CN116284522A - In-situ polymethyl methacrylate master batch with Rayleigh scattering effect and preparation method thereof - Google Patents
In-situ polymethyl methacrylate master batch with Rayleigh scattering effect and preparation method thereof Download PDFInfo
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- CN116284522A CN116284522A CN202310091767.9A CN202310091767A CN116284522A CN 116284522 A CN116284522 A CN 116284522A CN 202310091767 A CN202310091767 A CN 202310091767A CN 116284522 A CN116284522 A CN 116284522A
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- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 46
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 46
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 42
- 230000000694 effects Effects 0.000 title claims abstract description 34
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000004381 surface treatment Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- NMJKIRUDPFBRHW-UHFFFAOYSA-N titanium Chemical compound [Ti].[Ti] NMJKIRUDPFBRHW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 17
- 239000002245 particle Substances 0.000 abstract description 10
- 238000000149 argon plasma sintering Methods 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 1
- 238000009792 diffusion process Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 206010016322 Feeling abnormal Diseases 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application discloses an in-situ polymethyl methacrylate master batch with Rayleigh scattering effect and a preparation method thereof. Firstly, preparing a light scattering agent with the particle size of 3-4.5 nm by titanate through sol-gel reaction, carrying out proper hydrophilic modification on the surface, blending with Methyl Methacrylate (MMA), and preparing the polymethyl methacrylate Rayleigh scattering master batch with narrow particle size distribution, uniform dispersion and high light scattering agent content by adopting a suspension polymerization mode. The preparation method provided by the invention solves the problems of poor compatibility of light scattering agents such as titanium dioxide and the like and light scattering base materials, uneven light scattering, insufficient scattering effect and the like.
Description
Technical Field
The application relates to preparation of a light diffusion plate raw material for improving indoor environment, in particular to an in-situ polymethyl methacrylate master batch with Rayleigh scattering effect and a preparation method thereof.
Background
In recent years, with the improvement of the physical living standard of people, smart home has been in the field of view of thousands of people, and the blue sky is no longer a sky patent, so that the artificial indoor blue sky has become reality, and a comfortable indoor environment is brought. With the continuous evolution of lighting technology, the demand for LED lighting has evolved from initial brightness and light efficiency, to the pursuit of natural light environments and their effects on human physical and mental health. Thus, sky lights, which simulate natural sunlight and blue sky clouds, begin to appear in the general public's view and gradually become a "star" rising in the illumination world. When the white light of the lamp light source passes through a high-molecular transparent panel added with titanium dioxide nano particles, the blue light in the LED is cut off by the micro particles, so that the blue light is scattered on the surface, the surface of the lamp finally presents a blue sky effect, the color temperature of the white light is basically not influenced, and the panel containing the nano particles acts like the atmosphere of the earth. The sky lamp designed based on the principle can only make people feel abnormal and real blue sky and sunlight as in nature.
However, in the prior art, serious agglomeration problems can occur in direct blending, and the problem of uneven distribution of titanium dioxide nano particles also exists. Meanwhile, in the prior art, such as CN112980125A, the excessive or insufficient size of titanium dioxide nano particles, the control of the addition amount and the like can lead to uneven particle distribution, and abnormal and real blue sky and sunlight are difficult to feel.
The technical scheme of the application avoids a plurality of defects of the traditional direct blending preparation of the light diffusion raw material, realizes the nanoscale distribution of the light diffusion agent in the polymer matrix, and efficiently realizes the Rayleigh scattering effect.
