CN112863621B - Polymethyl methacrylate photopolymer material and preparation and application thereof - Google Patents
Polymethyl methacrylate photopolymer material and preparation and application thereof Download PDFInfo
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- CN112863621B CN112863621B CN202110140447.9A CN202110140447A CN112863621B CN 112863621 B CN112863621 B CN 112863621B CN 202110140447 A CN202110140447 A CN 202110140447A CN 112863621 B CN112863621 B CN 112863621B
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920003229 poly(methyl methacrylate) Polymers 0.000 title claims abstract description 12
- 239000004926 polymethyl methacrylate Substances 0.000 title claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 48
- 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 abstract description 44
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 25
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 21
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 38
- 230000010355 oscillation Effects 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 30
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000006185 dispersion Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000377 silicon dioxide Substances 0.000 abstract description 11
- 238000003860 storage Methods 0.000 abstract description 5
- 239000012952 cationic photoinitiator Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
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- 229920000642 polymer Polymers 0.000 description 16
- 238000002156 mixing Methods 0.000 description 13
- 239000003504 photosensitizing agent Substances 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000007822 coupling agent Substances 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- YYVYAPXYZVYDHN-UHFFFAOYSA-N 9,10-phenanthroquinone Chemical compound C1=CC=C2C(=O)C(=O)C3=CC=CC=C3C2=C1 YYVYAPXYZVYDHN-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
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- 239000002861 polymer material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 102100029469 WD repeat and HMG-box DNA-binding protein 1 Human genes 0.000 description 1
- 101710097421 WD repeat and HMG-box DNA-binding protein 1 Proteins 0.000 description 1
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- 230000007670 carcinogenicity Effects 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
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Classifications
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- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C60/00—Computational materials science, i.e. ICT specially adapted for investigating the physical or chemical properties of materials or phenomena associated with their design, synthesis, processing, characterisation or utilisation
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Abstract
The invention discloses a polymethyl methacrylate photopolymer material and preparation and application thereof. Wherein the photopolymer material comprises the following components: polymethyl methacrylate obtained by polymerizing methyl methacrylate, azodiisobutyronitrile, methyl isobutyl ketone and a cationic photoinitiator and silica nanoparticles contained therein and treated by a silane coupling agent. The prepared photopolymer has higher diffraction efficiency, refractive index modulation, low shrinkage and high stability, and is suitable for the field of holographic storage.
Description
Technical Field
The invention relates to the technical field of holographic recording materials.
Background
The advent of the three-dimensional display era has led to an exponential rise in information content. People have a larger and larger demand for information, and methods for recording, reading and storing information more quickly and effectively are required by society. The research and development of novel organic memory materials with large information memory capacity, high reading speed, high data transmission efficiency and high redundancy are necessary ways. The optical information storage uses light waves as carriers and has a plurality of characteristic parameters such as phase, amplitude, polarization and the like. The stability of the stored data, the transmission speed, the storage capacity and other characteristics of the holographic storage depend on the holographic material
The quality, density, etc. of holograms recorded in a carrier depend to a large extent on the characteristics of the material, and an ideal holographic storage material should have the characteristics of high grating sensitivity, high resolution, non-erasable grating, high diffraction efficiency, wide dynamic range, low noise, fast response speed, good volume shrinkage, etc. The preparation method also needs the process characteristics of low preparation cost, simple preparation process, no subsequent treatment, long preservation time and the like. Holographic storage materials have been developed to date to develop various recording materials such as silver salt dry plates, dichromated gelatin, photorefractive crystals and the like, and the traditional recording materials have high photosensitivity and mature preparation proportion, but have main defects such as severe later wet chemical treatment, environmental influence, high noise, low diffraction efficiency, strong water absorption, unstable grating and the like.
Disclosure of Invention
The invention aims to provide a photopolymer which can be used as a holographic recording material, a preparation method and application thereof, wherein the preparation process of the photopolymer is simple, post-treatment is not needed, the shape and thickness are flexibly regulated and controlled, and the obtained material has a high refractive index modulation degree and diffraction efficiency.
