KR101768439B1 - composition containing a silicone resin which is prepared from the surface-modified silicon quantum dots and method for preparing the same - Google Patents
composition containing a silicone resin which is prepared from the surface-modified silicon quantum dots and method for preparing the same Download PDFInfo
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- KR101768439B1 KR101768439B1 KR1020150133844A KR20150133844A KR101768439B1 KR 101768439 B1 KR101768439 B1 KR 101768439B1 KR 1020150133844 A KR1020150133844 A KR 1020150133844A KR 20150133844 A KR20150133844 A KR 20150133844A KR 101768439 B1 KR101768439 B1 KR 101768439B1
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Abstract
The present invention relates to a composition containing a silicone resin prepared from a surface-modified silicon quantum dot, and a method of manufacturing the same, and the composition of the present invention includes a surface-modified silicon quantum dot, so that the transmittance and the refractive index are extremely high.
Description
The present invention relates to a composition containing a silicone resin prepared from a surface-modified silicon quantum dot and a method for producing the same.
BACKGROUND ART Light emitting diodes (LEDs) having advantages of high efficiency, high speed response, long life, small size, light weight and low power consumption have been applied to backlight and illumination of display devices.
These light emitting diode packages consist largely of LED chips, adhesives, encapsulants, phosphors, and heat dissipation accessories. Among them, the LED encapsulant protects the LED chip from external impact and environment. Since LED light is emitted from the LED package through the LED encapsulant, the LED encapsulant must have optical transparency, that is, have high light transmittance, and particularly have a high refractive index in order to increase light extraction efficiency.
BACKGROUND ART Conventionally, epoxy resins having high refractive index and low cost have been widely used as LED encapsulants. However, since the epoxy resin has low heat resistance, there is a problem that it is deteriorated by heat in a high power LED, and the white light LED is yellowed by the light in the vicinity of blue and ultraviolet rays to lower the brightness.
Therefore, in order to overcome the problem of the epoxy resin, a silicone resin having excellent light resistance in a low wavelength region is being studied as a substitute for the epoxy resin.
However, the bonding energy of the siloxane bond (Si-O-Si) of the silicone resin and silicone resin is 106 kcal / mol, which is higher than the bonding energy of carbon-carbon (CC) by 20 kcal / mol and is excellent in heat resistance and light resistance, There is a problem that adhesion is weak.
The present invention provides a composition containing a silicone resin produced from a surface-modified silicon quantum dot that is excellent in mechanical properties such as adhesiveness and high in refractive index and can be used as a sealing material for a light emitting device, and a method for producing the same.
The present invention provides a composition containing a silicone resin produced from a surface-modified silicon quantum dot, and more specifically, the present invention provides a silicone resin composition comprising a surface-modified silicon quantum dot and having high adhesiveness, light transmittance and refractive index do.
The surface-modified silicon quantum dots according to one embodiment of the present invention may be surface-modified with a compound represented by Chemical Formula 1 or Chemical Formula 2.
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ar 1 is (C6-C12) arylene or (C3-C12) heteroarylene;
R 1 to R 4 independently of one another are hydrogen, halogen, hydroxy (C 1 -C 10) alkyl, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R 5 and R 6 are independently from each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R < 7 > is (C1-C10) alkoxy;
n and m are independently an integer of 0 to 5, and when n and m are 2 or more, R 1 to R 6 may be mutually different or the same;
The arylene or heteroarylene of Ar 1 is further substituted with halogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) alkyl or (C 1 -C 10) aryl You can.
In the formula (1) according to an embodiment of the present invention, Ar 1 is (C6-C12) arylene; R 1 to R 4 independently of one another are hydrogen, halogen or (C 1 -C 10) alkyl;
R 5 and R 6 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 6 -C 12) aryl;
R < 7 > may be (C1-C10) alkoxy.
In view of having a high refractive index, R 5 and R 6 in
From the viewpoint of having a high refractive index, the above-mentioned
(3)
[Formula 3]
Wherein R 11 is hydrogen, halogen, (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) alkyl or (C1-C10) aryl (C1-C10) alkyl;
o is an integer of 1 to 4, and when o is 2 or more, R < 11 > may be mutually different or the same.]
