CN117700744A - Polysilsesquioxane and photopolymer holographic recording medium containing same - Google Patents

Polysilsesquioxane and photopolymer holographic recording medium containing same Download PDF

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CN117700744A
CN117700744A CN202311785361.7A CN202311785361A CN117700744A CN 117700744 A CN117700744 A CN 117700744A CN 202311785361 A CN202311785361 A CN 202311785361A CN 117700744 A CN117700744 A CN 117700744A
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recording medium
polysilsesquioxane
photopolymer
holographic recording
formula
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张荻琴
郭斌
黄星
施盟泉
张玉玺
张云龙
赵榆霞
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Technical Institute of Physics and Chemistry of CAS
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses polysilsesquioxane and a photopolymer type holographic recording medium containing the same. The polysilsesquioxane is selected from one of general structures shown in T1-T4, wherein the polysilsesquioxane with a structure shown in a formula T1 or a formula T2 can be connected to an epoxy resin-amine film-forming resin through an epoxy group or an amino group in a covalent bond manner to prepare the photopolymer type holographic recording medium, and the polysilsesquioxane with a structure shown in a formula T3 or a formula T4 can be connected to an isocyanate-alcohol film-forming resin through an isocyanate group or a hydroxyl group in a covalent bond manner to prepare the photopolymer type holographic recording medium, so that the volume shrinkage of the photopolymer type holographic recording medium in the holographic exposure process can be reduced, the sensitivity and the dynamic range of the photopolymer type holographic recording medium can be improved, and the rapid and high-capacity high-density holographic optical storage can be effectively realized.

Description

Polysilsesquioxane and photopolymer holographic recording medium containing same
Technical Field
The present invention relates to the field of high density optical storage. And more particularly, to a polysilsesquioxane and a photopolymer type hologram recording medium including the same.
Background
With the rapid development of the human society information age, the realization of high-capacity, rapid and low-energy-consumption information storage and transmission becomes a urgent problem to be solved in the current society. Photopolymers are currently the most practical holographic recording materials, and generally comprise film-forming resins, writing monomers, photoinitiating systems and the like, wherein light is used for polymerizing the monomers, and the monomers and the film-forming resins form phase holographic gratings with modulated refractive indexes to record and reproduce information. However, in practical applications, the monomer polymerization can generate unavoidable volume shrinkage, which can lead to deformation of the recorded holographic grating for thick film type volume hologram recording medium, affecting the fidelity of information reproduction, which is a challenge to be solved. The incorporation of inorganic nanoparticles into a photopolymer by Tomita et al (Applied Optics,2004, 43, 2125) can effectively reduce the volume shrinkage of the recording medium, but inorganic nanoparticles have problems of poor size uniformity and dispersion stability, poor compatibility with film-forming resins, and the like.
Polysilsesquioxane (POSS) is an organic/inorganic hybrid nanoparticle with good size uniformity, and the core of the polysilsesquioxane is an inorganic cage-shaped substance constructed by Si-O bonds, and functional organic groups such as acrylate groups, hydroxyl groups, mercapto groups, epoxy groups, amino groups and the like can be introduced around the Polysilsesquioxane (POSS), or the polysilsesquioxane can be connected to a polymer through covalent bonds, so that the compatibility between the POSS and film-forming resin is greatly improved. Researchers are currently focusing more on doping writing monomers with POSS modified polymerizable groups to control the polymerization of the monomers, and less on modifying film-forming resins to adjust the relative between the components during exposureAnd (5) migration. Xie Xiaolin et al (CN 201710765386.9) control the initial viscosity of recording media to 200-800 mPas in a photopolymer using thiol or alkene monomers as writing monomers by doping thiol-or alkene-modified POSS, and improve the information storage quality, but have a small dynamic range. Tan Xiaode et al (ACS Applied Materials)&Interface, 2022, 14 th edition, 21544) doped with methacrylate-modified POSS in a photopolymer based on Methyl Methacrylate (MMA) as writing monomer, the photopolymer having a diffraction efficiency of 75% and a volume shrinkage of 0.09%, but a very low sensitivity of only 1.47×10 -3 cm/mJ. Therefore, in order to further improve the holographic performance such as sensitivity and dynamic range of the holographic recording medium, it is necessary to research a polysilsesquioxane POSS modified with an epoxy group, an amino group, an isocyanate group or a hydroxyl group, and further provide a photopolymer type holographic recording material using an epoxy resin-amine or an isocyanate-alcohol as a film forming resin and having excellent properties such as high sensitivity, large dynamic range, low volume shrinkage and the like.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a polysilsesquioxane. The polysilsesquioxane can be connected to film-forming resin of epoxy resin-amine or isocyanate-alcohol after being modified by epoxy group, amino group, isocyanate group or hydroxyl group, so that the volume shrinkage of the obtained photopolymer type holographic recording medium in the holographic exposure process is reduced, the sensitivity and dynamic range of the holographic recording medium are improved, and the rapid and high-capacity high-density holographic optical storage is effectively realized.