The invention firstly provides the following technical scheme:
a polymethyl methacrylate photopolymer material comprising the following components: polymethyl methacrylate obtained by polymerizing methyl methacrylate, azodiisobutyronitrile, methyl isobutyl ketone and a cationic photoinitiator and silica nanoparticles contained therein and treated by a silane coupling agent.
According to some preferred embodiments of the invention, the photoinitiator has the following chemical formula:
According to some preferred embodiments of the invention, the photopolymer comprises the following raw materials in mass percent: 90.909-98.04% of methyl methacrylate, 0.49-6.5% of photoinitiator, 0.49-3.6% of azodiisobutyronitrile, 0.0467-0.8% of SiO 2 nano particles treated by a silane coupling agent and 0.9333-0.8% of methyl isobutyl ketone.
According to some preferred embodiments of the invention, the SiO 2 nanoparticles in the feedstock have a particle size of 18-22nm.
The photo-induced polymer material takes polymethyl methacrylate (PMMA) as a polymer substrate, a cationic photoinitiator is a photoinitiator, and SiO 2 nano particles with the size of 20nm are used as refractive index regulating parts. Wherein the methyl methacrylate (PMMA) polymer is produced by initiating the copolymerization of Methyl Methacrylate (MMA) and a photoinitiator through a thermal initiator Azobisisobutyronitrile (AIBN).
The invention further provides a preparation method of the photopolymer material, which comprises the following steps:
Carrying out ultrasonic oscillation on a mixed solution containing methyl methacrylate, a photoinitiator and azodiisobutyronitrile to obtain a first mixed solution;
adding SiO 2 nano particles treated by a silane coupling agent into methyl isobutyl ketone solution, and carrying out ultrasonic oscillation to obtain nano particle dispersion;
Adding the nanoparticle dispersion liquid into the first mixed liquid, and carrying out ultrasonic oscillation to obtain a second mixed liquid, wherein the mass of the nanoparticle dispersion liquid is 1-3% of the mass of Methyl Methacrylate (MMA) in the first mixed liquid;
The second mixed solution reacts for 40 minutes to 28 hours at constant temperature under the stirring action, and the obtained viscous basic reaction solution is filled into a mould for sealing;
and (3) reacting the sealed basic reaction solution for 48-72 hours at constant temperature to obtain the photopolymer.
According to some preferred embodiments of the invention, the silane coupling agent is KH570 coupling agent.
According to some preferred embodiments of the invention, the time of the ultrasonic oscillation in the step (1) is 20 to 60 minutes.
According to some preferred embodiments of the invention, the time of the ultrasonic oscillation in the step (2) is 2 to 3 hours.
According to some preferred embodiments of the invention, the time of the ultrasonic oscillation in the step (3) is 2 to 4 hours.
According to some preferred embodiments of the invention, the constant temperature in step (4) is 45-60 ℃.
According to some preferred embodiments of the invention, the constant temperature in step (4) is 55 ℃.
According to some preferred embodiments of the invention, the constant temperature in step (5) is 45-60 ℃.
According to some preferred embodiments of the invention, the constant temperature in step (5) is 55 ℃.
The preparation method can be used for preparing the photopolymer material with the thickness of several micrometers to tens of millimeters, the response wave band is 220-540nm, and compared with undoped polymer materials, the volume stability and the diffraction efficiency are higher, and the method is suitable for volume holographic storage application.
The invention further provides an application method of the photopolymer material and/or the photopolymer material prepared by the preparation method, wherein the photopolymer material is used as a holographic recording material.
Preferably, the material is used as a volume hologram memory material for the green light wavelength band.