Disclosure of Invention
Aiming at the problems existing in the prior art, the application aims to solve the problems that agglomeration, uneven distribution of titanium dioxide nano particles and difficulty in feeling abnormal and real blue sky and sunlight are caused by direct blending in the prior art, and provides an in-situ polymethyl methacrylate master batch with Rayleigh scattering effect and a preparation method thereof. Wherein, methyl methacrylate is abbreviated as MMA, and polymethyl methacrylate is abbreviated as PMMA.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 30-60 min at high speed, then placing in an ice-water bath, proportionally adding a certain amount of ferric salt aqueous solution, stopping stirring after gel appears, aging, drying and calcining at 400-450 ℃ to obtain the titanium-titanium alloy;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 3-4.5 nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Preparing hydrophilic anatase type nano titanium dioxide into dispersion liquid, then adding MMA, an initiator and a dispersing agent, and adopting a suspension polymerization process to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide.
Preferably, the reagents involved in step 1) are all chemically pure and above;
preferably, the steps 1) to 3) are all carried out by primary deionized water;
preferably, in the step 1), the ferric salt is one of ferric chloride and ferric nitrate, and the iron content is not higher than 0.05% of the titanium content;
preferably, in the step 3), the initiator is one of benzoyl peroxide or azobisisobutyronitrile;
preferably, the titanium dioxide is dispersed in water with a cationic dispersant in step 3) above.
Preferably, a 5wt% aqueous solution of the polyvinyl alcohol 1788 type is used as the dispersing agent for suspension polymerization in the above step 3).
Preferably, in the step, the content of the hydrophilic anatase type nano titanium dioxide is 0.005-0.01 wt% of the PMMA master batch; more preferably 0.008wt%.
Preferably, in the above step, the mass of MMA is 10 to 15wt% of the total reaction system; the total reaction system is a reaction system formed by compounding hydrophilic anatase type nano titanium dioxide into dispersion liquid, MMA, an initiator and a dispersing agent.
Preferably, in the suspension polymerization process, specific ones are: rapidly stirring for 1-3 h at 40-70 ℃, controlling the temperature at 78+/-2 ℃ after suspended particles appear in a reaction system, continuing to react for 3-4 h,
preferably, the in-situ polymethyl methacrylate master batch obtained in the step 3) needs to be repeatedly precipitated and washed for 3-5 times by deionized water, and then is filtered and dried.
The beneficial effects of this application:
1. according to the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect, the affinity between titanium dioxide and polymethyl methacrylate is improved from the source through in-situ polymerization, and the Rayleigh scattering effect of a light diffusion plate prepared subsequently is improved.
2. The method adopts the anatase type nano titanium dioxide with the size of 3-4.5 nm to carry out surface treatment by using plasma, endows the anatase type nano titanium dioxide with hydrophilicity, obtains the hydrophilic anatase type nano titanium dioxide, improves the uniform distribution of the titanium dioxide, leads the anatase type nano titanium dioxide with the oversized size to have agglomeration tendency in MMA, and limits the application of the light diffusion plate in the subsequent preparation. An undersized anatase nano titanium dioxide may result in poor hydrophilicity after surface treatment with plasma. The optimal anatase type nano titanium dioxide size is 4nm.
3. The content of the hydrophilic anatase type nano titanium dioxide adopted by the method is 0.005-0.01 wt% of that of PMMA master batch, and the too small content of the hydrophilic anatase type nano titanium dioxide can cause poor Rayleigh scattering effect; excessive hydrophilic anatase type nano titanium dioxide content can cause excessive increase of light scattering intensity, additional other treatment is needed to reduce agglomeration, the effect is poor, and even agglomeration is eliminated, the effect is unfavorable for displaying a real blue sky effect. The optimal hydrophilic anatase type nano titanium dioxide content is 0.008wt% of the PMMA master batch.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto. The detailed description is to be regarded as illustrative in nature and not as restrictive.