Another object of the present invention is to provide a photopolymer type hologram recording medium.
In order to achieve the first object, the present invention adopts the following technical scheme:
the invention discloses polysilsesquioxane, which is selected from one of the following general structures:
wherein the R is 1 ～R 7 And may be the same or different, each independently selected from one of the following structures:
the R is 8 ～R 14 And may be the same or different, each independently selected from one of the following structures:
the A is 1 、A 2 、A 3 Can be the same or different, and are each independently selected from any one of hydrogen, methyl, ethyl, methoxy, ethoxy and amino;
the A is 4 、A 5 、A 6 Can be the same or different, and are each independently selected from any one of hydrogen, methyl, ethyl, methoxy, ethoxy and hydroxy;
the X is selected from C 1 ～C 8 Alkyl of C number of carbon atoms 1 ～C 8 Alkoxy, alkyl substituted or unsubstituted C 6 ～C 14 Any one of the phenyl groups of (a);
the n represents an integer of 1 to 8, and the m represents an integer of 1 to 4.
Further, the polysilsesquioxane is selected from one of the structures shown below:
in order to achieve the second object, the present invention adopts the following technical scheme:
the invention discloses a photopolymer type holographic recording medium, which comprises polysilsesquioxane. According to the difference of modification groups on polysilsesquioxane, the invention provides two formulations of photopolymer holographic recording media, in particular as follows:
(1) When the structure of polysilsesquioxane is selected from formula T1 or formula T2, the photopolymer holographic recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane is 0.5-10wt% of the photopolymer type holographic recording medium.
The POSS of the formula T1 or the formula T2 has at least one epoxy group or amino group, and can be connected to the epoxy resin-amine film-forming resin through the epoxy group or the amino group in a covalent bond mode, so that the volume shrinkage of the photopolymer type holographic recording medium in the holographic exposure process is reduced, the sensitivity and the dynamic range of the holographic recording medium are improved, and the rapid high-capacity high-density holographic optical storage is effectively realized.
Further, when the structure of the polysilsesquioxane is selected from formula T1 or formula T2, the photopolymer type hologram recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane comprises 0.5-5wt% of the photopolymer holographic recording medium; illustratively, it may be 0.5wt%, 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, or 5wt%, etc.
The epoxy resin of the present invention is a commercially available epoxy resin such as various epoxy group-containing mono-functional or multi-functional epoxy resins and having a relatively low refractive index, including but not limited to n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, pentanediol diglycidyl ether, glycerol triglycidyl ether, 3, 4-epoxycyclohexenemethyl-3, 4-epoxycyclohexenoate, and the like, and may also be a self-made fluorine-containing epoxy resin (e.g., cn202110168835. X).
The amine curing agent is a medium-low temperature amine curing agent with the curing temperature less than or equal to 60 ℃, such as at least one selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, divinylpropylamine, 2-methylpentanediamine, 1, 3-pentanediamine, 1, 2-cyclohexanediamine, isophoronediamine and the like, or a mixture thereof.
The polymerizable monomer is various monofunctional or polyfunctional aromatic monomers containing C=C unsaturated double bonds and having higher refractive index, and comprises at least one of or a mixture of alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic acid ester compounds, methacrylic acid ester compounds, self-made high refractive index monomers, diffractions thereof and the like; exemplary polymerizable monomers include, but are not limited to, 2-vinylanthracene, 9-vinylanthracene, 1-vinylnaphthalene, 2-vinylnaphthalene, N-vinylpyrrole, N-vinylcarbazole, N-vinylimidazole, N-vinylindole, N-vinylpyrrolidone, trans-N-3-acetylbutenylcarbazole, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate, epoxybisphenol A methacrylate, epoxybisphenol F methacrylate, commercially available SR348, SR349, SR540, SR541, SR542, SR601, SR602, and the like, and also homemade high refractive index monomers and their diffractates, see 2-carbazolylethyl mercapto ethyl acrylate, 2-thiophenylethyl mercapto ethyl acrylate, 2-carbazolylethyl ethoxy methyl acrylate, and the like, prepared in ZL202210077437.X, ZL202210077188.4, ZL202210972623.X, ZL202210076846.8, CN202210077411.5, CN202310685655.6, and the like.
