CN107226908B - High-refraction material and synthesis method thereof - Google Patents
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- C08G77/04—Polysiloxanes
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- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Abstract
The invention relates to the technical field of high-refraction materials, and aims to solve the problems of easy crosslinking, easy sublimation, difficult dissolution, difficult processing and the like in the development of high-refraction materials based on polysilsesquioxane.
Description
Technical Field
The invention relates to the technical field of high-refraction materials, in particular to a high-refraction material based on polysilsesquioxane.
Background
High refractive materials have important applications in light emitting diode encapsulation materials. Polysilsesquioxane has the advantages of heat resistance, oxidation resistance, ultraviolet radiation resistance and the like, and is an important polymer matrix material in high-refraction materials. Polysilsesquioxanes are commonly used in the development of high refractive materials in cage, ring, branched, etc. structures. However, polysilsesquioxanes of these structures generally suffer from the disadvantages of being easily cross-linked, sublimable, insoluble, and difficult to process. For example, J-S Kim et al published in Chemistry of Materials (2010, 22, 3549-. Also, as shown in Organometallics by M.Unno et al (Organometallics, 2014, 33, 4148-4151), the sublimation tendency of cage-and ring-type polysilsesquioxanes is a problem.
Disclosure of Invention
The invention provides a high-refraction material and a synthesis method thereof, aiming at solving the problems of easy crosslinking, easy sublimation, difficult dissolution, difficult processing and the like existing in the development of the high-refraction material based on polysilsesquioxane.
The invention is realized by the following technical scheme: the high-refraction material is a polymer 1 with a structural formula shown in (I), or a polymer 2 with a structural formula shown in (II), or a polymer 3 with a structural formula shown in (III),
in the above formula, X, Y, Z are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, epoxy, ester, sulfonic group, carboxyl, nitrile, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, mercapto, nitro, amino and C60One of the above two methods; r is selected from hydrogen, alkyl silicon base and alkenyl silicon baseAlkynyl silicon base, alkoxy silicon base, aromatic silicon base, epoxy silicon base, ester silicon base, sulfonic silicon base, carboxyl silicon base, nitrile silicon base, halogenated alkyl silicon base, halogenated alkenyl silicon base, halogenated alkynyl silicon base, mercapto silicon base, nitro silicon base, amino silicon base and C60One of silicon bases; a. b, c, d, e, f, g, h, i, j, k, m, n, p, q are integers equal to or greater than 0.
The synthesis method of the high-refraction material comprises the following steps:
(1) the double-deck polyhedral oligomeric silsesquioxane with the structural formula shown In (IV) is subjected to polymerization reaction in an organic solvent under the catalysis of a catalyst A, and the polymer 1 with the structural formula shown in (I) is obtained after post-treatment. The double-deck polyhedral oligomeric silsesquioxane with the structural formula shown as (IV) has the structure that one side is hydrogen and the other side is two parallel silicon hydroxyl groups.
The reaction structural formula is as follows:
(2) the polymer 1 and a double-bond or triple-bond compound react in an organic solvent under the action of a catalyst A, and a polymer 2 shown as a structural formula (II) is obtained after post-treatment, wherein the reaction structural formula is as follows:
(3) the polymer 2 and silane with the structural formula shown as (V) react in an organic solvent under the action of a catalyst B, and after post-treatment, the polymer 3 with the structural formula shown as (III) is obtained, wherein the reaction structural formula is as follows:
in the structural formula (V), A is selected from one of halogen, pseudohalogen, hydrogen and alkoxy; B. c, D are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, epoxy, ester, sulfonic acid, carboxyl, nitrile, halogenAlkyl, halogenated alkenyl, halogenated alkynyl, sulfydryl, nitro, amino and C60One of them.