The present invention also provides a method for producing a composition containing a silicone resin produced from the surface modified silicon quantum dots of the present invention,
a) preparing a silicon compound by reacting the surface-modified silicon quantum dots with a trialkoxysilane in the presence of a catalyst, and
b) reacting the silicon compound alone or the silicon compound with a silane coupling agent to prepare a silicone resin.
Another aspect of the method for producing the composition of the present invention includes a step of reacting a surface modified silicon quantum dot with a silane coupling agent in the presence of a catalyst to prepare a silicone resin, ≪ / RTI >
In one embodiment of the composition of the present invention, specifically, the method for producing a light emitting device encapsulant composition, the surface modified silicon quantum dots include,
a1) preparing a silica nanoparticle by reacting a surfactant with a silicon precursor in the presence of a base;
a2) reducing the silica nanoparticles with magnesium to prepare silica nanocrystals;
a3) etching the silica nanocrystals with an acid solution to produce silicon quantum dots; and
a4) preparing a surface-modified silicon quantum dots by surface-modifying the silicon quantum dots with the compound represented by Formula 1 or Formula 2.
The catalyst according to an embodiment of the process for preparing the composition of the present invention may be selected from the group consisting of H 2 PtCl 6 Or platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.
The trialkoxysilane according to an embodiment of the present invention may be trimethoxysilane or triethoxysilane, and the silicon precursor may be tetramethoxysilane or tetraethoxysilane.
The silane coupling agent according to an embodiment of the present invention may be an organic alkoxysilane containing tetraalkoxysilane, trialkoxysilane, methyldimethoxysilane, vinylsilane, aminosilane, ethoxysilane or vinyl group, May be a hydrofluoric acid solution.
The composition of the present invention contains a silicone resin prepared from the surface-modified silicon quantum dots and has high light transmittance, high heat resistance and high adhesiveness as compared with the conventional epoxy resin.
In addition, since the composition of the present invention contains a surface-modified silicon quantum dot in a silicone resin, the low refractive index of a general silicone resin is improved, and the composition of the present invention has a very high refractive index.
1 is a view showing 1 H-NMR of the surface-modified silicon quantum dots prepared in Example 1 and Comparative Example 1,
FIG. 2 is a view showing the FT-IR of the surface-modified silicon quantum dot prepared in Example 3 of the present invention,
3 is a view showing the FT-IR of the silicone resin thin film produced in Example 4 of the present invention,
4 is a view showing spectroscopic ellipsometry (SE) of the silicon thin film manufactured in Example 4 of the present invention.
Hereinafter, the present invention will be described in more detail. Unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the following description, And a description of the known function and configuration will be omitted.
The present invention provides a composition prepared by containing a silicone resin produced from a surface modified silicon quantum dot.
The composition according to an embodiment of the present invention has high light transmittance, heat resistance, and adhesiveness, and can be used as a composition of a sealing member for a light emitting device.
The surface modified silicon quantum dot of the present invention is a compound in which a compound having a functional group (for example, a functional group having a vinyl group and a Si compound containing an alkoxy group) capable of producing a silicone resin on the surface of a silicon quantum dot is covalently bonded to the surface of a silicon quantum dot it means.
More specifically, the surface-modified silicon quantum dots according to one embodiment of the present invention may be surface-modified with a compound represented by Formula 1 or Formula 2 below.
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ar 1 is (C6-C12) arylene or (C3-C12) heteroarylene;
R 1 to R 4 independently of one another are hydrogen, halogen, hydroxy (C 1 -C 10) alkyl, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R 5 and R 6 are independently from each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R < 7 > is (C1-C10) alkoxy;
n and m are independently an integer of 0 to 5, and when n and m are 2 or more, R 1 to R 6 may be mutually different or the same;
The arylene or heteroarylene of Ar 1 is further substituted with halogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) alkyl or (C 1 -C 10) aryl You can.
The composition of the present invention contains a silicone resin prepared from the above-described surface-modified silicon quantum dots, so that when the composition of the present invention is used as a light emitting element encapsulant, .
In
R 5 and R 6 are independently of each other hydrogen, (C 1 -C 10) alkyl or (C 6 -C 12) aryl;
R < 7 > may be (C1-C10) alkoxy.
In order to have a high adhesive strength and a high refractive index, the formula (1) may be represented by the following formula (3).