The photoinitiator comprises at least one of onium salt compounds, biimidazole compounds, organic metal compounds, organic borides, benzophenone, michaelis ketone, C1-C10 alkyl substituted thioxanthone, acetophenone derivatives, benzoin ether compounds, alpha-aminoketone compounds, alpha-hydroxyketone compounds, self-made photoinitiators (CN 202210539780.1) and the like, wherein the onium salt compounds are selected from iodonium salts, sulfonium salts or mixtures thereof; the bisimidazoles are selected from hexaarylbisimidazoles; the organic metal compound is selected from titanocene compound, ferrocene salt or their mixture; the organic boride is selected from butyl triphenylborate; the acetophenone derivative is selected from alpha-hydroxycyclohexyl acetophenone; the benzoin ether compound is selected from benzoin dimethyl ether; the alpha-aminoketone compound is selected from I-907 and I-369 produced by German Ciba company or the mixture thereof; the alpha-hydroxy ketone compound is selected from Darocur-1173, darocur-2959, darocur-4265 or their mixture.
The photosensitizer is at least one of various dyes with higher electron transfer efficiency, including but not limited to cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, benzylidene cycloalkanone compounds, coumarin dyes connected by cycloalkanone (such as ZL200310122499.5 and ZL 200310122498.0), coumarin dyes connected by stilbene (such as ZL 200510135231.4) and the like or a mixture thereof.
The chain transfer agent is a mercaptan compound, including but not limited to at least one of dodecyl mercaptan, hexyl mercaptan, phenethyl mercaptan, 4-methyl-4H-1, 2, 4-triazole-3-mercaptan, 5- (4-pyridyl) -1,3, 4-oxadiazole-2-mercaptan and the like or a mixture thereof.
The defoamer is an organic silicon defoamer and comprises at least one or a mixture of BYK-065, BYK-066, BYK-088, BYK-141, BYK-W969, BYK-LP D24043 and the like produced by Pick company.
The leveling agent of the invention is an organosilicon surface auxiliary agent, including but not limited to BYK-306, BYK-310, BYK-344, BYK-358, BYK-1790, BYK-1794 produced by Pick company, and at least one of the group consisting of the courtesy 455, 466 and the like produced by the courtesy corporation of germany, or a mixture thereof.
The plasticizer is at least one selected from the group consisting of toluene, xylene, dimethylformamide, dimethylacetamide, phthalate and the like with low volatility or a mixture thereof.
(2) When the structure of polysilsesquioxane is selected from formula T3 or formula T4, the photopolymer holographic recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane is 0.5-10wt% of the photopolymer type holographic recording medium.
Further, when the structure of the polysilsesquioxane is selected from formula T3 or formula T4, the photopolymer type hologram recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane comprises 3-8wt% of the photopolymer holographic recording medium; illustratively, it may be 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, or the like.
The POSS of the formula T3 or the formula T4 has at least one isocyanate group or hydroxyl group, and can be connected to the isocyanate-alcohol film-forming resin through the isocyanate group or the hydroxyl group in a covalent bond mode, so that the volume shrinkage of the photopolymer type holographic recording medium in the holographic exposure process is reduced, the sensitivity and the dynamic range of the holographic recording medium are improved, and the rapid high-capacity high-density holographic optical storage is effectively realized.
The isocyanate is selected from compounds with low refractive index and two or more isocyanate groups; including but not limited to at least one of the group consisting of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2, 4, 6-trioxytriazine-1, 3,5 (2H, 4H, 6H) -tri) tris (hexamethylene) isocyanate, butane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and the like, or a mixture thereof.
The alcohol is selected from compounds with low refractive index and more than two hydroxyl functional groups; including but not limited to at least one of the group consisting of triethylene glycol, tetraethylene glycol, butanediol, hexanediol, trimethylolethane, glycerol, triethanolamine, polyester polyols having a molecular weight of 200 to 2000, polycarbonate polyols having a molecular weight of 200 to 2000, polyether polyols having a molecular weight of 200 to 2000, and the like, or mixtures thereof.