In the structural formula, X, Y, Z is independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, epoxy group, ester group, sulfonic group, carboxyl, nitrile group, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, mercapto, nitro, amino and C60One of the above two methods; r is selected from hydrogen, alkyl silicon base, alkenyl silicon base, alkynyl silicon base, alkoxy silicon base, aromatic silicon base, epoxy silicon base, ester silicon base, sulfonic silicon base, carboxyl silicon base, nitrile silicon base, halogenated alkyl silicon base, halogenated alkenyl silicon base, halogenated alkynyl silicon base, sulfydryl silicon base, nitro silicon base, amino silicon base, C60One of silicon bases; a. b, c, d, e, f, g, h, i, j, k, m, n, p, q are integers equal to or greater than 0,
the organic solvent is one or more selected from alkane, aromatic hydrocarbon, ether, cyclic ether and ketone. Preferably, the solute is dissolved in one or more selected from hexane, cyclohexane, toluene, diethyl ether, dibutyl ether, tetrahydrofuran, 1, 4-dioxane, acetone, and methyl isobutyl ketone.
The catalyst A is selected from one of Lewis acid, metal simple substance, metal oxide, metal salt and complex. Preferably, the element is selected from one element of boron, iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, osmium, iridium, gold, silver, copper, tin, zinc, titanium, chromium, manganese, indium and lanthanide metals or the corresponding compound,
the mass ratio of the double-deck type polyhedral oligomeric silsesquioxane with the structural formula shown In (IV) in the step (1) to the catalyst A is 1: 0.001-1.
The mass ratio of the polymer 1 with the structural formula shown in the formula (I) in the step (2) to the catalyst A is 1: 0.001-1, and the mass ratio of the two-bond or triple-bond compound to the polymer 1 is 1: 0.001-10.
Preferably, the two-or triple-bond compound is selected from one of alkenyl, alkynyl and carbonyl compounds.
The catalyst B is selected from one of inorganic ammonia, organic amine, quaternary ammonium base, Lewis acid, metal simple substance, metal oxide, metal salt and complex. Preferably, the metal is selected from ammonia, triethylamine, trimethylamine, pyridine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and a simple substance or a corresponding compound of one element of boron, iron, cobalt, nickel, ruthenium, rhodium, platinum, palladium, osmium, iridium, gold, silver, copper, tin, zinc, titanium, zirconium, chromium, manganese, indium and lanthanide metals,
in the step (3), the mass ratio of the silane with the structural formula shown as (V) to the catalyst B is 1: 0.001-10, and the mass ratio of the silane with the structural formula shown as (II) to the polymer 2 is 1: 0.001-10.
Preferably, the reaction temperature of each step in the organic solvent is-20 to 140 ℃, and the reaction time is 30 minutes to 24 hours.
Preferably, the post-treatment process is recrystallization, precipitation, chromatography, sublimation, or vacuum drying.
The invention takes double-deck polyhedral oligomeric silsesquioxane with one silicon-hydrogen bond and two parallel terminal hydroxyls as raw materials, and the high-refraction material with the polymer main chain structure of polysilsesquioxane and the branched chain and the side group functional group is obtained by polymerization, wherein the high-refraction material is respectively polymer 1, polymer 2 or polymer 3, and the high-refraction material has important application in the aspect of light-emitting diode packaging materials.
Compared with the prior art, the invention has the beneficial effects that: the high-refraction material has the advantages of excellent thermal stability, difficult sublimation, easy dissolution in common solvents, easy processing, further chemical modification and the like.
Drawings
FIG. 1 is a matrix-assisted time-of-flight mass spectrum of the polysilsesquioxane of example 1;
FIG. 2 is a gel permeation chromatogram of the polysilsesquioxane of example 1;
FIG. 3 is a hydrogen nuclear magnetic resonance spectrum of the polysilsesquioxane of example 1;
FIG. 4 is a nuclear magnetic resonance spectrum of the polysilsesquioxane of example 1;
FIG. 5 is a graph of the transmittance of polysilsesquioxane of example 1;
FIG. 6 is a graph of the thermogravimetric loss of the polysilsesquioxane of example 1;
FIG. 7 is a gel permeation chromatogram of the polysilsesquioxane of example 4;
FIG. 8 thermogravimetric plot of polysilsesquioxane in example 4;
FIG. 9 is a gel permeation chromatogram of the polysilsesquioxane of example 7;
FIG. 10 is a nuclear magnetic resonance spectrum of the polysilsesquioxane of example 7;
FIG. 11 thermogravimetric plot of polysilsesquioxane in example 7.