(3)
(3)
Wherein R 11 is hydrogen, halogen, (C1-C10) alkyl, (C1-C10) alkoxy, (C6-C12) alkyl or (C1-C10) aryl (C1-C10) alkyl;
o is an integer of 1 to 4, and when o is 2 or more, R < 11 > may be mutually different or the same.
The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both linear and branched forms and have from 1 to 10 carbon atoms, preferably from 1 to 7 carbon atoms . The term " aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen, and may be a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, A ring system, and a form in which a plurality of aryls are connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which one or more heteroaryl is connected to a single bond.
The composition of the present invention contains a silicone resin prepared from a surface-modified silicon quantum dot, more specifically, a compound having a functional group capable of producing a silicone resin, and the surface of the silicon quantum dots is modified to prepare a surface- The silicon quantum dots are contained in the silicone resin by producing the silicone resin from the surface-modified silicon quantum dots, and the refractive index is higher than that of the conventional silicone resin series.
The composition of the present invention may be a light emitting device encapsulant composition. In addition to the silicone resin prepared from the surface modified silicone quantum dots, the composition of the present invention may further comprise an adhesion enhancer; Inert filler; Reinforcing and non-reinforcing fillers; disinfectant; Browning; Rheological additive; Corrosion inhibitors; Antioxidants; Light stabilizers; Flame retardant; Agents affecting electrical properties; Dispersing agent; menstruum; Binder; Pigments; dyes; Plasticizers; Organic polymers; Thermal stabilizers; Nanoparticles of oxides or nitrides; resist; And a heat resisting agent. The additional additive is contained at a ratio of 0.0001 to 30 parts by weight based on 100 parts by weight of the silicone resin. The additive may be a known additive or may be prepared by a known method. For example, the additive may be selected from quartz powder, diatomaceous earth, clay, chalk, lithopone, carbon black, graphite, metal oxide, metal carbonate, Metal salts of carboxyic acid, metal dust, glass fibers, synthetic fibers, polymer powders, dyes, pigments and the like.
The present invention also provides a composition containing a silicone resin prepared from the surface-modified silicon quantum dots of the present invention, specifically a method for producing a light-emitting device encapsulant composition.
The method for producing a composition containing a silicone resin according to the present invention comprises:
a) preparing a silicon compound by reacting the surface-modified silicon quantum dots with a trialkoxysilane in the presence of a catalyst, and
b) preparing a silicon resin by reacting the silicon compound alone or the silicon compound with a silane coupling agent, or preparing a surface modified silicon quantum dot using the compound represented by the
The method for producing a composition containing a silicone resin according to the present invention is not limited to simply incorporating a silicon quantum dot capable of increasing the refractive index into a composition, particularly a light emitting element encapsulation material composition, but a compound having a functional group capable of producing a silicone resin, Silicon quantum dots are uniformly distributed by manufacturing a silicone resin from surface-modified silicon quantum dots that are covalently bonded to the surface, and silicon quantum dots are covalently bonded in the silicone resin and are very stable.
In addition, the method of the present invention can easily adjust the content of the surface-modified silicon quantum dots and easily adjust the refractive index of the silicone resin produced therefrom.
Preferably, the content of the surface-modified silicon quantum dots contained in the silicone resin of the present invention may be 0.5 to 50% by weight, more preferably 0.5 to 25% by weight.
One embodiment for producing the silicone resin from the surface modified silicon quantum dots is described in detail below.
First, a silicon compound is prepared by reacting a surface-modified silicon quantum dot with a trialkoxysilane in the presence of a catalyst.
[Reaction Scheme 1]
The catalyst at this time is not limited, but is preferably H 2 PtCl 6 Or platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex. The catalyst may be used in an amount of 0.002 to 0.004 mol per 1 mol of the surface-modified silicon quantum dots.
In the trialkoxysilane according to an embodiment of the present invention, the alkyl may be C1-C10 alkyl, and preferred examples thereof may be trimethoxysilane or triethoxysilane, and may be 100 to 1000 It can be used as a mall.
Next, the silicone compound prepared in step b) is reacted with a silane coupling agent alone or in combination to prepare a silicone resin.
