CN107033387A - Nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their preparation method and application - Google Patents
Nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their preparation method and application Download PDFInfo
- Publication number
- CN107033387A CN107033387A CN201611089693.1A CN201611089693A CN107033387A CN 107033387 A CN107033387 A CN 107033387A CN 201611089693 A CN201611089693 A CN 201611089693A CN 107033387 A CN107033387 A CN 107033387A
- Authority
- CN
- China
- Prior art keywords
- lanthanum oxide
- cerium
- nano lanthanum
- nano
- oxide cerium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention discloses a kind of nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their preparation method and application.The molecular formula of nano lanthanum oxide cerium is：LaxCe1‑0.75xO2, wherein, 0<x<0.5.Nano lanthanum oxide cerium material prepared by the present invention is presented specificity in ultra-violet (UV) band and absorbed, and can effectively reduce the catalytic oxidation activity of high polymer material, be a kind of brand-new uvioresistant absorbing material.The present invention is by having this nano-particle material of preferable uvioresistant absorbent properties to be added in high polymer material (such as BOPA films), so as to obtain the material with excellent anti-ultraviolet property.
Description
Technical field
It is anti-more particularly, to a kind of nano lanthanum oxide cerium, containing it the invention belongs to nano-functional material technical field
Ultraviolet materials and their preparation method and application.
Background technology
Two-way stretching polyamide film (BOPA films) is that yield is maximum in polyamide series, most popular kind it
One, it is good etc. with excellent resistance to rupture, impact resistance, draftability compared with traditional polyethylene (PE), polypropylene (PP) film etc.
Performance characteristics.Material is obstructed compared to low density polyethylene (LDPE), ethylene-vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC) etc.
Material, BOPA films also have outstanding barrier properties for gases, to O2And CO2Deng barrier it is higher than low density polyethylene (LDPE) 100 times；And
And temperature resistant range is wide, the transparency is good.Therefore, BOPA films are widely used as the neck such as food processing, medical and health, chemical products
The packaging material in domain, is particularly suitable for freezing, is vacuum-packed, and is far longer than conventional packaging to the fresh-keeping of food, the fragrant effect of guarantor
Material.At present, the huge market demand has been formed to BOPA films both at home and abroad, it is contemplated that the five-year whole world is to BOPA films
The market demand will be increased with annual 15-20% speed.
But, current BOPA films are faced with photo-aging problem, that is, are chronically exposed to aging when being used under ultraviolet and drop
Solution, discoloration is even brittle.On the one hand the problem forms white pollution everywhere and causes the waste of film, on the other hand causes BOPA
The class of film is not high, it is impossible to which lift technique added value simultaneously occupies high-end market.
The conventional method for improving material anti-photoluminescence ageing properties is addition organic uv absorbers or ultraviolet light screener.
For organic uv absorbers, antioxidant and light stabilizer can be divided into from mechanism, specific such as Hinered phenols,
Phosphorous acid esters, thio-based and hindered amines etc., it is fundamentally the work for generating high energy ultraviolet scissionable polymers strand
Free love base is captured or is quenched.It is a process for consumption as absorbed but this method has inborn deficiency, absorbent gradually can
Rotten deterioration, causes the transparency of material to decline or even change colour.
For ultraviolet light screener, such as based on nano inoganic particle (such as nano-ZnO, nano-TiO2Deng) ultraviolet screen
Cover agent, because its have the advantages that good chemical stability, heat endurance and shield ranges it is wide enjoy the favor of people.But
There is high catalytic activity while nano-ZnO is as light stabilizer, when UV energy is more than ZnO energy gaps
(3.0eV), electronics, which will be excited, to be crossed forbidden band and enters conduction band, produces electron-hole pair.Hole is by the OH in oxidation environment-, lead
Cause ultraviolet shielded failure.To nano-TiO2For, although its energy gap reaches 3.2eV, but its refractive index n is close to 2.5 (rutile titanias
Ore deposit) and 2.7 (Rutile Types).Color and luster seems unnatural after incorporation BOPA films, and then limits its application.Ceria
(CeO2) 4f electronics to visible ray without absorption, show excellent absorbability to ultraviolet, while energy gap reaches 3.4,
Catalytic activity can be preferably reduced, so as to be applied in uvioresistant new material.But, for nano Ce O2It is doped to height
In molecular material, still there is technical barrier to have to be solved.Such as nano Ce O2Still there is certain photocatalytic activity, to BOPA films
Still there is certain potential injury.Although once there is literature review report can be by nano Ce O2Surface parcel silica
To reduce its catalytic activity, but this method is cumbersome, is only applicable to laboratory research, it is impossible to be prepared on a large scale, therefore
It is not used to industrial production.
