CN107082833A - PMMA/oxidized zinc nano composite material and preparation method thereof - Google Patents
PMMA/oxidized zinc nano composite material and preparation method thereof Download PDFInfo
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- CN107082833A CN107082833A CN201710384673.5A CN201710384673A CN107082833A CN 107082833 A CN107082833 A CN 107082833A CN 201710384673 A CN201710384673 A CN 201710384673A CN 107082833 A CN107082833 A CN 107082833A
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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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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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
- 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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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/54—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing zinc or cadmium
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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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
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of PMMA/oxidized zinc nano composite material and preparation method thereof.The present invention preferably goes out suitable component and content, and the preparation method for heating up and being reacted again after ethanol using monomer, initiator, presoma and catalyst are dissolved in, so that the synthesis of zinc oxide and the polymerization of methyl methacrylate are carried out simultaneously, simplify preparation flow, shorten the reaction time, and only using ethanol as solvent, production cost is not only reduced, and be conducive to environmental protection.The particle diameter for the nano zine oxide that the preparation method is obtained is less than 10 nanometers, and has shielding ultraviolet radioactive, visible region transparent and luminescence generated by light performance.Extensively, with low cost, using effect is good for material source of the present invention.
Description
Technical field
The present invention relates to field of material technology, especially a kind of PMMA/oxidized zinc nano composite material
And preparation method thereof.
Background technology
Zinc oxide (ZnO) nano-particle has many excellent properties, is a kind of multi-functional inorganic filler.For example:Its
There is high transmitance in visible region, while there is strong absorbability to ultraviolet light;Low-k;Photoluminescence
Energy;Anti-microbial property;Photocatalysis performance etc..The application field of zinc oxide nano-particle is extensive, including solar cell, nanometer generating
Machine, field-effect transistor, gas detector, cosmetics, fluorescence labeling etc..
Polymethyl methacrylate (PMMA), also known as lucite, are a kind of common thermoplastic polymers, and it has
Transparency in visible-range is high, and density is small, and shock resistance, thermal conductivity is low, and refractive index is low, optical distortion after easy processing and shaping
It is small, the advantages of cheap.However, PMMA does not possess the specific functions such as shielding ultraviolet rays but.
Using appropriate method, mix what polymethylmethacrylate matrix was obtained using zinc oxide nano-particle as filler
PMMA/oxidized zinc nano composite material can combine zinc oxide advantage and polymethyl methacrylate into
Type performance, making the optics, calorifics, mechanical property of polymeric matrix is improved, and one or more work(with Nano filling
Can property.
At present, existing many preparations and property on PMMA/oxidized zinc nano composite material both at home and abroad
The report that can be studied.The preparation method of PMMA/oxidized zinc nano composite material mainly have situ aggregation method and
Solution blended process.
The content of the invention
The purpose of the present invention is:There is provided a kind of PMMA/oxidized zinc nano composite material and its preparation
Method, the material possesses the performances such as uvioresistant, luminescence generated by light, and the preparation method technique of the material is simple, and only using ethanol as
Solvent, had not only reduced cost but also environmentally friendly.
What the present invention was realized in:PMMA/oxidized zinc nano composite material, according to the mass fraction
Calculate, including 1000 parts of methyl methacrylates, 1-50 parts 2,2'- azodiisobutyronitriles, 5-500 parts of acetic acid dihydrate zinc, 1-
The ethanol that 1000 parts of catalyst and 50-200000 parts of mass percents are more than 50% is preparing raw material.
Described catalyst is a hydronium(ion) lithia, sodium hydroxide, the alkali of the class of potassium hydroxide one.
The preparation method of PMMA/oxidized zinc nano composite material, each component is taken by above-mentioned mass fraction,
Comprise the steps of:
1) 2,2'- azodiisobutyronitriles, methyl methacrylate, acetic acid dihydrate zinc and catalyst are dissolved completely in molten
In agent, reaction solution is obtained;
2) by step 1) reaction solution be warming up to 60~100 DEG C and react more than 1h;After reaction terminates, at 20~100 DEG C
Evaporative removal solvent, that is, obtain PMMA/oxidized zinc nano composite material.
Step 1) in solution temperature be 0~50 DEG C.
Compared with prior art, the present invention preferably goes out suitable component and content, and using by monomer, initiator, preceding
Drive body and catalyst is dissolved in the preparation method for heating up and being reacted again after ethanol so that the synthesis of zinc oxide and methyl methacrylate
The polymerization of ester is carried out simultaneously, simplifies preparation flow, shortens the reaction time, and only not only reduce life using ethanol as solvent
Cost is produced, and is conducive to environmental protection.The particle diameter for the nano zine oxide that the preparation method is obtained is less than 10 nanometers, and purple with shielding
External radiation, visible region be transparent and performance of luminescence generated by light.Extensively, with low cost, using effect is good for material source of the present invention.