The step b) proceeds in a sol-gel reaction, and in the present invention, the sol-gel reaction means that the sol-gel reaction starts from a sol, which is in a solution state, Refers to a form in which particles of 1 to 1,000 nm are generally uniformly dispersed on a solvent without precipitation by van der Waals attractive force or surface charge.
The sol-gel reaction of the present invention proceeds with an acid catalyst and water, wherein the acid catalyst is used to control the pH and the reaction rate. Generally, various catalysts can be selected for the sol-gel reaction, As the catalyst, for example, one or two or more selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, trifluorosulfonic acid, trifluoroacetic acid, and methanesulfonic acid may be used, and preferably trifluoroacetic acid or methanesulfonic acid The use of a nitric acid is highly compatible with each composition, the workability is excellent, and a milder reaction proceeds.
When the acid catalyst is produced using a silicone compound, it is preferable that the acid catalyst contains 0.3 to 2 parts by weight per 100 parts by weight of the silicone compound of the present invention. When the silicone resin is directly produced from the surface-modified silicon quantum dots, the acid catalyst may be used in an amount of 0.5 to 1 part by weight based on 100 parts by weight of the silane coupling agent.
The total temperature of the reaction solution should be maintained at 20 to 35 ° C. If it is less than 20, the reaction may be more than 70 hours, and the productivity may be lowered.
Water according to the present invention is mixed with a solvent to promote a sol-gel reaction, and it is preferable to use ultrapure water.
In the present invention, the ultrapure water is preferably added in an amount of 30 to 60 parts by weight based on 100 parts by weight of the silicone compound when the silicone compound is prepared from the surface-modified silicon quantum dots. When the amount of the ultrapure water is less than 30 parts by weight, the ultrapure water required for hydrolysis is insufficient to cause gelation. When the amount of the ultrapure water is more than 60 parts by weight, the viscosity of the liquid rapidly increases due to excess ultrapure water.
In the present invention, when the silicone resin is prepared from the surface-modified silicon quantum dots without passing through the silicon compound, ultrapure water may be added in an amount of 40 to 50 parts by weight based on 100 parts by weight of the silane coupling agent. When moisture is contained in the catalyst, It may not.
In the present invention, the solvent may be added to dilute the composition. For example, alcohols, ketones, cellosolves, and the like may be used. It is more preferable to use any one or two or more organic solvents selected from THF, methanol, ethanol, isopropyl alcohol, normal propyl alcohol, isobutanol, n-butanol, amyl alcohol, pentanol and hexanol.
In the present invention, the solvent is preferably 800 to 1,400 parts by weight based on 100 parts by weight of the silicone compound. When the amount is less than 100 parts by weight, unreacted matters precipitate due to instability of the solution. When the amount is more than 500 parts by weight, the reaction rate may be excessively slowed. When the silicone resin is prepared without passing through the silicone compound of the present invention, the solvent may be used in an amount of 2000 to 5000 parts by weight based on 100 parts by weight of the silane coupling agent.
The silane coupling agent that reacts with the silicone compound of the present invention may be an organosilane compound such as tetra (C1-C10) alkoxysilane, tri (C1-C10) alkoxysilane, methyldimethoxysilane, vinylsilane, aminosilane, ethoxysilane, Alkoxysilane.
The tetra (C1-C10) alkoxysilane according to an embodiment of the present invention may be tetra (C1-C5) alkoxysilane and the tri (C1-C10) alkoxysilane may be tri .
The organic alkoxysilane containing the vinyl group of the present invention may be a compound of the following formula (11), which is a silane compound having a functional group substituted or unsubstituted with an organic chain and an alkoxy group.
(11)
(In Formula 11, R 1 is comprising a vinyl group, (C 1 ~ C 20) alkyl, (C 3 ~ C 8) cycloalkyl, (C 3 ~ C 8) substituted with cycloalkyl (C 1 ~ C 20) alkyl, (C 2 ~ C 20) alkenyl, (C 2 ~ C 20) alkynyl, (C 6 ~ C 20) may have at least one functional group selected from an aryl group, R 2 to R 4 Is independently a straight or branched (C 1 -C 7 ) alkyl group.)