The content of the invention
The purpose of the present invention aims to provide a kind of nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their system
Preparation Method and application, nano lanthanum oxide cerium be it is a kind of specificity be presented in ultra-violet (UV) band absorb, and macromolecule can be reduced simultaneously urge
Change the uvioresistant absorbing material of oxidation activity, apply it in high polymer material (such as BOPA films), performance can be obtained
Excellent ultraviolet ray-resistant material.The present invention uses nano lanthanum oxide cerium, i.e., in molecular level mixed oxidization lanthanum (La2O3), titanium dioxide
Cerium (CeO2) turn into eutectic phase, by diluting CeO2Content reduce the catalytic oxidation activity of high polymer material.
To achieve these goals, the invention provides a kind of nano lanthanum oxide cerium, its molecular formula is：LaxCe1-0.75xO2,
Wherein, 0<x<0.5.Preferably, 0.1≤x≤0.45, more preferably 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4.
Further, the powder granularity of nano lanthanum oxide cerium is about 30~100nm, preferably 50~90nm, more preferably
60~80nm, still more preferably about 70nm.
The present invention also provides a kind of preparation method of nano lanthanum oxide cerium, and it is as original using lanthanum carbonate cerium mischmetal material
Material, decomposes by heating and the nano lanthanum oxide cerium is made.
Preferably, the total content of lanthanum carbonate cerium mischmetal material middle rare earth be more than 80wt%, preferably 90~
99wt%, more preferably 95~99wt%.
Alternatively, cerium lanthanum oxide account for rare earth oxide total content mass ratio be more than or equal to 50wt%, preferably 50~
90wt%, more preferably 55~80wt%, still more preferably 60~65wt%.
Further, the preparation method of nano lanthanum oxide cerium comprises the following steps：
S1, weigh lanthanum carbonate cerium mischmetal material, add deionized water, be put into ball mill and grind, obtain slurry；
S2, the slurry obtained by step S1 is warming up to 800~1000 DEG C, constant temperature 250~300 minutes is (such as by slurry liter
Temperature is to 800 DEG C, constant temperature 300 minutes；Or slurry is warming up to 1000 DEG C, constant temperature 250 minutes)；Afterwards with 20 DEG C/min of speed
Rate is down to room temperature, obtains cerium lanthanum oxide；
S3, the cerium lanthanum oxide obtained by step S2 crushed with high speed ball milling instrument, screening, then it is broken through airflow milling, it is classified out
Granularity is in 30~100nm, preferably 50~90nm, more preferably 60~80nm, still more preferably about 70nm nano lanthanum oxide
Cerium.
Further, in step sl, lanthanum carbonate cerium mischmetal material and the mass ratio of deionized water are 3:1~4:1；In ball
Grinding time in grinding machine is 6~8 hours.
The present invention also provides a kind of ultraviolet ray-resistant material, and it contains any of the above-described kind of nano lanthanum oxide cerium.
Further, the ultraviolet ray-resistant material is the BOPA films for being doped with nano lanthanum oxide cerium, also referred to as uvioresistant
BOPA films.
Further, the thickness of the uvioresistant BOPA films is 10~50 μm；Preferably 15~30 μm.
The uvioresistant BOPA films have following anti-ultraviolet property：The ultraviolet ray transmissivity between 280~360nm
Less than 20%；To the visible above light transmission rates of 400nm more than 90%.
Further, the doping of nano lanthanum oxide cerium is 0.2~3.0wt%, preferably 0.5 in the ultraviolet ray-resistant material
~2.0wt%.
Present invention also offers a kind of preparation method of uvioresistant BOPA films, including：
1) nano lanthanum oxide cerium is prepared, the molecular formula of the nano lanthanum oxide cerium is LaxCe1-0.75xO2, wherein, 0<x<0.5,
It is preferred that 0.1≤x≤0.45, preferred 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4；
2) by step 1) the middle nano lanthanum oxide cerium dopping prepared is into polyamide (PA, also referred to as nylon), through melting batch mixing,
Master batch is made on the twin screw extruder；
3) step 2 will be included) in the mixture of obtained master batch film is made, through biaxial tension, obtain the uvioresistant
Line BOPA films.
Further, step 3) in, the mixture is made up of master batch；Or by master batch and polyamide (PA, also referred to as Buddhist nun
Dragon) composition, the polyamide and step 2) in polyamide it is identical or different.
Further, the step 3) be specially：Master batch is put on thin film extruding machine, or by master batch and polyamide
Put into according to certain ratio on thin film extruding machine；Heated melting, master batch is converged with polyamide in adapter, melt warp
T-shaped mould head extrusion flow casting molding is crossed, curtain coating thick film is made after chilling roller is cooled down, thick film is and then by heating biaxial tension
Afterwards, the uvioresistant BOPA films are made.
Preferably, step 3) in, the master batch is with the polyamide according to mass ratio (1:1.5)~(1:9) ratio point
Do not put on thin film extruding machine.Preferably, the ratio is (1:2)~(1:7) it is also preferably, (1:3)~(1:6), for example
The input ratio of master batch and polyamide can be 1:4.