Brief description of the drawings
Fig. 1 is Fourier's INFRARED SPECTRUM of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure;
Fig. 2 is the transmission electron microscope photo of PMMA/oxidized zinc nano composite material prepared by embodiment 1;
Fig. 3 is the ultraviolet-ray visible absorbing of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Spectrogram;
Fig. 4 is the photoluminescence spectra of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure;
Fig. 5 is the x-ray diffraction pattern of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure;
Embodiment
Embodiments of the invention 1:PMMA/oxidized zinc nano composite material, is calculated according to the mass fraction, bag
Include 0.32g 2,2'- azodiisobutyronitriles, 15.9g methyl methacrylates, 0.88g acetic acid dihydrates zinc, the hydronium(ion)s of 0.59g mono-
The ethanol that lithia and 213g mass percents are 99.7% is preparing raw material.
The preparation method of PMMA/oxidized zinc nano composite material, by above-mentioned containing each component is measured, first will
The hydronium(ion) lithias of 0.59g mono- are added to 113g ethanol, and 30 DEG C of stirring and dissolvings obtain the ethanol solution of a hydronium(ion) lithia;
0.88g acetic acid dihydrates zinc, 15.9g methyl methacrylates and 0.32g 2,2'- azodiisobutyronitriles are added to 100g again
After ethanol, 30 DEG C of stirring and dissolvings, the ethanol solution of a hydronium(ion) lithia is eventually adding, and is warming up to 80 DEG C, in 80 DEG C of backflows
2 hours are stirred after 30 DEG C of evaporative removal ethanol.
The specific surface area of nano zine oxide is big, and surface can be high, thus easily reunites;And zinc oxide and polymethylacrylic acid
The polarity of methyl esters is different, poor compatibility, easily produces phase separation.By the polymethyl methacrylate prepared by simple blend/
Often transparency is relatively low for zinc oxide nanometer composite material.Therefore, many researchers are poly- using solution blending, surface modification, original position
The method of conjunction prepares PMMA/oxidized zinc nano composite material.However, can be consumed largely using solution blended process
Toxic solvent, is unfavorable for environmental protection;And the price of coating material is higher, the operation of surface modification is also relatively complicated.In-situ polymerization
Rule can overcome these problems.The present invention is based on situ aggregation method, and combines sol-gel (Sol-Gel) method, realizes
The polymerization of methyl methacrylate and the synthesis of zinc oxide are carried out simultaneously, and this method is simple and environmentally-friendly and economy, prepared
PMMA/oxidized zinc nano composite material has the properties such as uvioresistant, luminescence generated by light.
Fig. 1 is the FTIR spectrum of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure, positioned at 1143 and 1723cm-1Peak respectively correspond to polymethyl methacrylate C-O and C=O groups stretching vibration, this
Two peaks exist in PMMA/oxidized zinc nano composite material.Zinc oxide surface exist substantial amounts of zinc and with
Oxygen dangling bond.Wherein, zinc dangling bond can be coordinated with aceticoceptor.1577 and 1420cm-1The peak of left and right corresponds to the C of aceticoceptor respectively
=O and C-O stretching vibration, can determine whether that it is monodentate ligand with zinc ion according to the peak position of aceticoceptor.Fourier transformation is red
External spectrum shows the successful preparation of PMMA/oxidized zinc nano composite material.
Fig. 2 shines for the transmission electron microscope of the PMMA/oxidized zinc nano composite material of the preparation of embodiment 1
Piece.From transmission electron microscope photo it is observed that the presence of zinc oxide phase, its particle diameter about 3-6nm, interplanar distance is about 0.26nm, right
Answer (002) crystal face.
Fig. 3 is the ultraviolet-ray visible absorbing of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Spectrogram.PMMA/oxidized zinc nano composite material has higher saturating to visible ray as we can see from the figure
Bright property and there is screening ability to ultraviolet light.It is possible thereby to illustrate PMMA/oxidized zinc nano composite material tool
There is certain ultraviolet shielded ability.
Fig. 4 is the photoluminescence spectra of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure.The glow peak corresponding wavelength scope of PMMA/oxidized zinc nano composite material is substantially as we can see from the figure
For 429-521nm, belong to blue green light region.
Fig. 5 is the x-ray diffraction pattern of PMMA/oxidized zinc nano composite material prepared by embodiment 1
Figure;In figure 2 θ values be 32,34,36,48,57,63,67 respectively correspond to zinc oxide (100), (002), (101), (102),
(110), (103), (112) crystal face, this XRD standard card with zinc oxide (number by JCPDS cards:Result base 36-1451)
This is consistent, and it is hexagonal crystal system wurtzite structure to show prepared zinc oxide.