More specifically, the organic alkoxysilane containing the vinyl group may be at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, aryltrimethoxysilane, aryltriethoxysilane, N- (3-acryloxy- Hydroxypropyl) -3-aminopropyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) Acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropylmethylbis (trimethoxy) silane, 3-acryloxypropyltrimethoxysilane, 3- (Meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- Trimethoxysilane, and mixtures thereof.
Hereinafter, a method of preparing the surface modified silicon quantum dot according to one embodiment of the present invention, more specifically, a method of manufacturing a light emitting device encapsulant composition will be described in detail.
The surface-modified silicon quantum dots of the present invention can be obtained by,
a1) preparing a silica nanoparticle by reacting a surfactant with a silicon precursor in the presence of a base;
a2) reducing the silica nanoparticles with magnesium to prepare silica nanocrystals;
a3) etching the silica nanocrystals with an acid solution to produce silicon quantum dots; and
a4) preparing a surface modified silicon quantum dots by surface modifying the silicon quantum dots with a compound represented by the formula (1).
First, a1) a silica precursor is reacted with a surfactant in the presence of a base to prepare silica nanoparticles.
The silicon precursor may be any silicon-containing compound capable of producing silicon quantum dots, but may be preferably tetramethoxysilane or tetraethoxysilane, and may be carried out at 0.4 to 0.6 moles per mole of the surfactant.
The surfactant according to an embodiment of the present invention may be any conventional surfactant, but may preferably be a nonionic surfactant Brij 30 (polyoxyethylene (4) lauryl ether) or Brij 35 (polyoxyethylene (23) lauryl ether) have.
The base according to one embodiment of the present invention may preferably be NH 4 OH, and may be 0.2 to 0.4 mol per 1 mol of the silicon precursor.
Second, a2) silica nanoparticles are reduced with magnesium to produce silica nanocrystals.
In this case, magnesium may preferably be a powder. More specifically, the silica nanoparticles and the magnesium powder prepared in step a1) are heated and reduced in a vacuum tube furnace, and washed with an acid solution to remove magnesium oxide as a by- Can be added.
Next, the silica nanocrystals are etched with an acid solution to prepare silicon quantum dots.
The acid solution may be a hydrofluoric acid solution.
Next, a4) the silicon quantum dots are surface-modified with the compound represented by
The present invention will be described in detail with reference to the following examples. However, the following examples are only illustrative of the present invention and the scope of the present invention is not limited thereby.
[Example 1] Production of silicon quantum dots surface-modified with divinylbenzene
In a 1 L flask, Brij 30, 24 g of surfactant Brij and 6.4 mL of 1-hexanol were sonicated for approximately 90 minutes and dispersed in 400 mL of cyclohexane solvent. Add 8 mL of distilled water, ultrasonicate until transparent, add 10 mL of tetraethoxysilane (TEOS), and stir for 2 hours. 2 mL of NH 4 OH was slowly added thereto, and the reaction was completed by stirring for 24 hours. 40 mL of acetone was added to the reaction mixture to precipitate the silica nanoparticles, followed by centrifugal separation.
1 g of the prepared silica nanoparticles and 0.8 g of magnesium powder were finely ground using a pestle bowl, mixed in a vacuum tube furnace, and heated at 675 ° C for 15 hours under argon gas flow. Then, the mixture was stirred in a mixed solution of 100 mL of distilled water and 10 mL of 35% HCl for 12 hours to remove magnesium oxide, which is a by-product. This mixed solution was centrifuged to obtain only a powder, and washing was repeated until it became neutral with ethanol. Then, 0.2 g of the obtained powder was added to a mixed solution of hydrofluoric acid (6 mL): ethanol (6 mL): distilled water (6 mL) After stirring for 90 minutes, 18 mL of toluene was added to extract pure silicon nano-crystals from which the silica around the silica nanocrystals had been removed. This procedure was repeated three times and connected to the Schlenk line. The vacuum / argon process was repeated three times to remove oxygen and water as much as possible.
4 mL of divinylbenzene (DVB) and 0.6 mL of H 2 PtCl 6 (dissolved in 0.05M methanol) as a platinum catalyst were added to the pure silicon nanocrystals solution extracted with 18 mL of the toluene, and the reaction was completed by stirring for 2 days. The toluene solvent was removed using a rotary evaporator, and the remaining unreacted DVB was removed by applying a vacuum for 3 days. Silicon nanocrystals, which were surface-modified with pure divinylbenzene, were obtained by dissolution / precipitation using toluene / methanol.