Preferably, step 2) in, nano lanthanum oxide cerium is doped in PA according to 0.5~5.0wt% ratio.
Preferably, step 2) or step 3) in PA it is identical or different, be independently from each other PA6, PA66, PA11,
PA12, PA46, PA610, PA612, PA1010, PA7, PA9, PA13 etc., preferably PA6 or PA66.
Further, the powder granularity of nano lanthanum oxide cerium is about 30~100nm, preferably 50~90nm, more preferably
60~80nm, still more preferably about 70nm.
Present invention also offers a kind of application of nano lanthanum oxide cerium in high polymer material or plastic material, preferably exist
Application in BOPA films, the molecular formula of the nano lanthanum oxide cerium is：LaxCe1-0.75xO2, wherein, 0<x<0.5, preferably
0.1≤x≤0.45, preferred 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4.
Further, the powder granularity of nano lanthanum oxide cerium is about 30~100nm, preferably 50~90nm, more preferably
60~80nm, still more preferably about 70nm.
Further, the doping of the nano lanthanum oxide cerium is 0.2~3.0wt%, preferably 0.5~2.0wt%.
Beneficial effects of the present invention：
(molecular formula is for nano lanthanum oxide cerium prepared by the present invention：LaxCe1-0.75xO2,0<x<0.5) particle is in ultra-violet (UV) band
Existing specificity absorbs, and can effectively reduce the catalytic oxidation activity of high polymer material, is that a kind of brand-new uvioresistant absorbs material
Material.The present invention is by having this nano lanthanum oxide cerium particle of preferable uvioresistant absorbent properties to be added to high polymer material
In (such as BOPA films), so as to obtain the material with excellent anti-ultraviolet property.
The thickness of ultraviolet ray-resistant material (such as uvioresistant BOPA films) prepared by the present invention is 10~50 μm, 280~
Ultraviolet ray transmissivity is less than 20% between 360nm, to the visible above light transmission rates of 400nm more than 90%.After weather-proof test,
The tensile strength of the ultraviolet ray-resistant material (such as uvioresistant BOPA films) can remain at more than 85%.Illustrate the present invention
Material there is excellent anti-ultraviolet property and highly stable mechanical property.
The present invention directly prepares nano lanthanum oxide on a large scale using Rare Earth Separation intermediate species (lanthanum carbonate cerium mischmetal material)
Cerium, can obtain feather weight product, realize the demand of industrialized production.
Brief description of the drawings
Fig. 1 is the transmitance figure of the different wavelengths of light of the BOPA films of doped or undoped nano lanthanum oxide cerium particle.
Embodiment
As it was previously stated, the present invention provides a kind of nano lanthanum oxide cerium, inventor has found that the nano lanthanum oxide cerium is in ultra-violet (UV) band
Specificity is presented to absorb, due to simple CeO2Problem is a lot, and such as catalytic activity is too strong.Nano lanthanum oxide prepared by the present invention
Cerium, compared to CeO2, the catalytic oxidation activity of high polymer material is significantly reduced.To find out its cause, mainly on the one hand by CeO2
Middle doped lanthanum and dilute CeO2Ratio, so as to reduce its catalytic oxidation activity；On the other hand by doped lanthanum, it can stablize
The ratio of ionic radii of eight-coordinate, CeO is reduced by generating lattice Lacking oxygen2Catalytic activity.
Therefore, can be while high polymer material catalytic oxidation activity be significantly reduced, also with excellent in order to obtain one kind
The nano lanthanum oxide cerium material of different UV absorbing properties, the present invention proposes the nano lanthanum oxide with following molecular formula
Cerium：LaxCe1-0.75xO2, wherein, 0<x<0.5, preferably 0.1≤x≤0.45, preferred 0.2≤x≤0.4, even more preferably from
0.3≤x≤0.4。
According to the present invention, the powder granularity of nano lanthanum oxide cerium is about 30~100nm.It is preferred that the powder of nano lanthanum oxide cerium
Granularity is 50~90nm, still more preferably about more preferably 60~80nm, 70nm or so.If powder granularity is too big, it can cause
UV absorbing properties drastically decline, and are unfavorable for maintaining the function of film.If on the contrary, powder granularity is too small, easily rolled into a ball
It is poly-, with good adherence of causing to be difficult to feed together, equally it is unfavorable for nano-powder scattered in dopant material such as PA.
In an embodiment of the invention there is provided a kind of preparation method of nano lanthanum oxide cerium, it is to use carbon
Sour lanthanum cerium mischmetal material decomposes the nano lanthanum oxide cerium for being made described as raw material by heating.The lanthanum carbonate cerium mischmetal material
Material is the intermediate species in Rare Earth Separation, nano lanthanum oxide cerium can be directly prepared on a large scale using it, it is hereby achieved that public
Jin level product, realizes the demand of industrialized production.