Detailed Description
The present invention will be described in further detail by way of examples.
Example 1: synthesis of high refractive material with end group of silicon-hydrogen bond and silicon hydroxyl and side group of phenyl
At-20 ℃, 10 ml of 1, 4-dioxane solution containing 0.01 g of boron tris (pentafluorophenyl) fluoride is slowly added dropwise to a 500 ml three-neck flask containing 10 g of double-deck polyhedral oligomeric silsesquioxane with silicon hydrogen bonds on one side and parallel silicon hydroxyl groups on the other side and phenyl groups on the side groups and 100 ml of 1, 4-dioxane, and then the mixture is stirred for reaction for 30 minutes, the reaction solution is poured into 500 ml of methanol, solid is separated out, and the mixture is filtered to obtain white solid (namely polymer 1), the yield is 95%, and the product refractive index is 1.5601.
The matrix-assisted flight time mass spectrum of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl is shown in fig. 1, the gel permeation chromatogram of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl is shown in fig. 2, the hydrogen spectrum nuclear magnetic resonance chromatogram of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl is shown in fig. 3, the silicon spectrum nuclear magnetic resonance chromatogram of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl is shown in fig. 4, the transmittance curve of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl is shown in fig. 5, and the thermal weight loss curve of the high refractive material with the end group of silicon hydrogen bond and silicon hydroxyl and the side group of phenyl.
Example 2: synthesis of high refractive material with end group of silicon-hydrogen bond and silicon hydroxyl and side group of methyl
10 ml of toluene solution containing 1 g of hexahydrate and chloroplatinic acid was slowly dropped into a 50 ml three-neck flask containing 10 g of bis-methyl polyhedral oligomeric silsesquioxane having a silicon-hydrogen bond on one side and a parallel silicon hydroxyl group on the other side and methyl groups on the side group and 20 ml of toluene, and then stirred to react for 12 hours, the catalyst was removed by column chromatography, and the solvent was removed by vacuum drying to obtain a white solid (i.e., polymer 1) with a yield of 75% and a refractive index of the product of 1.3702.
Example 3: synthesis of high refractive material with end group of silicon-hydrogen bond and silicon hydroxyl and side group of vinyl
100 ml of methyl isobutyl ketone solution containing 50 g of zinc chloride is slowly dripped into a 500 ml three-neck flask containing 50 g of double-deck polyhedral oligomeric silsesquioxane with one side being a silicon-hydrogen bond and the other side being a parallel silicon hydroxyl group and the side group being a vinyl group and 200 ml of methyl isobutyl ketone, then the mixture is stirred and reacted for 24 hours, the catalyst is removed by column chromatography, and the solvent is removed by vacuum drying, so that white solid (namely polymer 1) is obtained, the yield is 45%, and the refractive index of the product is 1.3945.
Example 4: synthesis of high refractive material with end group of 3-chloropropyl and silicon hydroxyl and side group of phenyl
10 ml of 1, 4-dioxane solution containing 0.01 g of boron tris (pentafluorophenyl) fluoride was slowly added dropwise to a 500 ml three-neck flask containing 10 g of a double-deck polyhedral oligomeric silsesquioxane having a silicon-hydrogen bond on one side and a parallel silicon hydroxyl group on the other side and having a phenyl group as a side group and 100 ml of 1, 4-dioxane, and then the mixture was stirred for reaction for 30 minutes, and the reaction solution was poured into 500 ml of methanol to precipitate a solid, which was filtered to obtain a white solid (i.e., polymer 1).