The invention obtains the polymethyl methacrylate substrate through the combined action of the cationic photoinitiator, especially the bis 2, 6-difluoro-3-pyrrolyl titanocene and the thermal initiator, especially the azo diisobutyronitrile, and compared with the photoinitiator Phenanthrenequinone (PQ) commonly used for MMA monomer polymerization, the invention has higher diffraction efficiency, shorter response time and better photosensitive effect in green light wave band.
In the prior art, a photo-induced polymer is also usually obtained through a photosensitizer acrylamide (AA), the polymer obtained by the photosensitizer is a water-soluble polymer, the strong water absorbability of the photo-induced polymer can cause recorded grating deformation and information distortion, meanwhile, the obtained polymer cannot be made into a thick material, so that the recorded information quantity is greatly limited, and in addition, the photosensitizer has high photosensitivity and toxicity and carcinogenicity, and is not suitable for popularization and use. The invention obtains the photopolymer which is oil-soluble polymer through the low-toxicity bis 2, 6-difluoro-3-pyrrolyl titanocene photoinitiator, the recording process is not affected by moisture, the shape is stable, the information recording is accurate, the thickness of the material can be from millimeter to centimeter, and the recordable information amount is large.
After the preparation and forming of the photopolymeric material containing the nano particles, the photopolymeric material also contains 10-20% of unpolymerized and monomeric MMA, the unpolymerized and monomeric MMA is irradiated by constructive and destructive bright and dark fringes in the interference recording process, residual MMA monomers in the material can diffuse and polymerize into chains towards a high-intensity light region, meanwhile, the silicon dioxide nano particles are effectively pushed into the destructive interference region to strive for balance, good diffraction effect is generated, meanwhile, the silicon dioxide nano particles used by the invention have a refractive index of approximately 1.46, a higher refractive index difference exists between the silicon dioxide nano particles and methyl methacrylate, the absorption or scattering of the silicon dioxide nano particles in a visible light wavelength region is completely negligible, and the diffraction effect of the material can be effectively enhanced.
The silicon dioxide nano particles contained in the photopolymer material can effectively reduce shrinkage of the material generated in the photopolymerization process when the material is used for recording gratings, and can further improve the accuracy of holographic recording by being matched with MMA monomers with low shrinkage capacity.
The photopolymer material is an organic glass material added with inorganic nano particles, has high temperature resistance, no water absorption, moisture resistance and good toughness, and is more stable and easy to store compared with other holographic storage materials in the prior art, such as a silver salt dry plate.
Drawings
FIG. 1 shows images of the product obtained in the example of 0 level and +1 level and-1 level of the volume hologram grating recorded by 532nm laser.
FIG. 2 is a graph showing diffraction efficiency of the product obtained in the example.
FIG. 3 is a diffraction efficiency detection light path diagram of the product obtained in the example.
FIG. 4 is a diagram of a hologram recorded for a product obtained in the example
Fig. 5 is a reproduction image of the real object.
FIG. 6 is an absorption spectrum of the product obtained in the example.
Detailed Description
The present invention will be described in detail with reference to the following examples and drawings, but it should be understood that the examples and drawings are only for illustrative purposes and are not intended to limit the scope of the present invention in any way. All reasonable variations and combinations that are included within the scope of the inventive concept fall within the scope of the present invention.