, according to the invention it is preferred to which the total content of lanthanum carbonate cerium mischmetal material middle rare earth is more than 80wt%, further
Preferably 90~99wt%, more preferably 95~99wt%.The total content of rare earth oxide is limited herein, primarily to reducing
The interference of non-rare earth and adverse effect.
In lanthanum carbonate cerium mischmetal material, preferably cerium lanthanum oxide accounts for the mass ratio of rare earth oxide total content and is more than or equal to
50wt%, preferably 50~90wt%, more preferably 55~80wt%, still more preferably 60~65wt%.The present invention is to oxidation
The content of lanthanum cerium is defined, mainly in view of anti-ultraviolet property, can be caused finally if the content of cerium lanthanum oxide is too low
The anti-uv-ray of product nano cerium lanthanum oxide drastically declines.
According to the present invention, such as total content of lanthanum carbonate cerium mischmetal material middle rare earth can be 99%, lanthana
The ratio that cerium accounts for rare earth oxide total content can be 65wt%.The total content of lanthanum carbonate cerium mischmetal material middle rare earth
Can be 95%, the ratio that cerium lanthanum oxide accounts for rare earth oxide total content can also be 60wt%.
According to the present invention, the preparation method of nano lanthanum oxide cerium comprises the following steps：
S1, weigh lanthanum carbonate cerium mischmetal material, add deionized water, be put into ball mill and grind, obtain slurry.It is preferred that carbon
Sour lanthanum cerium mischmetal material and the mass ratio of deionized water are (3：1)~(4：1), it is put into ball mill and grinds 6~8 hours.
S2, slurry is warming up to 800~1000 DEG C, and constant temperature 250~300 minutes (slurry is for example warming up to 800 DEG C, it is permanent
Temperature 300 minutes；Or slurry is warming up to 1000 DEG C, constant temperature 250 minutes)；Room temperature is down to 20 DEG C/min of speed afterwards,
Obtain cerium lanthanum oxide.In this step by the calcining heat of slurry and constant temperature time control within the above range, mainly consider
The factors such as the distribution of nano-particle yardstick, else if calcining heat is too high or too low particle aggregation or granularity mistake occurs
Greatly, it is unfavorable for strengthening its anti-ultraviolet property.Constant temperature time it is oversize or it is too short will also result in particle aggregation or granularity is excessive, no
Beneficial to the holding of nanoparticle morphology, the anti-ultraviolet property of final product nano lanthanum oxide cerium is equally influenced whether.
S3, the cerium lanthanum oxide of acquisition crushed with high speed ball milling instrument, screening, then it is broken through airflow milling, it is classified out granularity and exists
30~100nm, preferably 50~90nm, more preferably 60~80nm, still more preferably about 70nm nano lanthanum oxide cerium.
In an embodiment of the invention there is provided a kind of preparation method of uvioresistant BOPA films, including：
1) nano lanthanum oxide cerium is prepared, the molecular formula of the nano lanthanum oxide cerium is LaxCe1-0.75xO2, wherein 0 ＜ x ＜ 0.5,
Preferably, 0.1≤x≤0.45, preferred 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4.Wherein nano lanthanum oxide
Cerium can be adopted and prepared with the aforedescribed process.
2) by step 1) in prepare nano lanthanum oxide cerium mix in polyamide (PA), through melt batch mixing, twin-screw squeeze
Go out and the master batch containing the nano lanthanum oxide cerium is made on machine.
3) master batch and polyamide (PA) are put on thin film extruding machine respectively according to certain mass ratio, heated melting,
Master batch is converged with polyamide raw materials in adapter, and melt is made by T-shaped mould head extrusion flow casting molding after chilling roller is cooled down
Thick film is cast, and then thick film after heating biaxial tension, is made uvioresistant BOPA films；
Wherein, step 3) in polyamide and step 2) in polyamide it is identical or different.
Preferably, step 2) in, nano lanthanum oxide cerium is mixed in PA according to 0.5~5.0wt% ratio.If nanometer
The doping ratio of cerium lanthanum oxide is too high, it may appear that the too low problem of light transmission rate；If on the contrary, doping ratio is too low, it may appear that anti-
It is imparted can be too weak.
, according to the invention it is preferred in step 3) in by master batch and polyamide according to mass ratio (1:1.5)~(1：9) put into
On thin film extruding machine.So, in obtained film nano lanthanum oxide cerium doping be 0.2~3.0wt%, preferably 0.5~
2.0wt%, for example, 0.75wt%.If master batch and polyamide ratio are too high or too low, visible light transmissivity can be equally influenceed
Or UV absorbing properties.
Present invention also offers a kind of ultraviolet ray-resistant material containing above-mentioned nano lanthanum oxide cerium, such as uvioresistant
BOPA films, with excellent uvioresistant absorbent properties, ultraviolet ray transmissivity is right less than 20% between 280~360nm
The visible above light transmission rates of 400nm are more than 90%.