20 ℃ C, containing 10 g of the reaction process product obtained in 20 ml tetrahydrofuran solution slowly added to the containing 1 g allyl chloride, 0.01 g five carbonyl iron, 100 ml tetrahydrofuran 500 ml three-necked flask, then stirred reaction for 8 hours, the reaction liquid poured into 500 ml methanol, solid separation, filtration, white solid (polymer 2). Yield 35% product refractive index 1.5559.
The gel permeation chromatogram of the high refractive material with the end group of 3-chloropropyl and silicon hydroxyl and the side group of phenyl is shown in figure 7, and the thermal weight loss curve of the high refractive material with the end group of 3-chloropropyl and silicon hydroxyl and the side group of phenyl is shown in figure 8.
Example 5: synthesis of high refractive index material with terminal group of epoxy group and silicon hydroxyl group and side group of ethyl group
A10 ml toluene solution containing 1 g of hexahydrate and chloroplatinic acid was slowly dropped into a 50 ml three-neck flask containing 10 g of a double-deck type polyhedral oligomeric silsesquioxane having a silicon-hydrogen bond on one side and a parallel silicon hydroxyl group on the other side and an ethyl group on the side group and 20 ml of toluene, followed by stirring and reaction for 12 hours, the catalyst was removed by column chromatography, and the solvent was removed by vacuum drying to obtain a white solid (i.e., polymer 1).
100 ml of acetone solution containing 1 g of the product obtained in the preceding reaction was slowly dropped into a 500 ml three-necked flask containing 1000 g of vinyloxirane, 0.01 g of nickel chloride and 100 ml of acetone at 50 ℃, and then the mixture was stirred for reaction for 15 hours, and the reaction solution was poured into 500 ml of methanol to precipitate a solid, which was then filtered to obtain a white solid (i.e., polymer 2). Yield 20% product refractive index 1.3909.
Example 6: synthesis of high refractive index material with terminal ester group and silicon hydroxyl group and side group as butenyl group
100 ml of cyclohexanone solution containing 1 g of cuprous chloride is slowly dropped into a 500 ml three-neck flask containing 70 g of double-deck polyhedral oligomeric silsesquioxane with one side being a silicon-hydrogen bond and the other side being a parallel silicon hydroxyl group and a side group being a butenyl group and 100 ml of toluene, and then the mixture is stirred to react for 18 hours, the catalyst is removed by column chromatography, and the solvent is removed by vacuum drying to obtain a white solid (namely, polymer 1).
100 ml of acetone solution containing 50 g of the product obtained in the above reaction process was slowly dropped into a 500 ml three-necked flask containing 10 g of vinyl butyl acetate, 50 g of palladium chloride and 100 ml of acetone at 30 ℃, and then the mixture was stirred and reacted for 20 hours, and the reaction solution was poured into 500 ml of methanol to precipitate a solid, and then filtered to obtain a white solid (i.e., polymer 2). Yield 60% product refractive index 1.4349.
Example 7: synthesis of high refractive index material with phenylethyl and trimethylsilyl as end groups and epoxy as side group
30 ml of 1, 4-dioxane solution containing 3 g of zinc chloride is slowly dripped into a 200 ml three-neck flask containing 10 g of double-deck polyhedral oligomeric silsesquioxane with one side being a silicon-hydrogen bond and the other side being a parallel silicon hydroxyl group and the side group being an epoxy group and 50 ml of 1, 4-dioxane, then the mixture is stirred and reacted for 6 hours, the reaction solution is poured into 500 ml of methanol, solid is separated out, and the white solid (namely the polymer 1) is obtained by filtration.
20 ml of tetrahydrofuran solution containing 10 g of the product obtained in the preceding reaction was slowly dropped into a 200 ml three-neck flask containing 10 g of styrene, 5 g of nickel acetylacetonate and 80 ml of tetrahydrofuran at 60 ℃, and then the reaction was stirred for 18 hours, and the reaction solution was poured into 500 ml of methanol to precipitate a solid, which was then filtered to obtain a white solid (i.e., polymer 2).