The polymerizable monomer is various aromatic monomers containing a monofunctional group or a multifunctional group of C=C unsaturated double bond and having higher refractive index; at least one of the group consisting of, but not limited to, alkenyl naphthalene compounds, alkenyl anthracene compounds, alkenyl benzene compounds, acrylic compounds, methacrylic compounds, self-made high refractive index monomers, and the like, or mixtures thereof; including but not limited to N-vinylpyrrole, N-vinylcarbazole, N-vinylimidazole, N-vinylindole, N-vinylpyrrolidone, trans-N-3-acetylenecarbazole, styrene, 2-chlorostyrene, 2-bromostyrene, 3-chlorostyrene, 3-bromostyrene, 4-chlorostyrene, 4-bromostyrene, p- (chloromethyl) styrene, p- (bromomethyl) styrene, pentabromophenyl acrylate, pentachlorophenyl acrylate, phenoxyethyl acrylate, pentabromobenzyl acrylate, 2-naphthyl acrylate, 1, 4-bis (2-thionaphthyl) 2-butyl acrylate, phenoxyethoxyethyl acrylate bisphenol A diacrylate, tetrabromobisphenol A diacrylate, 2-phenoxyethyl acrylate, benzyl acrylate, p-chlorophenyl acrylate, 2,4, 6-trichlorophenyl acrylate, p-bromophenyl acrylate, 2,4, 6-tribromophenyl acrylate, propane-2, 2-diylbis [ (2, 6-dibromo-4, 1-phenylene) oxy (2- { [3, 3-tris (4-chlorophenyl) propionyl ] oxy } propane-3, 1-diyl) oxy ethane-2, 1-diyl ] diacrylate, 2-phenoxyethyl methacrylate, benzyl methacrylate, p-bromophenyl methacrylate, p-chlorophenyl methacrylate, 2,4, 6-trichlorophenyl methacrylate, pentabromophenyl methacrylate, commercially available polymerizable monomers such as pentachlorophenyl methacrylate, phenoxyethyl methacrylate, phenoxyethoxyethyl methacrylate, 1, 4-bis (2-thionaphthyl) 2-butyl methacrylate, pentabromobenzyl methacrylate, 2-naphthyl methacrylate, bisphenol A dimethacrylate, tetrabromobisphenol A dimethacrylate, 2-vinylanthracene, 9-vinylanthracene, 1-vinylnaphthalene, 2-vinylnaphthalene, and the like, and also self-made high refractive index monomers such as ZL202210077437.X, ZL202210077188.4, ZL202210972623.X, ZL202210076846.8, CN202210077411.5, and CN202310685655.6, and the like, and diffractions thereof.
The photoinitiator according to the present invention is an initiator capable of being activated by actinic radiation and initiating polymerization of the corresponding polymerizable groups; including but not limited to at least one of the group consisting of aromatic ketones, benzoin and its derivatives, benzil ketals, acylphosphine oxides, aryl ammonium borates, chromium salts, aryl diazonium salts, onium salts, organometallic compounds, self-made initiators (CN 202210539780.1), and the like, or mixtures thereof.
Illustratively, at least one of the group consisting of benzophenone, alkyl benzophenone, 4' -bis (dimethylamino) benzophenone, anthrone and halogenated benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, bisacylphosphine oxide, phenyl dihydroxyacetate, camphorquinone, a-aminoalkylphenone, α -dialkoxyacetophenone, a-hydroxyalkyl phenone, tetrabutylammonium triphenylhexyl borate, tetrabutylammonium tris- (3-fluorophenyl) hexyl borate, tetrabutylammonium tris- (3-chloro-4-methylphenyl) hexyl borate, ferrocenyl compound, iodonium salt, sulfonium salt, hexaarylbisimidazole, and the like, or a mixture thereof.
The photosensitizer is at least one of various dyes with higher electron transfer efficiency, including but not limited to cyanine dyes, fluorescein dyes, coumarin ketone dyes, nitrogen-containing aromatic heterocyclic compounds, aromatic amine compounds, benzylidene cycloalkanone compounds, coumarin dyes connected by cycloalkanone (such as ZL200310122499.5 and ZL 200310122498.0), coumarin dyes connected by stilbene (such as ZL 200510135231.4), homemade photosensitizers and the like or a mixture thereof.
The chain transfer agent is a mercaptan compound, including but not limited to at least one of dodecyl mercaptan, mercaptoethanol, hexanethiol, phenethyl mercaptan, 5- (4-pyridyl) -1,3, 4-oxadiazole-2-mercaptan, 4-methyl-4H-1, 2, 4-triazole-3-mercaptan and the like or a mixture thereof.
The defoamer provided by the invention is an organic silicon defoamer and comprises at least one or a mixture of BYK-011, BYK-012, BYK-014, BYK-023, BYK-051N, BYK-085, BYK-1610, BYK-1707, BYK-1740, BYK-1760 and DC65, AFE-7820 produced by Dow Corning company.
The leveling agent is an organosilicon surface auxiliary agent, and comprises at least one of BYK-302, BYK-306, BYK-307, BYK-327, BYK-329, BYK-333, BYK-356, BYK-358, BYK-378, BYK-3455, BYK-3566 and the like or a mixture thereof, which are produced by Pick corporation.
The catalyst of the present invention is a tertiary amine catalyst and/or an organometallic catalyst, including but not limited to at least one of the group consisting of triethylenediamine, bis (dimethylaminoethyl) ether, dimethylethanolamine, 2- (2-dimethylamino-ethoxy) ethanol, trimethylhydroxyethyl propylenediamine, N-bis (dimethylaminopropyl) isopropanolamine, dibutyltin dilaurate, stannous octoate, potassium carboxylate catalyst, bismuth carboxylate catalyst, and the like, or a mixture thereof.
The water scavenger of the invention comprises at least one or a mixture of p-toluenesulfonyl isocyanate, triethyl orthoformate, CUWR-WB20 water scavenger of Guangzhou super wet synthetic material, ALT-201 water scavenger of Initer chemical industry, shanghai luer chemical industry trade, PCCI water scavenger of Shanghai, and the like.