According to the present invention, the thickness of uvioresistant BOPA films is 10~50 μm.Preferably 15~30 μm.If prepared
The thickness of uvioresistant BOPA films is too big, can influence the background absorption of film, but can also strengthen ultraviolet absorption ability.Typically
For if uvioresistant BOPA films are too thin or too thick, anti-uv-ray or transmittancy can be influenceed, so as to be unfavorable for
Production is promoted.
Invention further provides a kind of application of above-mentioned nano lanthanum oxide cerium in high polymer material or plastic material, preferably
Application in BOPA films.The nano lanthanum oxide cerium is compared to CeO2, color substantially shoals, and be more beneficial for it is in light color
Application into colourless BOPA films.
Technical scheme is described in detail below by way of exemplary specific embodiment.But should not be by these
Embodiment is construed to limiting the scope of the invention.All technologies realized based on the above of the present invention are encompassed by this
Invention is intended in the range of protection.
Unless otherwise indicated, raw material and reagent described in embodiment are commercially available prod.
Embodiment 1
1) nano lanthanum oxide cerium is prepared
Lanthanum carbonate cerium mischmetal material is used for raw material, the total content of raw material middle rare earth is 99%, and cerium lanthanum oxide is accounted for
The ratio of rare earth oxide total content is 65wt%.
The quality of deionized water, wherein lanthanum carbonate cerium mischmetal material and deionized water is added into lanthanum carbonate cerium mischmetal material
Than for 4：1.Insert in ball mill and grind 6 hours, obtain slurry.
Slurry is pressed into temperature programming to 800 DEG C, constant temperature 300 minutes in electric furnace；Afterwards with 20 DEG C/min of rate program
Room temperature is down to, calcining is completed, obtains cerium lanthanum oxide.
The cerium lanthanum oxide of acquisition is crushed with high speed ball milling instrument, screening.It is broken through airflow milling again, it is classified out nano lanthanum oxide
Cerium (granularity is in 70nm or so).The molecular formula of the nano lanthanum oxide cerium is La0.35Ce0.65O2。
2) uvioresistant BOPA films are prepared
By step 1) in obtain nano lanthanum oxide cerium with 5wt% ratio be incorporated into PA6 mix, through melt batch mixing,
Master batch is made on the twin screw extruder.
Compare 1 according to weight on the extruder of film:9 ratios put into master batch and PA6, heated melting, in adapter
Master batch is converged with PA6, and by T-shaped mould head extrusion flow casting molding curtain coating thick film is made, thick film is immediately in melt after chilling roller is cooled down
After heating biaxial tension, uvioresistant BOPA films are made.
The thickness of uvioresistant BOPA films is 15 μm.From figure 1 it appears that uvioresistant BOPA films exist
Ultraviolet ray transmissivity is less than 20% between 280~360nm, to the visible above light transmission rates of 400nm more than 90%.And undoped with
The BOPA films of nano lanthanum oxide cerium ultraviolet ray transmissivity between 280~360nm is more than 80%.
Weather-proof test is carried out to uvioresistant BOPA films prepared by biaxial tension in embodiment 1, test condition is as follows：Make
With ASTM D-4329 standard ultraviolet ageing programs, its setting program is：First exposed 8 hours under UV at 60 DEG C, afterwards at 50 DEG C
Exposure 4 hours under lower high humility, are transferred after being circulated 252 hours by conditions above in 33%RH (i.e. relative humidity is 33%) condition
Detected after putting 4 days.
The mechanical property (tensile strength) of uvioresistant BOPA films is tested, this biaxially oriented film is in experience ASTM
The weather-proof tests of D-4329, thin film mechanical performance (tensile strength) is maintained at more than 85%, using the method for the present invention by that will receive
Rice cerium lanthanum oxide, which is added in PA6, forms function film, and obvious drop will not also occur for accelerated burn-in test, its tensile strength
It is low.Illustrate that doping Post functionalization film can significantly resist uv damage.Accelerated ageing rear film tensile property is maintained,
Illustrate that it has good mechanical property, its practical application is not influenceed.
Embodiment 2
1) nano lanthanum oxide cerium is prepared
Lanthanum carbonate cerium mischmetal material is used for raw material, the total content of raw material middle rare earth is 95%, and cerium lanthanum oxide is accounted for
The ratio of rare earth oxide total content is 60wt%.
Add deionized water into lanthanum carbonate cerium mischmetal material, the mass ratio of lanthanum carbonate cerium mischmetal raw material and deionized water is
3：1.Insert in ball mill and grind 8 hours, obtain slurry.
Slurry is pressed into temperature programming to 950 DEG C, constant temperature 250 minutes in electric furnace；Afterwards with 20 DEG C/min of rate program
Room temperature is down to, calcining is completed, obtains cerium lanthanum oxide.
The cerium lanthanum oxide of acquisition is crushed with high speed ball milling instrument, screening.It is broken through airflow milling again, it is classified out nano lanthanum oxide
Cerium (granularity is in 70nm or so).The molecular formula of the nano lanthanum oxide cerium is La0.40Ce0.60O2。
2) uvioresistant BOPA films are prepared
By step 1) proportionally 5wt% is mixed the middle nano lanthanum oxide cerium obtained with PA66, through melting batch mixing, in double spiral shells
Master batch is made on bar extruder.