Embodiments of the invention 2:PMMA/oxidized zinc nano composite material, is calculated according to the mass fraction, bag
Include 0.13g 2,2'- azodiisobutyronitriles, 6.2g methyl methacrylates, 0.88g acetic acid dihydrates zinc, the hydronium(ion)s of 0.59g mono-
The ethanol that lithia and 213g mass percents are 99.7% is preparing raw material.
The preparation method of PMMA/oxidized zinc nano composite material, by above-mentioned containing each component is measured, first will
The hydronium(ion) lithias of 0.59g mono- are added to 113g ethanol, and 30 DEG C of stirring and dissolvings obtain the ethanol solution of a hydronium(ion) lithia;
0.88g acetic acid dihydrates zinc, 6.2g methyl methacrylates and 0.13g 2,2'- azodiisobutyronitriles are added to 100g second again
After alcohol, 30 DEG C of stirring and dissolvings, the ethanol solution of a hydronium(ion) lithia is eventually adding, and is warming up to 80 DEG C, is stirred in 80 DEG C of backflows
2 hours are mixed after 50 DEG C of evaporative removal ethanol.
Embodiments of the invention 3:PMMA/oxidized zinc nano composite material, is calculated according to the mass fraction, bag
Include 0.32g 2,2'- azodiisobutyronitriles, 15.9g methyl methacrylates, 0.88g acetic acid dihydrates zinc, the hydronium(ion)s of 0.59g mono-
The ethanol that lithia and 213g mass percents are 99.7% is preparing raw material.
The preparation method of PMMA/oxidized zinc nano composite material, by above-mentioned containing each component is measured, is incited somebody to action
The hydronium(ion) lithias of 0.59g mono-, 0.88g acetic acid dihydrates zinc, 6.2g methyl methacrylates and 0.13g 2,2'- azos two are different
Butyronitrile is added to 100g ethanol and is added to after 113g ethanol, 30 DEG C of stirring and dissolvings, is warming up to 80 DEG C, small in 80 DEG C of return stirrings 2
When after 50 DEG C of evaporative removal ethanol.
Claims (4)
1. a kind of PMMA/oxidized zinc nano composite material, it is characterised in that:Calculate according to the mass fraction, including
1000 parts of methyl methacrylates, 1-50 parts of 2,2'- azodiisobutyronitriles, 5-500 parts of acetic acid dihydrate zinc, 1-1000 parts of catalysis
The ethanol that agent and 50-200000 parts of mass percents are more than 50% is preparing raw material.
2. nano composite material according to claim 1, it is characterised in that:Described catalyst aoxidizes for a hydronium(ion)
Lithium, sodium hydroxide or potassium hydroxide.
3. a kind of preparation method of PMMA/oxidized zinc nano composite material as claimed in claim 1, it is special
Levy and be:Each component is taken by above-mentioned mass fraction, is comprised the steps of:
1) 2,2'- azodiisobutyronitriles, methyl methacrylate, acetic acid dihydrate zinc and catalyst are dissolved completely in solvent
In, obtain reaction solution;
2) by step 1) reaction solution be warming up to 60~100 DEG C and react more than 1h;After reaction terminates, in 20~100 DEG C of evaporations
Solvent is removed, that is, obtains PMMA/oxidized zinc nano composite material.
4. preparation method according to claim 3, it is characterised in that:Step 1) in solution temperature be 0~50 DEG C.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109705287A (en) * | 2018-12-25 | 2019-05-03 | 杨记周 | A kind of new-energy automobile pmma material and preparation method thereof |
Citations (1)
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CN104250329A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院化学研究所 | Polymer nanocomposite optical material and preparation method thereof |
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Patent Citations (1)
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CN104250329A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院化学研究所 | Polymer nanocomposite optical material and preparation method thereof |
Non-Patent Citations (3)
Title |
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KIYOSHI MATSUYAMA 等: "Transparent polymeric hybrid film of ZnO nanoparticle quantum dots and PMMA with high luminescence and tunable emission color", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
YU ZHANG 等: "Highly transparent bulk PMMA/ZnO nanocomposites with bright visible luminescence and efficient UV-shielding capability", 《J. MATER. CHEM.》 * |
陈枭 等: "多功能nano ZnO/PMMA复合材料的制备与性能", 《复合材料学报》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109705287A (en) * | 2018-12-25 | 2019-05-03 | 杨记周 | A kind of new-energy automobile pmma material and preparation method thereof |
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