The plasticizer is at least one of toluene, xylene, dimethylformamide, dimethylacetamide, glycerol, phthalate and the like or a mixture thereof.
The invention also provides a preparation method of the photopolymer type holographic recording medium, which comprises the following steps:
the photopolymer type volume hologram recording medium of the present invention is a circular optical disk or a square optical disk, which is referred to as 202110168835. X, in which each raw material component is recorded by a photopolymer type hologram having a certain thickness sandwiched between two optical substrates.
The beneficial effects of the invention are as follows:
the polysilsesquioxane POSS modified by epoxy group, amino group, isocyanate group or hydroxyl group can be connected to epoxy resin-amine or isocyanate-alcohol film-forming resin in a covalent bond mode through an active functional group in the structure, so that the low-volume shrinkage, high-sensitivity and large-dynamic-range photopolymer type holographic recording medium is obtained, the volume shrinkage is less than 0.4%, the sensitivity is more than or equal to 0.18cm/mJ, the dynamic range is more than 15, the angle multiplexing of 60 holograms can be realized, and the invention has wide application prospects in the fields of high-density optical storage and the like.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
Fig. 1 shows X-ray elemental energy spectra and silicon content of the photopolymer type hologram recording media of examples 1 to 4.
FIG. 2 shows 532nm laser exposure characteristic curves of the photopolymer type hologram recording media of examples 1 to 4 of the present invention and comparative example 1.
FIG. 3 shows the angular selectivity curves of the photopolymer type holographic recording media of examples 1-4 and comparative example 1 of the present invention recording 2000lp/mm gratings.
Fig. 4 shows a graph of diffraction efficiency of 60 pieces of angle-multiplexed photopolymer type hologram recording medium according to example 1 of the present invention according to a rotation angle at ±30° with a laser of 405 nm.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The structure of the polysilsesquioxane POSS modified by the epoxy group is shown as a formula T1-a:
the preparation method comprises the following steps:
10g (propyl glycidyl ether) trimethoxysilane and 0.2g tetramethyl ammonium hydroxide are dissolved in 100mL of mixed solution of isopropanol and water, stirred for 12h at room temperature, heated to 60 ℃ and stirred until a large amount of white solid is precipitated, filtered and washed to obtain the product.
Specific steps in the preparation of photopolymer holographic recording media are referred to 202110168835. X.
Preparation of photopolymer mixture: in a dark room, the materials of Table 1 were successively charged into 500ml of a vessel equipped with a stirring device. Stirring at room temperature for 10-15 min to mix them uniformly, filtering with a filter with aperture of 0.22 μm, vacuum degassing the filtrate in a vacuum vessel, injecting nitrogen into the filtrate, and standing.
TABLE 1
Butanediol diglycidyl ether 45 g
T1-a 2g
Tetraethylenepentamine 15 g
N-vinylcarbazole 25 g
2-carbazolylethyl mercapto ethyl acrylate 8g
2, 5-bis [4- (diethylamino) -benzylidene]Cyclopentanone (CNG) 0.01 g
Hexaarylbisimidazoles 0.9 g
4-methyl-4H-1, 2, 4-triazole-3-thiol 0.9 g
BYK-066 0.1g
BYK-344 0.1g
Dimethylformamide 3 g
Preparation of a holographic recording medium mold: selecting 20 circular substrates with the diameter of 120mm and the thickness of 1mm, 10 large circular gaskets with the outer diameter of 120mm, the inner diameter of 110mm and the thickness of 0.5mm, and 10 small circular gaskets with the outer diameter of 20mm, the inner diameter of 15mm and the thickness of 0.5mm, wherein the substrates are all K9 optical glass, the gasket materials are polytetrafluoroethylene, a small opening is formed in the large circular gaskets, the large circular gaskets are correspondingly placed between two circular substrates, and 10 hollow circular dies with the outer diameter of 110mm and the inner diameter of 20mm are assembled, and are fixed by a clamp for later use.
Preparation of photopolymer holographic recording Medium: the above-mentioned hologram recording medium mold and photopolymer mixture was placed in a glove box filled with nitrogen gas, and the mixture was injected into the mold through a small opening in a gasket in the mold with a syringe. After the pouring, the obtained sample wafer is placed in a constant temperature and humidity box at 35 ℃ for 48 hours, the film forming resin in the pouring liquid is completely solidified, the clamp is removed, the small opening is sealed, the sample wafer is wrapped by aluminum foil paper and stored in a dark place, and the photopolymer holographic recording medium is prepared, and the holographic performance parameters of the photopolymer holographic recording medium are shown in table 6.
Fig. 1 shows X-ray elemental energy spectra and silicon content of the photopolymer type hologram recording media of examples 1 to 4.