Compare 1 according to weight on the extruder of film:4 ratios put into master batch and PA66, heated melting, in adapter
Master batch is converged with PA66, and by T-shaped mould head extrusion flow casting molding curtain coating thick film is made, thick film is tight in melt after chilling roller is cooled down
It is then passed through after heating biaxial tension, uvioresistant BOPA films is made.
The thickness of uvioresistant BOPA films is 15 μm.
Similar with the moderate resistance UV-B OPA film performances of embodiment 1, its ultraviolet ray transmissivity between 280~360nm is small
In 20%, to the visible above light transmission rates of 400nm more than 90%.And the BOPA films undoped with nano lanthanum oxide cerium are 280
Ultraviolet ray transmissivity is more than 80% between~360nm.
Weather-proof test is carried out to uvioresistant BOPA films prepared by biaxial tension in embodiment 2, test condition is as follows：Make
With ASTM D-4329 standard ultraviolet ageing standards, its setting program is：First exposed 8 hours under UV at 60 DEG C, afterwards at 50 DEG C
Exposure 4 hours under lower high humility, are transferred after being circulated 252 hours by conditions above in 33%RH (i.e. relative humidity is 33%) condition
Detected after putting 4 days.
The mechanical property (tensile strength) of uvioresistant BOPA films is tested, this biaxially oriented film is in experience ASTM
The weather-proof tests of D-4329, thin film mechanical performance (tensile strength) is maintained at more than 85%, illustrates to pass through using the method for the present invention
Nano lanthanum oxide cerium is added in PA66, the anti-ultraviolet property of BOPA films is proved through ultraviolet ray ageing Acceleration study, its
Tensile strength will not also change with the change of temperature or humidity, illustrate that stability is good.
Therefore, it can be seen that the nano lanthanum oxide with uv absorption property prepared by the present invention from above performance test
Cerium may apply in BOPA films, and extend in the materials such as other high polymer materials, plastic material.
Claims (10)
1. a kind of nano lanthanum oxide cerium, it is characterised in that the molecular formula of the nano lanthanum oxide cerium is：LaxCe1-0.75xO2, its
In, 0<x<0.5,0.1≤x≤0.45 preferably, preferred 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4.
2. nano lanthanum oxide cerium according to claim 1, it is characterised in that the powder granularity of the nano lanthanum oxide cerium is
30~100nm, preferably 50~90nm, more preferably 60~80nm, still more preferably about 70nm.
3. a kind of preparation method of nano lanthanum oxide cerium, it is characterised in that methods described uses lanthanum carbonate cerium mischmetal material conduct
Raw material, decomposes by heating and the nano lanthanum oxide cerium is made；
Preferably, the total content of the lanthanum carbonate cerium mischmetal material middle rare earth be more than 80wt%, preferably 90~
99wt%, more preferably 95~99wt%；
Alternatively, cerium lanthanum oxide account for rare earth oxide total content mass ratio be more than or equal to 50wt%, preferably 50~90wt%,
More preferably 55~80wt%, still more preferably 60~65wt%.
4. preparation method according to claim 3, it is characterised in that comprise the following steps：
S1, weigh lanthanum carbonate cerium mischmetal material, add deionized water, be put into ball mill and grind, obtain slurry；
S2, the slurry obtained by step S1 is warming up to 800~1000 DEG C, slurry (is for example warming up to 800 by the clock of constant temperature 250~300
DEG C, constant temperature 300 minutes；Or slurry is warming up to 1000 DEG C, constant temperature 250 minutes)；It is down to afterwards with 20 DEG C/min of speed
Room temperature, obtains cerium lanthanum oxide；
S3, the cerium lanthanum oxide obtained by step S2 crushed with high speed ball milling instrument, screening, then it is broken through airflow milling, it is classified out granularity
For 30~100nm, preferably 50~90nm, more preferably 60~80nm, still more preferably about 70nm nano lanthanum oxide cerium.
5. preparation method according to claim 4, it is characterised in that
In step sl, lanthanum carbonate cerium mischmetal material and the mass ratio of deionized water are 3:1~4:1；Crushing in ball mill
Time is 6~8 hours.
6. a kind of ultraviolet ray-resistant material, it contains the nano lanthanum oxide cerium described in claim 1 or 2.
7. ultraviolet ray-resistant material according to claim 6, it is characterised in that the ultraviolet ray-resistant material is described to be doped with
The BOPA films of nano lanthanum oxide cerium, also referred to as uvioresistant BOPA films.
8. ultraviolet ray-resistant material according to claim 7, it is characterised in that the thickness of the uvioresistant BOPA films is
10~50 μm；Preferably 15~30 μm；
Preferably, uvioresistant BOPA films ultraviolet ray transmissivity between 280~360nm is less than 20%；To 400nm with
Upper visible light transmissivity is more than 90%.