1 H-NMR of the prepared surface-modified silicon quantum dots is shown in Fig.
From FIG. 1, it can be seen that the vinyl group proton was present between 7.1 ppm and 5 ~ 6.7 ppm, respectively, indicating that a silicon quantum dot surface-modified with divinylbenzene was produced.
[Example 2] Production of silicone compound
0.8 g of the silicon quantum dot surface-modified with divinylbenzene prepared in Example 1, 0.8 g of TES (triethylsilane) was added to 12 g of toluene, and the mixture was stirred at room temperature for 1 hour. Then, H 2 PtCl 6 Dissolved) was added thereto and stirred for 4 hours to prepare a silicone compound.
≪ 1 > H-NMR of the silicon compound thus prepared is shown in Fig.
As shown in Fig. 1 (b), the proton peaks of b, a ', and a carbon, which were present in 1 H-NMR of silicon quantum dots modified with divinylbenzene, disappeared due to the disappearance of vinyl group by hydrogen silylation reaction. It can be seen that a silicon compound is produced.
[Example 3] Production of silicon quantum dots surface-modified with dimethylethoxyvinylsilane
In a 1 L flask, Brij 30, 24 g of surfactant Brij and 6.4 mL of 1-hexanol were sonicated for approximately 90 minutes and dispersed in 400 mL of cyclohexane solvent. Add 8 mL of distilled water, ultrasonicate until transparent, add 10 mL of tetraethoxysilane (TEOS), and stir for 2 hours. 2 mL of NH 4 OH was slowly added thereto, and the reaction was completed by stirring for 24 hours. 40 mL of acetone was added to the reaction mixture to precipitate the silica nanoparticles, followed by centrifugal separation.
1 g of the prepared silica nanoparticles and 0.8 g of magnesium powder were finely ground using a pestle bowl, mixed in a vacuum tube furnace, and heated at 675 ° C for 15 hours under argon gas flow. Then, the mixture was stirred in a mixed solution of 100 mL of distilled water and 10 mL of 35% HCl for 12 hours to remove magnesium oxide, which is a by-product. This mixed solution was centrifuged to obtain a powder, and washing was repeated until it became neutral with ethanol. Then, 0.5 g of the obtained powder was added to a mixed solution of 20 mL of ethanol (20 mL): distilled water (20 mL) After stirring for 5 hours, 50 mL of toluene was added to extract pure silicon nano-crystals from which silica around the silica nanocrystals had been removed. This procedure was repeated 3 times, centrifuged, and 20 mL of toluene was added and connected to the Schlenk line. The vacuum / argon procedure was repeated 3 times to remove oxygen and water as much as possible.
15 mL of dimethylethoxyvinylsilane and 0.6 mL of H 2 PtCl 6 (dissolved in 0.05M methanol) as a platinum catalyst were added to a pure silicon nanocrystal solution dispersed in 20 mL of toluene and stirred for 2 days to complete the reaction. After filtering with a syringe filter, toluene solvent and unreacted dimethylethoxyvinylsilane were removed using a rotary evaporator to obtain silicon nanocrystals modified with divinylbenzene.
The FT-IR of the prepared surface-modified silicon quantum dots is shown in Fig.
From FIG. 2, absorption peaks of Si-CH 3 and Si-OCH 2 CH 3 are shown, indicating that silicon quantum dots were surface-modified with dimethylethoxyvinylsilane.
[Example 4] Production of silicone resin from surface-modified silicon quantum dots and silane coupling agent
In the above reaction formula, n may be an integer of 1 to 1000. The silicon quantum dots modified with dimethylethoxyvinylsilane prepared in Example 2 and methyltrimethoxysilane (MTMS), which is a silane coupling agent, were reacted in different amounts as shown in Table 1 to prepare silicone resins.