Example 2
The structure of the amino modified polysilsesquioxane POSS is shown as a formula T2-a:
the preparation method comprises the following steps:
8g of isobutyl trichlorosilane, 1g of (propylamino) trimethoxysilane and 0.1g of tetramethylammonium hydroxide are dissolved in 100mL of mixed solution of isopropanol and water, stirred for 12h at room temperature, heated to 60 ℃ and stirred until a large amount of white solid is precipitated, filtered and washed to obtain the product.
A photopolymer type hologram recording medium was prepared according to the method described in example 1, except that the raw materials thereof are shown in table 2, unlike example 1. The hologram performance parameters of the obtained photopolymer type hologram recording medium are shown in table 6.
TABLE 2
Hexanediol diglycidyl ether 47 g
Triethylene tetramine 16 g
T2-a 3 g
N-vinylcarbazole 20 g of
2-carbazolylethyl mercapto ethyl acrylate 10g
2, 5-bis [ 9-julolidine-2-methylidene]Cyclopentanone (CNG) 0.02 g
IR 784 0.9 g
Phenethyl mercaptan 0.9 g
BYK-141 0.1g
BYK-358 0.1g
Dimethylacetamide 2g
Example 3
The structure of the polysilsesquioxane POSS modified by the isocyanate group is shown as a formula T3-a:
the preparation method comprises the following steps:
4g of n-butyltrichlorosilane, 4g of (propylisocyanato) trimethoxysilane and 0.1g of tetrabutylammonium bromide are dissolved in a mixed solution of 100mL of tetrahydrofuran and water, stirred for 12 hours at room temperature, heated to 50 ℃ and stirred until a large amount of white solid is precipitated, filtered and washed to obtain the product.
A photopolymer type hologram recording medium was prepared according to the method described in example 1, except that the raw materials thereof are shown in table 3, unlike example 1. The hologram performance parameters of the obtained photopolymer type hologram recording medium are shown in table 6.
TABLE 3 Table 3
Hexamethylene diisocyanate 30 g
T3-a 4g
Polyethylene glycol (molecular weight 400) 29 g
2-Phenoxyethyl methacrylate 20 g of
2-carbazolylethyl mercapto ethyl acrylate 10g
2, 5-bis [4- (dimethylamino) -thiophene-2-methylene]Cyclopentanone (CNG) 0.01 g
2,4, 6-trimethylbenzoyl diphenyl phosphine oxide 0.9 g
5- (4-pyridinyl) -1,3, 4-oxadiazole-2-thiol 0.9 g
BYK-011 0.1g
BYK-329 0.1g
ALT-201 2.5 g
Dimethylethanolamine 0.5 g
Phthalic acid esters 2g
Example 4
The hydroxyl modified polysilsesquioxane POSS has a structure shown as a formula T4-a:
the preparation method comprises the following steps:
10g of hydroxypropyl trimethoxysilane and 0.1g of tetrabutylammonium bromide are dissolved in 100mL of mixed solution of tetrahydrofuran and water, stirred for 12 hours at room temperature, heated to 50 ℃ and stirred until a large amount of white solid is precipitated, filtered and washed to obtain the aqueous solution.
A photopolymer type hologram recording medium was prepared according to the method described in example 1, except that the raw materials thereof are shown in table 4, unlike example 1. The hologram performance parameters of the obtained photopolymer type hologram recording medium are shown in table 6.
TABLE 4 Table 4
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Fig. 1 shows the X-ray element spectra and the silicon content of the photopolymer type hologram recording medium of examples 1 to 4, and it can be seen that the silicon element of example 1 accounts for 0.19% by mass of all elements of the photopolymer type hologram recording medium (i.e., the silicon content), the silicon content of example 2 is 0.32%, the silicon content of example 3 is 0.39%, and the silicon content of example 4 is 0.59%.
Comparative example 1
A photopolymer type hologram recording medium was prepared according to the method described in example 1, except that the raw materials thereof are shown in table 5, unlike example 1. The hologram performance parameters of the obtained photopolymer type hologram recording medium are shown in table 6.
TABLE 5
Butanediol diglycidyl ether 45 g
Tetraethylenepentamine 15 g
N-vinylcarbazole 25 g
2-carbazolylethyl mercapto ethyl acrylate 8g
2, 5-bis [4- (dimethylamino) -benzylidene]Cyclopentanone (CNG) 0.01 g
Hexaarylbisimidazoles 0.9 g
4-methyl-4H-1, 2, 4-triazole-3-thiol 0.9 g
BYK-066 0.1g
BYK-344 0.1g
Dimethylacetamide 3 g
Test example 1
Holographic exposure performance test of photopolymer type holographic recording Medium:
by expanding with 532nm wavelength solid laser as light sourceThe beam device obtains a laser spot with the diameter of 8mm, then two beams of light are obtained by using a beam splitter, a half-wave plate and a diaphragm, the two beams of light are intersected in a photopolymer type holographic recording medium to be measured for exposure, the normal line of the recording medium bisects the two beams of light, the included angle of the two beams of light is 27 degrees, and the light intensity is 1.2mW/cm 2 And simultaneously, the light intensity of the transmitted light and the diffracted light of the holographic grating in the exposure area is monitored in real time by using a photoelectric detector, and the monitoring is carried out every 2 s. The diffraction efficiency (eta) of the single grating is calculated by diffraction light/(diffraction light+transmission light) max ) By means ofThe photosensitivity (S) of the recording medium is calculated, where E is the exposure required to achieve maximum diffraction efficiency and d is the material photosensitive layer thickness.