The following examples prepare photopolymer holographic recording materials by the following steps:
(1) The weight percentages of the Methyl Methacrylate (MMA) and the photoinitiator bis-2, 6-difluoro-3-pyrrolyl titanocene are 90.909 to 98.04 percent, 0.49 to 6.5 percent and 0.49 to 3.6 percent respectively
Irgacure 784 (TI)) and Azobisisobutyronitrile (AIBN) and performing ultrasonic oscillation with a power of 70w and an ultrasonic frequency of 40kHz to uniformly mix Irgacure 784 and Azobisisobutyronitrile (AIBN), and then filtering undissolved photosensitizer to obtain a first mixed solution;
(2) Adding 20nm SiO 2 nano particles with mass fraction of 0.0467-0.8% after being treated by a silane coupling agent into methyl isobutyl ketone (MIBK) solution with mass fraction of 0.9333-0.8%, and carrying out ultrasonic oscillation to obtain nano particle dispersion liquid;
(3) Adding the nanoparticle dispersion liquid into the first mixed liquid, and carrying out ultrasonic oscillation to uniformly mix the solutions to obtain a second mixed liquid, wherein the mass of the nanoparticles is 1-3% of that of the first mixed liquid;
(4) The second mixed solution reacts for 2-3 hours at constant temperature under the stirring action, and the obtained viscous basic reaction solution is filled into a glass mold for sealing;
(5) Baking the sealed basic reaction solution for about 2 hours at a constant temperature to obtain a precursor polymer;
(6) And (3) baking the precursor polymer for 48 hours at a constant temperature to fully polymerize and solidify the precursor polymer into blocks, thereby obtaining the photopolymer.
In particular use, the material may be removed from the die and cut and polished to a thickness and shape that may be determined by the thickness and shape of the die, and polymer samples generally having a thickness of a few microns to tens of millimeters may be prepared according to the above procedure.
Wherein the photosensitizer bis 2, 6-difluoro-3-pyrrolyl titanocene has the following structural formula:
the azodiisobutyronitrile and the methyl isobutyl ketone have the following structural formula:
The polymethyl methacrylate photopolymer obtained by methyl methacrylate has the following structural formula:
The mixed solution obtained by mixing the raw materials is orange or orange.
Example 1
A photopolymer holographic recording material is prepared by the steps of:
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 1g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing 1g of photosensitizer Irgacure 784 (TI), mixing with the obtained organic mixed solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 20 minutes to uniformly mix the organic mixed solution to obtain a first mixed solution;
(4) Weighing 1g of 20nm amphiphilic SiO 2 nano-particles treated by KH570 coupling agent, adding the nano-particles into 15g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano-particle dispersion;
(5) Adding 1g of the obtained SiO 2 nano particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 2 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 55 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 2 to 3 hours until the polymer solution becomes glycerol-like viscous; obtaining a basic reaction solution;
(6) And (3) keeping the obtained basic reaction liquid at a constant temperature, filling the basic reaction liquid into a mold, sealing the mold, putting the mold into a constant temperature oven at 55 ℃, baking the mold at the constant temperature for about 50 hours until the mold is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
Example 2
A photopolymer holographic recording material is prepared by the steps of:
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 1g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing a photosensitizer Irgacure 784 (TI) with the mass of 2g, mixing with the obtained organic mixed solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 20 minutes to uniformly mix the mixture to obtain a first mixed solution;
(4) Weighing 1g of 20nm amphiphilic SiO 2 nano-particles treated by KH570 coupling agent, adding the nano-particles into 15g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano-particle dispersion;
(5) Adding 1g of the obtained SiO 2 nano particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 2 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 55 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 2 to 3 hours until the polymer solution becomes glycerol-like viscous; obtaining precursor liquid;
(6) And (3) keeping the constant temperature of the obtained precursor liquid, filling the precursor liquid into a mold, sealing the mold, loading the mold into a constant temperature oven at 55 ℃, baking the mold at the constant temperature for about 50 hours until the precursor liquid is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
Example 3
A photopolymer holographic recording material is prepared by the steps of:
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 1g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing 3g of photosensitizer Irgacure 784 (TI), mixing with the obtained organic mixed solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 20 minutes to uniformly mix the organic mixed solution to obtain a first mixed solution;