50 ml of ether solution containing 5 g of trimethylchlorosilane was slowly added dropwise at-20 ℃ to a 150 ml three-neck flask containing 0.5 g of the product obtained in the preceding reaction, 0.005 g of pyridine and 30 ml of ether, and then the mixture was stirred for reaction for 16 hours, and the reaction solution was poured into 100 ml of methanol to precipitate a solid, which was then filtered to obtain a white solid (i.e., polymer 3) with a yield of 38% and a refractive index of the product of 1.4636.
A gel permeation chromatogram of the high refractive material with the terminal groups of phenethyl and trimethylsilyl groups and the side groups of epoxy groups is shown in fig. 9, a silicon spectrum nuclear magnetic resonance chromatogram of the high refractive material with the terminal groups of phenethyl and trimethylsilyl groups and the side groups of epoxy groups is shown in fig. 10, and a thermal weight loss curve of the high refractive material with the terminal groups of phenethyl and trimethylsilyl groups and the side groups of epoxy groups is shown in fig. 11.
Example 8: synthesis of high-refraction material with end group of cyclohexyl and tripropylene alkynyl silicon base and side group of acetonitrile group
At 50 ℃, slowly dripping 100 ml of butyl ether solution containing 5 g of oxidation pickaxe into a 500 ml three-neck flask containing 10 g of double-deck polyhedral oligomeric silsesquioxane with one side being a silicon-hydrogen bond and the other side being parallel silicon hydroxyl and the side group being acetonitrile group and 100 ml of butyl ether, then stirring for reaction for 9 hours, pouring the reaction solution into 500 ml of methanol, separating out solids, and filtering to obtain white solids (namely polymer 1).
At 30 ℃, 100 ml of butyl ether solution containing 10 g of the product obtained in the reaction process is slowly added dropwise into a 300 ml three-neck flask containing 30 g of cyclohexene, 1 g of palladium/carbon and 80 ml of butyl ether, then the mixture is stirred and reacted for 12 hours, the reaction solution is poured into 500 ml of methanol, solid is separated out, and the white solid (namely the polymer 2) is obtained by filtration.
500 ml of an ether solution containing 200 g of tripropylenemethoxymethylsilane was slowly dropped into a 3000 ml three-necked flask containing 0.2 g of the product obtained in the preceding reaction, 2000 g of indium chloride and 1000 ml of ether at 20 ℃, followed by stirring and reaction for 3 hours, the catalyst was removed by column chromatography, and vacuum drying was carried out to obtain a white solid (i.e., polymer 3) in a yield of 79% and a product refractive index of 1.4903.
Example 9: synthesis of high refractive index material with heptenyl and trivinyl silicon as end group and methyl methacrylate as side group
100 ml of butyl ether solution containing 10 g of iron oxide is slowly dripped into a 500 ml three-neck flask containing 100 g of double-deck polyhedral oligomeric silsesquioxane with one side being a silicon-hydrogen bond and the other side being a parallel silicon hydroxyl group and the side group being methyl methacrylate group and 100 ml of butyl ether at 100 ℃, then the mixture is stirred and reacted for 19 hours, reaction liquid is poured into 500 ml of methanol, solid is separated out, and white solid (namely polymer 1) is obtained by filtering.
100 ml of an ether solution containing 10 g of the product obtained in the above reaction was slowly dropped into a 300 ml three-necked flask containing 30 g of 1-heptyne, 0.5 g of silver nitrate and 80 ml of ether at 20 ℃, and then the reaction mixture was stirred for 15 hours, poured into 500 ml of methanol to precipitate a solid, and filtered to obtain a white solid (i.e., polymer 2).