Fig. 2 shows 532nm laser exposure characteristic curves (single grating diffraction efficiency versus exposure variation curves) of the photopolymer type hologram recording media in examples 1 to 4 and comparative example 1. The smaller the exposure amount required for the photopolymer type recording medium to reach the maximum diffraction efficiency, the higher the sensitivity. The photopolymer type recording media of examples 1-4 all have diffraction efficiency greater than 85% and sensitivity greater than 0.18cm/mJ, and experimental results show that the photopolymer type holographic recording media doped with POSS have the characteristics of high diffraction efficiency and high sensitivity.
Table 6 shows the holographic performance parameters of the photopolymer type holographic recording media of examples 1-4 and comparative example 1, including the sensitivity of the media, volume shrinkage, dynamic range, and diffraction efficiency, selection angle of the recorded gratings.
TABLE 6
Test item Comparative example 1 Example 1 Example 2 Example 3 Example 4
Diffraction efficiency eta max (％) 92.0 86.9 92.2 92.6 88.3
Reach eta max Exposure E (mJ/cm) 2 ) 121.1 102.6 95.5 100.6 90.7
Sensitivity S (cm/mJ) 0.15 0.18 0.24 0.20 0.22
2000lp/mm grating selection angle delta theta (°) 0.85 0.46 0.11 0.23 0.32
Volume shrinkage (%) 0.52 0.38 0.31 0.36 0.37
Dynamic range M/# (/ 0.5 mm) 13.6 15.8 18.8 16.9 16.5
Test example 2
Grating angle selectivity of 2000lp/mm recorded by photopolymer holographic recording media:
using a solid laser with 532nm wavelength as a light source, obtaining two laser beams with the size of 5 multiplied by 5 (length multiplied by width, unit: mm) through a beam expander, a beam splitter, a half-wave plate and the like, wherein the laser intensity is 1:1, intersecting the two laser beams in a photopolymer type holographic recording medium to be detected for exposure, dividing the two laser beams by the normal line of the recording medium, and forming an included angle of 64 degrees and the light intensity of 10mW/cm by the two laser beams 2 A holographic grating with a spatial frequency of 2000lp/mm is recorded, a solid laser with a wavelength of 633nm is used as a detection light source (the recording medium does not react with the holographic grating), an exposure area is irradiated from a Bragg angle, exposure is stopped when the diffraction light intensity is maximum, the incidence angle of the detection light is slowly changed (the angle resolution is 0.01 DEG), the diffraction light gradually decreases to a minimum value from a maximum value to two sides, an angle selectivity curve is obtained at the moment, and the angle interval corresponding to the half-peak width is the selection angle (delta theta) of the recording medium.
Fig. 3 shows the angular selectivity curves (grating diffraction efficiency versus rotation angle) of 2000lp/mm gratings recorded by the photopolymer type holographic recording media of examples 1-4 and comparative example 1. The smaller the selection angle, the wider the range of angular multiplexing of the photopolymer type recording medium at the same position, the larger the dynamic range thereof. The selection angle half-peak width of the photopolymer type recording medium in examples 1 to 4 is only 0.11 to 0.46 degrees, which shows that the photopolymer type volume hologram recording medium provided by the invention has the characteristic of large dynamic range.
Test example 3
Angle multiplexing of photopolymer type holographic recording medium:
using a solid laser with 405nm wavelength as a light source, obtaining two laser beams with the diameter of 10mm through a beam expander, a beam splitter, a half wave plate and the like, wherein the laser intensity is 1:1, intersecting the two laser beams in a photopolymer type holographic recording medium to be detected for exposure, dividing the two laser beams by the normal line of the recording medium, and forming an included angle of 60 degrees and the light intensity of 1.3mW/cm by the two laser beams 2 In the same position, the sample is rotated by a rotary translation stage device, a hologram is recorded on the normal line of a recording medium at + -30 DEG and every 30s of exposure at 1 DEG, a solid laser with 633nm wavelength is used as a detection light source after the recording is completed, the incidence angle of the detection light is slowly changed (the angular resolution is 0.01 DEG), the diffraction efficiency of 60 holograms is tested, and the diffraction efficiency of the hologram is tested byCalculating the dynamic range of the recording medium, wherein i represents the ith hologram, eta i Representing the diffraction efficiency of the ith hologram.