(4) Weighing 1g of 20nm amphiphilic SiO2 nano particles treated by KH570 coupling agent, adding the particles into 15g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano particle dispersion;
(5) Adding 1g of the obtained SiO 2 nano particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 2 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 55 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 2 to 3 hours until the polymer solution becomes glycerol-like viscous; obtaining a basic reaction solution;
(6) And (3) keeping the obtained basic reaction liquid at a constant temperature, filling the basic reaction liquid into a mold, sealing the mold, putting the mold into a constant temperature oven at 55 ℃, baking the mold at the constant temperature for about 50 hours until the mold is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
Example 4
A photopolymer holographic recording material is prepared by the steps of:
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 1g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing photosensitizer Irgacure 784 (TI) with the mass of 4g, mixing with the obtained organic solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 20 minutes to uniformly mix the organic solution to obtain a first mixed solution;
(4) Weighing 1g of 20nm amphiphilic SiO 2 nano-particles treated by KH570 coupling agent, adding the nano-particles into 10g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano-particle dispersion;
(5) Adding 1g of the obtained SiO 2 nano particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 2 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 55 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 2 to 3 hours until the polymer solution becomes glycerol-like viscous; obtaining a basic reaction solution;
(6) And (3) keeping the obtained basic reaction liquid at a constant temperature, filling the basic reaction liquid into a mold, sealing the mold, putting the mold into a constant temperature oven at 55 ℃, baking the mold at the constant temperature for about 50 hours until the mold is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
Example 5
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 0.8g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing 5g of photosensitizer Irgacure 784 (TI), mixing with the obtained organic mixed solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 20 minutes to uniformly mix the organic mixed solution to obtain a first mixed solution;
(4) Weighing 1g of 20nm amphiphilic SiO 2 nano particles treated by KH570 coupling agent, adding the particles into 20g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano particle dispersion;
(5) Adding 2g of the obtained SiO 2 nanometer particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 2 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 60 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 40 to 120 minutes until the polymer solution becomes glycerol-like viscous; obtaining a basic reaction solution;
(6) And (3) keeping the obtained basic reaction liquid at a constant temperature, filling the basic reaction liquid into a mold, sealing the mold, loading the mold into a constant temperature oven at 60 ℃, baking the mold at the constant temperature for about 48 hours until the mold is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
Example 6
(1) Ultrasonically oscillating and cleaning a mould, a glass substrate and the like which are required to be used in the preparation process in absolute ethyl alcohol, flushing with deionized water, and putting into a constant-temperature oven for drying for later use;
(2) Weighing 100g and 1g of Methyl Methacrylate (MMA) and Azobisisobutyronitrile (AIBN) respectively, and mixing the two to obtain an organic mixed solution;
(3) Weighing 3.6g of photosensitizer Irgacure 784 (TI), mixing with the obtained organic mixed solution, and carrying out ultrasonic oscillation in an ultrasonic cleaner for 30 minutes to uniformly mix the organic mixed solution to obtain a first mixed solution;
(4) Weighing 2g of 20nm amphiphilic SiO2 nano particles treated by KH570 coupling agent, adding the particles into 10g of methyl isobutyl ketone (MIBK), and carrying out ultrasonic oscillation for 3 hours to obtain uniform SiO 2 nano particle dispersion;
(5) Adding 2g of the obtained SiO 2 nano particle dispersion liquid into the obtained first mixed liquid, carrying out ultrasonic oscillation for 4 hours, then placing the obtained orange liquid which is uniformly mixed into a constant-temperature water bath kettle with a magnetic stirring function at 45 ℃, heating the mixture in the constant-temperature water bath, and stirring the mixture for 20-28 hours until the polymer solution becomes glycerol-like viscous; obtaining a basic reaction solution;
(6) And (3) keeping the obtained basic reaction liquid at a constant temperature, filling the basic reaction liquid into a mold, sealing the mold, putting the mold into a constant temperature oven at 45 ℃, baking the mold at the constant temperature for about 72 hours until the mold is completely thermally polymerized into a solid block material, and taking the solid block material out of the mold, and cutting and polishing the solid block material to obtain the holographic recording material.
