraction ratio of 1:10, as Flowing liquid；
The solid target is set to be impregnated into the Flowing liquid, the height that solid target is immersed in the part in Flowing liquid is
1mm, the flow of Flowing liquid are 0.04ml/s；
With the surface for the solid target that high energy laser beam bombardment is immersed in the Flowing liquid continuously flowed, obtain
The suspension of cerium oxide surface grafting upper surface modifying agent, and cerium oxide is decomposed into nanometer due to being bombarded by superlaser
Size, modified cerium oxide partial size are D50=150nm, while D97=170nm, D5=130nm；
Suspension liquid obtained is washed, is filtered, it is dry, obtain surface-modified nano cerium oxide.
(2) by 1.5% step (1) preparation the modified oxidized cerium in surface, 96.5% acrylic resin, 1.0% antioxidant,
1.0% lubricant is uniformly mixed by high-speed mixer, uses double screw extruder extruding pelletization, extrusion temperature are as follows: 180 DEG C,
195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C, are prepared polypropylene particles；
(3) particle prepared by step (2) is fabricated to film using casting machine, uvioresistant as of the present invention is poly-
Polypropylene film.
Wherein, the high energy laser beam is CO2Pulse gas-laser beam.
Wherein, described in the laser beam is bombarded under the protection of nitrogen and is immersed in the Flowing liquid continuously flowed
The surface of solid target.
Wherein, the surface modifier is methacryloxypropyl silane.
Wherein, polypropylene film with a thickness of 50 μm.
Comparative example 1
By 3% commercially available nano-cerium oxide (average grain diameter is about 80nm), 95% acrylic resin, 1.0% antioxidant,
1.0% lubricant is uniformly mixed by high-speed mixer, uses double screw extruder extruding pelletization, extrusion temperature are as follows: 180 DEG C,
195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C, are prepared polypropylene particles；Reuse casting machine particle is fabricated to it is thin
Film.
Wherein, polypropylene film with a thickness of 50 μm.
Comparative example 2
By 2% commercially available nano-cerium oxide (average grain diameter is about 80nm), 1% nano-titanium dioxide, (average grain diameter is about
80nm), 95% acrylic resin, 1.0% antioxidant, 1.0% lubricant are uniformly mixed by high-speed mixer, use twin-screw
Extruder extruding pelletization, extrusion temperature are as follows: polypropylene is prepared in 180 DEG C, 195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C
Particle；It reuses casting machine and particle is fabricated to film.
Wherein, polypropylene film with a thickness of 50 μm.
Comparative example 3
By 3% commercially available nano-cerium oxide (average grain diameter is about 80nm), 1% nano-titanium dioxide, (average grain diameter is about
80nm), 95% acrylic resin, 1.0% antioxidant, 1.0% lubricant are uniformly mixed by high-speed mixer, use twin-screw
Extruder extruding pelletization, extrusion temperature are as follows: polypropylene is prepared in 180 DEG C, 195 DEG C, 195 DEG C, 200 DEG C, 190 DEG C, 195 DEG C
Particle；It reuses casting machine and particle is fabricated to film.
Wherein, polypropylene film with a thickness of 50 μm.
Comparative example 4
The commercially available uvioresistant polypropylene film using the organic anti ultraviolet agent of addition, 50 μm of thickness.
The performance test results of the polypropylene film of table 1 embodiment 1-3 and comparative example 1-4
From the data of table 1 as it can be seen that polypropylene film prepared by the present invention has excellent anti-ultraviolet property, process is ultraviolet
After aging, the fall of properties is far below commercially available use and adds organic anti ultraviolet agent product produced and add it
The polypropylene film of his nano particle.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (29)
1. a kind of preparation method of surface-modified nano cerium oxide, which is characterized in that described method includes following steps:
(a) Flowing liquid is prepared, the Flowing liquid includes surface modifier and ethyl alcohol；
(b) cerium oxide is impregnated in the Flowing liquid of step (a), is immersed in the flow fluid continuously flowed with high energy laser beam bombardment
The cerium oxide of surface grafting surface modifier is prepared in the surface of cerium oxide in phase；
Wherein, the surface modifier is selected from amino silane, epoxy radicals silicone hydride, methacryloxypropyl silane, vinyl silanes
At least one of with isocyanato silanes.
2. preparation method according to claim 1, which is characterized in that in step (a), surface is modified in the Flowing liquid
The mass ratio of agent and ethyl alcohol is 1:(5-20).
3. preparation method according to claim 2, which is characterized in that in step (a), surface is modified in the Flowing liquid
The mass ratio of agent and ethyl alcohol is 1:(10-15).
4. preparation method according to claim 3, which is characterized in that in step (a), surface is modified in the Flowing liquid
The mass ratio of agent and ethyl alcohol is 1:10.
5. preparation method according to claim 1, which is characterized in that in step (b), the stream for being impregnated in step (a)
Cerium oxide in hydrodynamic phase is the form for aoxidizing cerium tablet.
6. preparation method according to claim 5, which is characterized in that the cerium oxide tabletting that partial size is 1~3 μm to be prepared into
Columned oxidation cerium tablet, uses as solid target.
7. preparation method according to claim 5, which is characterized in that the oxidation cerium tablet is impregnated in the portion in Flowing liquid
The height divided is 0.2mm~1mm.