Fig. 4 shows a diffraction efficiency versus rotation angle curve of 60 holograms angle multiplexed at ±30° with 405nm laser light for the photopolymer type holographic recording medium of example 1. The dynamic range of the recording media in examples 1 to 4 in table 6 is greater than 15, indicating that the photopolymer type volume hologram recording medium provided by the present invention has a large dynamic range. In the embodiment 1, when 60 holograms are multiplexed at the same position + -30 DEG, diffraction peaks of 60 holograms are not mutually crosstalked, and each diffraction efficiency is more than 2%, which indicates that the photopolymer type holographic recording medium provided by the invention has the application potential of high-density holographic data storage. In addition, if only 2-carbazolylethyl mercapto ethyl acrylate in examples 1 to 4 is replaced with 2-thiophenylethyl mercapto ethyl acrylate or 2-carbazolylethoxy methyl acrylate, the performance of the resulting photopolymer type volume hologram recording medium is equivalent to that of the corresponding examples 1 to 4, and this is not necessarily exemplified here.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.

Claims (10)

1. A polysilsesquioxane, wherein said polysilsesquioxane is selected from one of the following general structures:
wherein the R is 1 ～R 7 And may be the same or different, each independently selected from one of the following structures:
the R is 8 ～R 14 And may be the same or different, each independently selected from one of the following structures:
the A is 1 、A 2 、A 3 May be the same or different and are each independently selected from hydrogen, methyl, ethylAny one of methoxy, ethoxy and amino;
the A is 4 、A 5 、A 6 Can be the same or different, and are each independently selected from any one of hydrogen, methyl, ethyl, methoxy, ethoxy and hydroxy;
the X is selected from C 1 ～C 8 Alkyl of C number of carbon atoms 1 ～C 8 Alkoxy, alkyl substituted or unsubstituted C 6 ～C 14 Any one of the phenyl groups of (a);
the n represents an integer of 1 to 8, and the m represents an integer of 1 to 4.
2. The polysilsesquioxane of claim 1, selected from one of the following structures:
3. a photopolymer type hologram recording medium, characterized in that the photopolymer type hologram recording medium contains the polysilsesquioxane according to claim 1 or 2;
when the structure of polysilsesquioxane is selected from formula T1 or formula T2, the photopolymer holographic recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane comprises 0.5-10wt% of the photopolymer holographic recording medium;
when the structure of polysilsesquioxane is selected from formula T3 or formula T4, the photopolymer holographic recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane is 0.5-10wt% of the photopolymer type holographic recording medium.
4. The photopolymer type hologram recording medium according to claim 3, wherein when the structure of the polysilsesquioxane is selected from the formula T1 or the formula T2, the photopolymer type hologram recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane is 0.5-5wt% of the photopolymer type holographic recording medium.
5. The photopolymer type hologram recording medium according to claim 3, wherein when the structure of the polysilsesquioxane is selected from the formula T3 or the formula T4, the photopolymer type hologram recording medium comprises the following raw material components in parts by weight:
wherein the polysilsesquioxane comprises 3-8wt% of the photopolymer type holographic recording medium.
6. The photopolymer holographic recording medium of claim 3, wherein the epoxy resin is selected from one or more of n-butyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, diglycidyl ester, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, pentanediol diglycidyl ether, glycerol triglycidyl ether, 3, 4-epoxycyclohexenemethyl-3, 4-epoxycyclohexenoate.
7. The photopolymer holographic recording medium of claim 3, wherein the amine curing agent is selected from one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, divinylpropylamine, 2-methylpentanediamine, 1, 3-pentanediamine, 1, 2-cyclohexanediamine, isophoronediamine, and has a curing temperature of 60 ℃ or less.
8. The photopolymer hologram recording medium according to claim 3, wherein the polymerizable monomer is selected from one or more of an alkenyl naphthalene compound, an alkenyl anthracene compound, an alkenyl benzene compound, an acrylic compound, and a methacrylic compound.
9. The photopolymer holographic recording medium of claim 3, wherein the isocyanate is selected from one or more of hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, (2, 4, 6-trioxytriazine-1, 3,5 (2 h,4h,6 h) -triyl) tris (hexamethylene) isocyanate, butane-1, 4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate.
10. The photopolymer hologram recording medium according to claim 3, wherein the alcohol is one or more selected from triethylene glycol, tetraethylene glycol, butanediol, hexanediol, trimethylolethane, glycerol, triethanolamine, a polyester polyol having a molecular weight of 200 to 2000, a polycarbonate polyol having a molecular weight of 200 to 2000, and a polyether polyol having a molecular weight of 200 to 2000.
CN202311785361.7A 2023-12-22 2023-12-22 Polysilsesquioxane and photopolymer holographic recording medium containing same Pending CN117700744A (en)

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