The diffraction efficiency of the products of examples 1-6 was measured and calculated by the detection light path shown in fig. 3, which produced a laser source by a 532nm green laser 1, and the source was split into two beams in the direction perpendicular to each other by a beam splitter 2, and the beams were irradiated to the resulting product photopolymer 5 by a first mirror 3 and a second mirror 4, respectively, and the transmitted light and the diffraction average power were obtained by two first laser power meters 6 and second laser power meters 7 placed behind the photopolymer 5 at a certain angle to each other.
The diffraction efficiency is obtained by:
Wherein I +1 represents the first order diffraction light intensity. I 0 is the transmitted light intensity.
Comparing the diffraction efficiency of the different products, it is found that the product obtained in example 4, namely the photo-initiator Irgacure 784 (TI) with the content of 4wt% of monomer MMA, and the diffraction efficiency of the product obtained by adding 1wt% of 10% silica nanoparticle dispersion liquid and reacting at the constant temperature of 55 ℃ can reach the best effect. The product is characterized in that a 0 level and a +1 level and a-1 level obtained by reproduction of a 532nm laser recorded volume holographic grating through reference light are shown in a graph of fig. 1, a diffraction efficiency-exposure time graph is shown in fig. 2, a light absorption spectrum is shown in fig. 6, and it can be seen that: the absorption spectrum band of the photopolymer added with the silica nanoparticles is 220-540nm, and the photopolymer has quick response time and higher diffraction efficiency.
The object shown in fig. 4 is selected, the product of the embodiment 4 is used as a holographic storage material to record the object through a holographic light path, a reproduced image of the object shown in fig. 5 can be obtained, and the image can fully show the shape and details of the object, so that the recording effect is excellent.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (8)
1. A method for preparing a polymethyl methacrylate photopolymer material comprising the steps of:
(1) Carrying out ultrasonic oscillation on a mixed solution containing methyl methacrylate, a photoinitiator and azodiisobutyronitrile to obtain a first mixed solution;
(2) Adding SiO 2 nano particles treated by a silane coupling agent into methyl isobutyl ketone solution, and carrying out ultrasonic oscillation to obtain nano particle dispersion;
(3) Adding the nanoparticle dispersion liquid into the first mixed liquid, and carrying out ultrasonic oscillation to obtain a second mixed liquid, wherein the mass of the nanoparticle dispersion liquid is 1-3% of the mass of methyl methacrylate in the first mixed liquid;
(4) The second mixed solution reacts for 40 minutes to 28 hours at constant temperature under the stirring action, and the obtained viscous basic reaction solution is filled into a mould for sealing;
(5) Reacting the sealed basic reaction solution for 48-72 hours at constant temperature to obtain the photopolymer material;
Wherein the photoinitiator has the following chemical structural formula:
；
The ultrasonic oscillation time in the step (2) is 2-3 hours; the constant temperature in the step (4) is 45-60 ℃; the constant temperature in the step (5) is 45-60 ℃.
2. The method of manufacturing according to claim 1, characterized in that: the ultrasonic oscillation time in the step (1) is 20-60 minutes; and/or the time of the ultrasonic oscillation in the step (3) is 2 to 4 hours.
3. The method of manufacturing according to claim 1, characterized in that: the constant temperature in the step (4) is 55 ℃.
4. The method of manufacturing according to claim 1, characterized in that: the constant temperature in the step (5) is 55 ℃.
5. The method of manufacturing according to claim 1, characterized in that: the photopolymer material comprises the following raw materials in percentage by mass: 90.909-98.04% of methyl methacrylate, 0.49-6.5% of photoinitiator, 0.49-3.6% of azodiisobutyronitrile, 0.0467-0.8% of SiO 2 nano particles treated by a silane coupling agent and 0.9333-0.8% of methyl isobutyl ketone.
6. The method of manufacturing according to claim 1, characterized in that: the particle size of the SiO 2 nano particles is 18-22nm.
7. A photopolymer material prepared by the preparation method according to any one of claims 1 to 6.
8. Use of the photopolymer material of claim 7 as holographic recording material.
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