500 ml of an ether solution containing 200 g of trivinylbromosilane was slowly dropped into a 5000 ml three-necked flask containing 2000 g of the product obtained in the preceding reaction process, 10 g of zinc oxide and 1000 ml of ether at 20 ℃, and then stirred to react for 8 hours, the catalyst was removed by column chromatography, and vacuum-dried to obtain a white solid (i.e., polymer 3) at a yield of 87%, and the refractive index of the product was 1.5103.
Claims (6)
1. A method for synthesizing a high refractive material, characterized in that the high refractive material is a polymer 1 having a structural formula shown as (I), or a polymer 2 having a structural formula shown as (II), or a polymer 3 having a structural formula shown as (III),
the synthesis method comprises the following steps:
(1) carrying out polymerization reaction on the double-deck polyhedral oligomeric silsesquioxane with the structural formula shown In (IV) in an organic solvent under the catalysis of a catalyst A, and carrying out post-treatment to obtain a polymer 1 with the structural formula shown in (I);
(2) reacting the polymer 1 with a two-bond or three-bond compound in an organic solvent under the action of a catalyst A, and carrying out post-treatment to obtain a polymer 2 with a structural formula shown as (II);
(3) the polymer 2 and silane with the structural formula shown as (V) react in an organic solvent under the action of a catalyst B, and after post-treatment, the polymer 3 with the structural formula shown as (III) is obtained,
wherein X, Y, Z are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, epoxy, ester, sulfonic acid, carboxyl, nitrile, halogenated alkyl, halogenated alkeneRadical, halogenated alkynyl, mercapto, nitro, amino, C60One of the above two methods; r is selected from hydrogen, alkyl silicon base, alkenyl silicon base, alkynyl silicon base, alkoxy silicon base, aromatic silicon base, epoxy silicon base, ester silicon base, sulfonic silicon base, carboxyl silicon base, nitrile silicon base, halogenated alkyl silicon base, halogenated alkenyl silicon base, halogenated alkynyl silicon base, sulfydryl silicon base, nitro silicon base, amino silicon base, C60One of silicon bases; a is an integer greater than 1; b. c and d are integers equal to or greater than 0; e. f, g, h, i, j, k, m, n, p, q are equal to 0,
in the structural formula (V), A is selected from one of halogen, pseudohalogen, hydrogen and alkoxy; B. c, D are independently selected from hydrogen, alkyl, alkenyl, alkynyl, aryl, epoxy, ester, sulfonic acid, carboxyl, nitrile, halogenated alkyl, halogenated alkenyl, halogenated alkynyl, mercapto, nitro, amino, and C60One of the above two methods;
the organic solvent is one or more selected from alkane, aromatic hydrocarbon, ether, cyclic ether and ketone, the catalyst A is one selected from Lewis acid, a metal simple substance, a metal oxide, a metal salt and a complex, and the mass ratio of the double-deck polyhedral oligomeric silsesquioxane with the structural formula shown as (IV) to the catalyst A is 1: 0.001-1.
2. The method for synthesizing a high refractive material according to claim 1, wherein the mass ratio of the polymer 1 to the catalyst A is 1: 0.001-1, the mass ratio of the two-or triple-bond compound to the polymer 1 is 1: 0.001-10, and the two-or triple-bond compound is selected from one of alkenyl, alkynyl and carbonyl compounds.
3. The method for synthesizing a high refractive material according to claim 1, wherein the catalyst B is selected from one of inorganic ammonia, organic amine, quaternary ammonium base, Lewis acid, metal simple substance, metal oxide, metal salt and complex.
4. The method for synthesizing a high refractive material according to claim 1 or 3, wherein the mass ratio of the silane represented by the structural formula (V) to the catalyst B is 1: 0.001 to 10, and the mass ratio to the polymer 2 is 1: 0.001 to 10.
5. The method for synthesizing a high refractive material according to claim 1, wherein the reaction temperature is-20 to 140 ℃ and the reaction time is 30 minutes to 24 hours.
6. The method for synthesizing a high refractive material according to claim 1, wherein the post-treatment process is recrystallization, precipitation, chromatography, sublimation, or vacuum drying.
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