8. preparation method according to claim 1, which is characterized in that the flow of the Flowing liquid is 0.01~0.04mL
/s。
9. preparation method according to claim 1, which is characterized in that the high energy laser beam is CO2Pulse gas-laser beam
Or nd yag doubled-frequency laser beam.
10. preparation method according to claim 9, which is characterized in that the laser beam bombards leaching under the protection of nitrogen
The surface of the cerium oxide of the stain in the Flowing liquid continuously flowed.
11. preparation method according to claim 1, which is characterized in that the preparation method specifically comprises the following steps:
(a ') by the oxidation cerium tablet that partial size is that 1~3 μm of cerium oxide is pressed into tablet press machine cylindrical pellets structure, as solid
Target；Surface modifier and ethyl alcohol are mixed according to the mass fraction ratio of 1:10, as Flowing liquid；
The solid target of step (a ') is impregnated in the Flowing liquid by (b '), and the solid target is impregnated in the portion in Flowing liquid
The height divided is 0.2mm~1mm, and the flow of Flowing liquid is 0.01~0.04ml/s；The company of being immersed in is bombarded with high energy laser beam
The surface of the solid target in the dynamic Flowing liquid of afterflow, obtains the suspension of cerium oxide surface grafting upper surface modifying agent
Liquid；The suspension of acquisition is washed, is filtered, it is dry, obtain surface-modified nano cerium oxide.
12. a kind of surface-modified nano cerium oxide uses the described in any item methods of claim 1-11 to be prepared；It is described
Surface-modified nano cerium oxide is the nano-cerium oxide of surface grafting surface modifier；The grain of the surface-modified nano cerium oxide
Diameter is distributed as D50=80nm~150nm, meanwhile, D97=D50+ 20nm, D5=D50-20nm。
13. surface-modified nano cerium oxide according to claim 12, which is characterized in that the surface-modified nano oxidation
The pattern of cerium is hollow ball shape or cubic.
14. the purposes of surface-modified nano cerium oxide described in claim 12 or 13, is used to prepare uvioresistant product.
15. the purposes of surface-modified nano cerium oxide described in claim 12 or 13 is used to prepare anti-ultraviolet poly- third
Ene compositions.
16. a kind of polypropene composition, which is characterized in that the composition includes following components according to mass percent meter:
(1) the described in any item methods of claim 1-11 be prepared or claim 12 or 13 described in surface-modified nano
Cerium oxide, 0.1%~1.5%；(2) acrylic resin, 96.5%~99.2%；(3) antioxidant, 0.2~1.0%；(4) it lubricates
Agent, 0.5%~1.0%.
17. polypropene composition according to claim 16, which is characterized in that the acrylic resin is selected from homopolymerization poly- third
At least one of alkene, copolymer polypropylene.
18. polypropene composition according to claim 16, which is characterized in that the molecular weight of the acrylic resin is
200000~600000g/mol.
19. polypropene composition according to claim 16, which is characterized in that the antioxidant is selected from tetrapentaerythritol
Ester, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, propionic acid is just by β-(4- hydroxyl -3,5- di-tert-butyl-phenyl)
Octadecanol ester, 1,3,5- tri- (4- tert-butyl -3- hydroxyl -2,6- dimethyl benzyl) -1,3,5-triazines -2,4,6 triketones are thio
Dipropionic acid tin dilaurate, triphenyl phosphite, pentaerythritol bis-phosphite, one of misery diphenyl ester of phosphorous or its group
It closes.
20. polypropene composition according to claim 16, which is characterized in that the lubricant be selected from stearic amide,
Erucyl amide, oleamide, paraffin, N-N '-ethylenebisstearamide, three hydroxy stearic acid ester of glycerol, polyethylene wax, oxidation are poly-
Ethylene waxes, methyl-silicone oil, one of polymethylphenyl siloxane fluid or combinations thereof.
21. a kind of polypropylene, which is characterized in that the polypropylene is prepared by the described in any item compositions of claim 16-20
It obtains.
22. polyacrylic preparation method described in claim 21, which is characterized in that described method includes following steps:
(1) each component in the described in any item compositions of claim 16-20 is weighed by weight percentage；
(2) each component in composition is uniformly mixed, extruding pelletization, the polypropylene is prepared.
23. polyacrylic preparation method according to claim 22, which is characterized in that described to be combined by mixed at high speed
What machine was uniformly mixed.
24. polyacrylic preparation method according to claim 22, which is characterized in that the extruding pelletization is by double spiral shells
Bar extruder extruding pelletization, the extrusion temperature are 180-195 DEG C.
25. a kind of polypropylene film, which is characterized in that polypropylene film polypropylene as described in claim 21 is prepared into
It arrives.
26. polypropylene film according to claim 25, which is characterized in that the polypropylene film with a thickness of 10 μm~
100μm。
27. polypropylene film according to claim 25, which is characterized in that the uv transmittance of the polypropylene film
≤ 10%, the uv transmittance is that test completion is carried out under conditions of 65%RH at 23 DEG C.
28. the preparation method of the described in any item polypropylene films of claim 25-27, which is characterized in that the method includes
Following steps:
After the processing of polypropylene fusion described in claim 21, through casting step, the polypropylene film is prepared.
29. the preparation method of polypropylene film according to claim 28, which is characterized in that after casting step, further include
Stretched polypropene film is prepared in stretching step.
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