Preferably, the PA is selected from PA6, PA66, PA11, PA12, PA46, PA610, PA612, PA1010, PA7, PA9, PA13
One or more in, preferably one or both of PA6 or PA66.
Preferably, in the ultraviolet ray-resistant material nano lanthanum oxide cerium doping be 0.2~3.0wt%, preferably 0.5~
2.0wt%.
9. a kind of preparation method of uvioresistant BOPA films, including：
1) nano lanthanum oxide cerium is prepared, the molecular formula of the nano lanthanum oxide cerium is LaxCe1-0.75xO2, wherein, 0<x<0.5, preferably
0.1≤x≤0.45, preferred 0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4.
2) by step 1) the middle nano lanthanum oxide cerium dopping prepared is into polyamide, through melting batch mixing, on the twin screw extruder
Master batch is made；
3) step 2 will be included) in the mixture of obtained master batch film is made, through biaxial tension, obtain the uvioresistant
BOPA films.
Further, step 3) in, the mixture is made up of master batch；Or by master batch and polyamide (PA, also referred to as nylon) group
Into the polyamide and step 2) in polyamide it is identical or different.
Preferably, the step 3) be specially：Master batch is put on thin film extruding machine, or master batch is put into polyamide
On thin film extruding machine；Heated melting, the master batch described in adapter or the master batch are converged with polyamide, and melt is by T-shaped
Die head extrudes flow casting molding, and curtain coating thick film is made after chilling roller is cooled down, and and then thick film after heating biaxial tension, is made
The uvioresistant BOPA films.
Preferably, step 2) in, the nano lanthanum oxide cerium is doped in PA according to 0.5~5.0wt% ratio.
Preferably, step 3) in, the master batch is with the polyamide according to weight ratio (1:1.5)~(1:9) ratio is thrown respectively
Enter onto thin film extruding machine；Preferably, the ratio is (1:2)~(1:7) it is also preferably, (1:3)~(1:6), such as master batch
Input ratio with polyamide can be 1:4.
Preferably, step 2) or step 3) in PA it is identical or different, be independently from each other PA6, PA66, PA11, PA12,
PA46, PA610, PA612, PA1010, PA7, PA9, PA13 etc., preferably PA6 or PA66.
It is preferred that, the powder granularity of the nano lanthanum oxide cerium is about 30~100nm, preferably 50~90nm, more preferably 60
~80nm, still more preferably about 70nm.
10. a kind of application of nano lanthanum oxide cerium in high polymer material or plastic material, the preferably application in BOPA films,
The molecular formula of the nano lanthanum oxide cerium is：LaxCe1-0.75xO2, wherein, 0<x<0.5,0.1≤x≤0.45 preferably, more preferably
0.2≤x≤0.4, even more preferably from 0.3≤x≤0.4；
It is preferred that, the powder granularity of the nano lanthanum oxide cerium is about 30~100nm, preferably 50~90nm, more preferably 60
~80nm, still more preferably about 70nm；
Preferably, the PA is selected from PA6, PA66, PA11, PA12, PA46, PA610, PA612, PA1010, PA7, PA9, PA13
One or more in, preferably one or both of PA6 or PA66；
Preferably, the doping of the nano lanthanum oxide cerium is 0.2~3.0wt%, preferably 0.5~2.0wt%.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2015109202624 | 2015-12-11 | ||
| CN201510920262 | 2015-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107033387A true CN107033387A (en) | 2017-08-11 |
Family
ID=59530951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611089693.1A Pending CN107033387A (en) | 2015-12-11 | 2016-12-01 | Nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107033387A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557862A (en) * | 2018-05-28 | 2018-09-21 | 东北大学 | A kind of rare-earth-based light absorbing material, preparation method and application |
| CN110804303A (en) * | 2019-11-25 | 2020-02-18 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PA6 material and preparation method thereof |
| CN113845847A (en) * | 2021-08-02 | 2021-12-28 | 北京工业大学 | Method for preparing lanthanum-cerium solid solution polishing powder with controllable particle size by roasting method |
| CN115724454A (en) * | 2022-09-30 | 2023-03-03 | 深圳市聚芯半导体材料有限公司 | Lanthanum-cerium oxide solid solution particle and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944533A (en) * | 2006-06-16 | 2007-04-11 | 湘潭大学 | Nylon 6/phthalocyanine nano composite material and its producing method |
| CN103253694A (en) * | 2013-05-19 | 2013-08-21 | 郭尧 | Roasting process of lanthanum-cerium oxide rear-earth polishing powder |
| CN103421311A (en) * | 2013-08-23 | 2013-12-04 | 厦门长塑实业有限公司 | Biaxially stretching polyamide film |
-
2016
- 2016-12-01 CN CN201611089693.1A patent/CN107033387A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944533A (en) * | 2006-06-16 | 2007-04-11 | 湘潭大学 | Nylon 6/phthalocyanine nano composite material and its producing method |