Example 1
The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 30min at high speed, then placing in an ice-water bath, proportionally adding 0.01wt% titanium chloride aqueous solution, stopping stirring after gel appears, aging at room temperature for 6h, drying at 80 ℃ for 6h, and calcining at 420 ℃ for 1h;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 3nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Dispersing titanium dioxide by sodium dodecyl benzene sulfonate to prepare a dispersion liquid, wherein the content of hydrophilic anatase type nano titanium dioxide is 0.005wt% of PMMA master batch, then adding MMA, an initiator adopts benzoyl peroxide, and a dispersing agent adopts polyvinyl alcohol 1788 type 5wt% aqueous solution, wherein the mass of MMA is 15wt% of the total reaction system; the balance of deionized water;
and (3) adopting a suspension polymerization process, rapidly stirring at 40 ℃ for 1h, controlling the temperature at 80 ℃ after suspended particles appear in a reaction system, and continuing to react for 3h, so as to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide, and then repeatedly washing for 5 times by using deionized water, and carrying out suction filtration and drying.
Example 2
The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 50min at high speed, then placing in an ice-water bath, proportionally adding 0.02wt% titanium chloride aqueous solution, stopping stirring after gel appears, aging at room temperature for 6h, drying at 80 ℃ for 6h, and calcining at 450 ℃ for 1h;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 4nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Dispersing titanium dioxide by sodium dodecyl benzene sulfonate to prepare a dispersion liquid, wherein the content of hydrophilic anatase type nano titanium dioxide is 0.01wt% of that of PMMA master batch, then adding MMA, an initiator and a dispersing agent, wherein the mass of MMA is 15wt% of that of the total reaction system, and the initiator adopts benzoyl peroxide and the dispersing agent adopts polyvinyl alcohol 1788 type 5wt% aqueous solution; the balance of deionized water;
and (3) adopting a suspension polymerization process, rapidly stirring at 60 ℃ for 2 hours, controlling the temperature at 78 ℃ after suspended particles appear in a reaction system, and continuing to react for 4 hours, so as to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide, and then repeatedly washing for 4 times by using deionized water, and carrying out suction filtration and drying.
Example 3
The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 50min at high speed, then placing in an ice-water bath, proportionally adding 0.02wt% titanium chloride aqueous solution, stopping stirring after gel appears, aging at room temperature for 6h, drying at 80 ℃ for 6h, and calcining at 450 ℃ for 1h;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 4nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Dispersing titanium dioxide by sodium dodecyl benzene sulfonate to prepare a dispersion liquid, wherein the content of hydrophilic anatase type nano titanium dioxide is 0.008wt% of PMMA master batch, then adding MMA, an initiator and a dispersing agent, wherein the mass of MMA is 15wt% of the total reaction system, and the initiator adopts benzoyl peroxide and the dispersing agent adopts polyvinyl alcohol 1788 type 5wt% aqueous solution; the balance of deionized water;
and (3) adopting a suspension polymerization process, rapidly stirring at 60 ℃ for 2 hours, controlling the temperature at 78 ℃ after suspended particles appear in a reaction system, and continuing to react for 4 hours, so as to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide, and then repeatedly washing for 3 times by using deionized water, and carrying out suction filtration and drying.
Comparative example 1
The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 30min at high speed, then placing in an ice-water bath, proportionally adding 0.01wt% titanium chloride aqueous solution, stopping stirring after gel appears, aging at room temperature for 6h, drying at 80 ℃ for 6h, and calcining at 420 ℃ for 1h;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 30nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Dispersing titanium dioxide by sodium dodecyl benzene sulfonate to prepare a dispersion liquid, wherein the content of hydrophilic anatase type nano titanium dioxide is 2wt% of PMMA master batch, then adding MMA, an initiator adopts benzoyl peroxide, and a dispersing agent adopts polyvinyl alcohol 1788 type 5wt% aqueous solution, wherein the mass of MMA is 15wt% of the total reaction system; the balance of deionized water;
and (3) adopting a suspension polymerization process, rapidly stirring at 40 ℃ for 1h, controlling the temperature at 80 ℃ after suspended particles appear in a reaction system, and continuing to react for 3h, so as to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide, and then repeatedly washing for 5 times by using deionized water, and carrying out suction filtration and drying.