The quantities of silicon quantum dots and MTMS as described in Table 1 above were added to 30 g of THF and stirred, then 0.9 g of 0.25 M HCl catalyst was added slowly and the mixture was stirred at room temperature for 1 hour. Transfer the solution to a separatory funnel, add 50 mL of diethyl ether, and wash three times with 20 mL of distilled water. After adding 4 g of anhydrous MgSO 4 and stirring for 30 minutes, the remaining water was removed, filtered, and dried with a rotary evaporator to prepare a silicone resin. The prepared silicone resin was dissolved in THF solvent at a concentration of 5 wt% and spin-coated (2,000 rpm, 30 sec) on a silicon wafer to prepare a silicone resin thin film. The silicon resin thin film was heated under vacuum at 150 ° C and 350 ° C for 1 hour And cured.
FIG. 3 shows the FT-IR of the silicone resin thin film cured at 150 ° C.
The same FT-IR results were obtained for the cured silicone resin thin film at 150 ° C and the cured silicone resin thin film at 350 ° C, indicating the absorption peaks of Si-CH 3 and Si-O-Si, It can be seen that the resin is produced.
The spectroscopic ellipsometry (SE) (M2000D, Woollam). The results are shown in FIG.
From FIG. 4, it can be seen that the refractive index and the extinction coefficient gradually increase as the content of silicon quantum dots in the silicone resin increases.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. And various modifications may be made to the invention. Therefore, modifications of the embodiments of the present invention will not depart from the scope of the present invention.
Claims (12)
b) reacting the silicone compound alone or the silicone compound with a silane coupling agent to prepare a silicone resin,
The surface-modified silicon quantum dots include,
a1) preparing a silica nanoparticle by reacting a surfactant with a silicon precursor in the presence of a base;
a2) reducing the silica nanoparticles with magnesium to prepare silica nanocrystals;
a3) etching the silica nanocrystals with an acid solution to produce silicon quantum dots; and
a4) preparing a surface modified silicon quantum dots by surface modifying the silicon quantum dots with a compound represented by the following general formula (1) or (2) to prepare a silicon-containing resin prepared from the surface-modified silicon quantum dots ≪ / RTI >
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ar 1 is (C6-C12) arylene or (C3-C12) heteroarylene;
R 1 to R 4 independently of one another are hydrogen, halogen, hydroxy (C 1 -C 10) alkyl, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R 5 and R 6 are independently from each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R < 7 > is (C1-C10) alkoxy;
n and m are independently an integer of 0 to 5, and when n and m are 2 or more, R 1 to R 6 may be mutually different or the same;
The arylene or heteroarylene of Ar 1 is further substituted with halogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) alkyl or (C 1 -C 10) aryl You can.
The surface-modified silicon quantum dots include,
a1) preparing a silica nanoparticle by reacting a surfactant with a silicon precursor in the presence of a base;
a2) reducing the silica nanoparticles with magnesium to prepare silica nanocrystals;
a3) etching the silica nanocrystals with an acid solution to produce silicon quantum dots; and
a4) preparing a surface modified silicon quantum dots by surface modifying the silicon quantum dots with a compound represented by the following general formula (1) or (2) to prepare a silicon-containing resin prepared from the surface-modified silicon quantum dots ≪ / RTI >
[Chemical Formula 1]
(2)
[In the above formulas (1) and (2)
Ar 1 is (C6-C12) arylene or (C3-C12) heteroarylene;
R 1 to R 4 independently of one another are hydrogen, halogen, hydroxy (C 1 -C 10) alkyl, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R 5 and R 6 are independently from each other hydrogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) aryl or (C 6 -C 12) aryl (C 1 -C 10) alkyl;
R < 7 > is (C1-C10) alkoxy;
n and m are independently an integer of 0 to 5, and when n and m are 2 or more, R 1 to R 6 may be mutually different or the same;
The arylene or heteroarylene of Ar 1 is further substituted with halogen, (C 1 -C 10) alkyl, (C 1 -C 10) alkoxy, (C 6 -C 12) alkyl or (C 1 -C 10) aryl You can.
The catalyst was H 2 PtCl 6 Or platinum (0) -1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex.
Wherein the silicon precursor is tetramethoxysilane or tetraethoxysilane.
Wherein the trialkoxy silane is trimethoxy silane or triethoxy silane.
Wherein the silane coupling agent is an organoalkoxysilane comprising a tetraalkoxysilane, a trialkoxysilane, a methyldimethoxysilane, a vinylsilane, an aminosilane, an ethoxysilane or a vinyl group.
Wherein the acid solution is a hydrofluoric acid solution.
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