| CN103253694A (en) * | 2013-05-19 | 2013-08-21 | 郭尧 | Roasting process of lanthanum-cerium oxide rear-earth polishing powder |
| CN103421311A (en) * | 2013-08-23 | 2013-12-04 | 厦门长塑实业有限公司 | Biaxially stretching polyamide film |
Non-Patent Citations (3)
| Title |
|---|
| PRAVEEN KUMAR,VIMAL CHANDRA SRIVASTAVA,INDRA MANI MISHRA: "《Synthesis and characterization of Ce-La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate》", 《CATALYSIS COMMUNICATIONS》 * |
| 周健，杨箐箐等: "《PA6/稀土氧化物复合材料力学与抗紫外老化性能》", 《工程塑料应用》 * |
| 郝仕油: "纳米Ce_(1-x)La_xO_(2-δ)的微波引诱燃烧合成及其性能表征", 《无机化学学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557862A (en) * | 2018-05-28 | 2018-09-21 | 东北大学 | A kind of rare-earth-based light absorbing material, preparation method and application |
| CN110804303A (en) * | 2019-11-25 | 2020-02-18 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PA6 material and preparation method thereof |
| CN110804303B (en) * | 2019-11-25 | 2022-08-12 | 南通复源新材料科技有限公司 | Regenerated carbon fiber reinforced PA6 material and preparation method thereof |
| CN113845847A (en) * | 2021-08-02 | 2021-12-28 | 北京工业大学 | Method for preparing lanthanum-cerium solid solution polishing powder with controllable particle size by roasting method |
| CN115724454A (en) * | 2022-09-30 | 2023-03-03 | 深圳市聚芯半导体材料有限公司 | Lanthanum-cerium oxide solid solution particle and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107033387A (en) | Nano lanthanum oxide cerium, the ultraviolet ray-resistant material containing it and their preparation method and application | |
| CN104262874B (en) | Dynamically PVB film intercepting infrared ray anti-ultraviolet and preparation method thereof | |
| JP4655105B2 (en) | Ultraviolet light shielding transparent resin molding and method for producing the same | |
| CN102504345B (en) | Disposable controlled completely-degradable plastic packing bag and preparation method thereof | |
| JP4632094B2 (en) | Manufacturing method of high heat-resistant masterbatch, heat ray shielding transparent resin molding, and heat ray shielding transparent laminate | |
| CN101445692B (en) | Super weatherability nano-compound modified polyester powder coating and preparation method thereof | |
| CN102911499B (en) | A kind of high stability uvioresistant high temperature resistant nylon and preparation method thereof | |
| CN107236297B (en) | Nano modified colored nylon composite material | |
| EP3214148A1 (en) | Heat-ray-shielding particles, heat-ray-shielding particle liquid dispersion, heat-ray-shielding particle dispersion, heat-ray-shielding particle dispersion laminate transparent substrate, infrared-absorbent transparent substrate, and method for manufacturing heat-ray-shielding particles | |
| CN101835824A (en) | Masterbatch with high heat resistance, heat-ray-shielding transparent molded resin, and heat-ray-shielding transparent layered product | |
| CN107418159B (en) | BOPET ultraviolet screener master batch and its manufacturing method | |
| DE10352319A1 (en) | Polyamide resin composition | |
| JP2011001551A (en) | Highly heat-resistant masterbatch, heat ray-shielding transparent resin molded body, and heat ray-shielding transparent laminate | |
| US8927628B2 (en) | Method for fabricating energy plastic masterbatch and plastic product derived therefrom | |
| CN108503892A (en) | A kind of sericite composite material and preparation method in plastic, transparent masterbatch | |
| CN109851944A (en) | A kind of antiultraviolet wall film and its processing technology | |
| JP5898397B2 (en) | Near-infrared shielding polyester resin composition, near-infrared shielding polyester resin laminate, molded article and method for producing the same | |
| CN106903959A (en) | A kind of solar energy backboard Obstruct membrane and preparation method thereof | |
| CN106317582A (en) | Polyethylene masterbatch with pumice powder as opening agent and preparation method thereof | |
| CN106750537B (en) | Surface-modified nano cerium lanthanum oxide, method of modifying, ultraviolet ray-resistant material and preparation method and application | |
| CN102152584B (en) | Nano fluorescent invisible anti-counterfeit polyester film with high permeability and preparation method thereof | |
| CN107236298B (en) | Modification and coloring method of nylon composite material | |
| CN111547771A (en) | Transparent heat-shielding fine particles, fine particle dispersion, process for producing the same, and use thereof | |
| CN107936495A (en) | A kind of uvioresistant high water resistant PBAT films and preparation method thereof | |
| CN109518357A (en) | A kind of processing method of light aging resisting polypropylene melt-blown nonwoven fabric |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170811 |