Comparative example 2
The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 30min at high speed, then placing in an ice-water bath, proportionally adding 0.01wt% titanium chloride aqueous solution, stopping stirring after gel appears, aging at room temperature for 6h, drying at 80 ℃ for 6h, and calcining at 420 ℃ for 1h;
2) No plasma surface treatment was performed: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step to obtain anatase type nano titanium dioxide with the size of 3 nm; no plasma surface treatment was performed;
3) Dispersing titanium dioxide by sodium dodecyl benzene sulfonate to prepare a dispersion liquid, wherein the anatase type nano titanium dioxide content is 0.001wt% of PMMA master batch, then adding MMA, an initiator adopts benzoyl peroxide, and a dispersing agent adopts polyvinyl alcohol 1788 type 5wt% aqueous solution, wherein the mass of MMA is 15wt% of the total reaction system; the balance of deionized water;
and (3) adopting a suspension polymerization process, rapidly stirring at 40 ℃ for 1h, controlling the temperature at 80 ℃ after suspended particles appear in a reaction system, and continuing to react for 3h, so as to prepare the PMMA master batch rich in anatase type nano titanium dioxide, and then repeatedly washing for 5 times by deionized water, and carrying out suction filtration and drying.
The PMMA master batches prepared in examples 1-3 and comparative examples 1-2 are prepared into a light diffusion plate with the thickness of 10mm by injection molding and other modes, and the light diffusion plates prepared in examples 1-3 have a real blue sky effect, have an excellent Rayleigh scattering effect, and have uniform anatase type nano titanium dioxide distribution and no agglomeration phenomenon after test. The light diffusion plate is tested in the aspects of light transmittance difference values, blue degree and the like of 390-492 nm wave bands and 492-760 nm wave bands, the light transmittance difference value is 36-42%, wherein the titanium dioxide in the embodiment 2 is distributed uniformly to a degree better than that in the embodiment 1, the Rayleigh scattering effect is also better than that in the embodiment 1, the light transmittance difference value in the embodiment 3 is 40-42%, the titanium dioxide is distributed uniformly most, and the Rayleigh scattering effect is the best in the embodiment. However, the light diffusion plate prepared in comparative example 1 has a light transmittance difference of 3 to 7%, comparative example 2 has a light transmittance difference of 4 to 9%, and the light diffusion plate in comparative example has a low light transmittance difference, which is difficult to satisfy the requirements. Correspondingly, the light diffusion plates prepared in examples 1 to 3 have excellent bluing degree, good blue sky effect, the plates prepared in comparative examples 1 and 2 have lower bluing degree, and the titanium dioxide particles are agglomerated and have lower light transmittance.
The embodiments set forth herein should be understood to be illustrative only and not limiting the scope of the present application, as modifications and adaptations may be made within the scope of the present application without departing from the scope of the present application.
Claims (10)
1. The preparation method of the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect comprises the following steps:
1) Preparation of anatase type nano titanium dioxide: mixing tetrabutyl titanate, ethanol, acetic acid and deionized water in proportion, magnetically stirring at room temperature for 30-60 min at high speed, then placing in an ice-water bath, proportionally adding a certain amount of ferric salt aqueous solution, stopping stirring after gel appears, aging, drying and calcining at 400-450 ℃ to obtain the titanium-titanium alloy;
2) Plasma surface treatment: grinding, ball milling and sieving the anatase type nano titanium dioxide calcined in the previous step, and then carrying out surface treatment on the anatase type nano titanium dioxide with the size of 3-4.5 nm by using plasma to endow the anatase type nano titanium dioxide with hydrophilicity to obtain hydrophilic anatase type nano titanium dioxide;
3) Preparing hydrophilic anatase type nano titanium dioxide into dispersion liquid, then adding MMA, an initiator and a dispersing agent, and adopting a suspension polymerization process to prepare the PMMA master batch rich in the hydrophilic anatase type nano titanium dioxide.
2. The method for preparing an in-situ polymethyl methacrylate masterbatch with Rayleigh scattering efficiency according to claim 1, characterized in that the reagents involved in step 1) are all chemically pure and above.
3. The method for preparing an in-situ polymethyl methacrylate masterbatch with Rayleigh scattering effect according to claim 1 or 2, characterized in that steps 1) to 3) are all carried out with primary deionized water.
4. The method for preparing the in-situ polymethyl methacrylate masterbatch with the Rayleigh scattering effect according to claim 1 or 2, wherein the ferric salt is one of ferric chloride and ferric nitrate, and the iron content is not higher than 0.05% of the titanium content.
5. The method for preparing an in-situ polymethyl methacrylate masterbatch with Rayleigh scattering effect according to claim 1 or 2, characterized in that in step 3), the initiator is one of benzoyl peroxide or azobisisobutyronitrile.
6. The method for preparing an in-situ polymethyl methacrylate masterbatch with Rayleigh scattering efficiency according to claim 1 or 2, characterized in that in step 3) titanium dioxide is dispersed in water with a cationic dispersant; the in-situ polymethyl methacrylate master batch obtained in the step 3) needs to be repeatedly precipitated and washed for 3-5 times by deionized water, and then is filtered and dried.
7. The method for preparing an in-situ polymethyl methacrylate masterbatch with Rayleigh scattering effect according to claim 1 or 2, characterized in that in step 3) a 5wt% aqueous solution of the polyvinyl alcohol 1788 type is used as dispersing agent for suspension polymerization; the mass of MMA is 10-15 wt% of the total reaction system.
8. The method for preparing the in-situ polymethyl methacrylate masterbatch with the Rayleigh scattering effect according to claim 1 or 2, characterized in that the content of the hydrophilic anatase type nanometer titanium dioxide is 0.005-0.01 wt% of the PMMA masterbatch.
9. The method for preparing the in-situ polymethyl methacrylate master batch with the Rayleigh scattering effect according to claim 1 or 2, wherein the content of the hydrophilic anatase type nanometer titanium dioxide is 0.008wt% of that of the PMMA master batch.
10. An in-situ polymethyl methacrylate masterbatch with Rayleigh scattering effect prepared by the preparation method of any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100674427B1 (en) * | 2005-12-08 | 2007-01-25 | 엘지엠엠에이 주식회사 | Light scattered methylmethacrylate suspension polymer and manufacturing method thereof |
| CN112876795A (en) * | 2021-01-20 | 2021-06-01 | 青岛易来智能科技股份有限公司 | Rayleigh scattering material master batch, preparation method thereof, light diffusion plate and lighting device |
| CN112980125A (en) * | 2021-02-22 | 2021-06-18 | 安徽新涛光电科技有限公司 | Rayleigh scattering PMMA plate and preparation method thereof |
| CN114644802A (en) * | 2022-03-22 | 2022-06-21 | 浙江华帅特新材料科技有限公司 | Manufacturing method of blue-phase synergistic PMMA heat-resistant plate and blue-phase synergistic PMMA heat-resistant plate |
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- 2023-02-10 CN CN202310091767.9A patent/CN116284522A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100674427B1 (en) * | 2005-12-08 | 2007-01-25 | 엘지엠엠에이 주식회사 | Light scattered methylmethacrylate suspension polymer and manufacturing method thereof |
| CN112876795A (en) * | 2021-01-20 | 2021-06-01 | 青岛易来智能科技股份有限公司 | Rayleigh scattering material master batch, preparation method thereof, light diffusion plate and lighting device |
| CN112980125A (en) * | 2021-02-22 | 2021-06-18 | 安徽新涛光电科技有限公司 | Rayleigh scattering PMMA plate and preparation method thereof |
| CN114644802A (en) * | 2022-03-22 | 2022-06-21 | 浙江华帅特新材料科技有限公司 | Manufacturing method of blue-phase synergistic PMMA heat-resistant plate and blue-phase synergistic PMMA heat-resistant plate |
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