CN106543440A - Annular oligomeric silsesquioxanes, its modified organic silicon packaging plastic and preparation method thereof - Google Patents
Annular oligomeric silsesquioxanes, its modified organic silicon packaging plastic and preparation method thereof Download PDFInfo
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- CN106543440A CN106543440A CN201610927462.7A CN201610927462A CN106543440A CN 106543440 A CN106543440 A CN 106543440A CN 201610927462 A CN201610927462 A CN 201610927462A CN 106543440 A CN106543440 A CN 106543440A
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- 238000004806 packaging method and process Methods 0.000 title claims abstract description 47
- 229920003023 plastic Polymers 0.000 title claims abstract description 47
- 239000004033 plastic Substances 0.000 title claims abstract description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 20
- 239000010703 silicon Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- 238000005538 encapsulation Methods 0.000 claims abstract description 18
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 33
- 239000013078 crystal Substances 0.000 claims description 32
- -1 polysiloxanes Polymers 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 claims description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 6
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 6
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229940030010 trimethoxybenzene Drugs 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000005374 membrane filtration Methods 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 14
- 238000007711 solidification Methods 0.000 abstract description 12
- 230000008023 solidification Effects 0.000 abstract description 12
- 238000002834 transmittance Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000002411 thermogravimetry Methods 0.000 abstract description 5
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 230000006837 decompression Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 125000006267 biphenyl group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000000462 Nertera granadensis Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/12—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
- C09J183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of annular oligomeric silsesquioxanes, its modified organic silicon packaging plastic and preparation method thereof.The annular oligomeric silsesquioxanes of present invention synthesis(MOSS)(Component A), synthesis terminal hydroxy ethylene polysiloxanes(Component B), then A, B component is according to 1:The mass ratio mixing of (1 ~ 5), recycles chloroplatinic acid catalyst to carry out Si―H addition reaction solidification and prepares LED encapsulation MOSS modified organic silicon packaging plastics.Preparation process is simple of the present invention, synthetic yield are high;The packaging plastic has good heat stability and higher refractive index, and light transmission preferably, can solidify at a lower temperature.The MOSS modified organic silicons packaging plastic of preparation 500 nm wavelength light transmittance more than 90%, refractive index at a temperature of 25 DEG C is 1.535, thermal gravimetric analysis results show that the heat decomposition temperature of the packaging plastic is 416 DEG C, it is 57% in 700 DEG C of residual rates, show preferable heat resistance, the tensile strength and elongation at break of the packaging plastic is respectively 1.88 MPa and 157%, Shore A hardness 36.
Description
Technical field
The present invention relates to a kind of annular oligomeric silsesquioxanes, its modified organic silicon packaging plastic and preparation method thereof.
Background technology
Light emitting diode (Lighting-Emitting Diode, LED) is because have efficient, environmental protection, life-span length etc. excellent
Point, the application prospect in fields such as illumination, display, electronic equipment backlight, and decorations get most of the attention, and LED has become the whole world
The trend and trend of change.The fast development of LED technology, luminous efficiency are stepped up.With LED towards high brightness, high-weatherability,
The directions such as high uniformity of luminance, high reliability are developed, and it is also proposed higher performance to the macromolecular material for LED encapsulation will
Ask.The encapsulating material of great power LED must possess high index of refraction, high transmission rate, preferable heat resistance, sealing property and good
Good mechanical property and adhesive property.China encapsulates big country as LED, during the LED component encapsulation in the whole world 80% is all concentrated on
State.But China but lags far behind the major countries such as the U.S., Japan, power type LED encapsulation in the research of LED encapsulation material
Material market is captured by Japan and U.S.'s product completely so that our product cost is raised, and profit margin is little, more crucial
It is that development is seriously restricted.
The LED encapsulation material being widely used at present mainly has epoxy resin and organic siliconresin.Wherein, epoxy resin is present
The defect that crosslink density is excessive after solidification, toughness of material is poor, in addition, aging xanthochromia easily occurs in epoxy encapsulation glue asking
Topic, causes light transmittance and luminance-reduction, reduction of service life;Although traditional organic siliconresin packaging plastic refractive index and light transmittance
It is higher, but it is difficult to the defect for overcoming its mechanical property not enough.And add nanometer particle-modified organo-mineral complexing packaging plastic, though
Can so have at a relatively high refractive index, while can also improve the heat-resisting and mechanical performance of packaging plastic, but encapsulating material can be affected
The transparency, cause light output efficiency to decline.
The content of the invention
In order to solve problems of the prior art, an object of the present invention is to provide a kind of New Ring-like Type oligomerisation
Silsesquioxane (MOSS).
The second object of the present invention is organic silica gel to be modified by annular oligomeric silsesquioxanes (MOSS), system
A kind of new MOSS modified organic silicon packaging plastics were obtained, the refractive index of the packaging plastic is up to 1.535, and light transmittance is more than 90%,
Heat decomposition temperature is 415 DEG C, and elongation at break is 160%, and solidification temperature is low, packaging plastic and commercially available phase obtained in the present invention
Close product and compare and have the advantages that high folding, heat-resisting, preferable mechanical property and solidification temperature are low.
The third object of the present invention is the preparation method for providing the packaging plastic.
For achieving the above object, the present invention adopts following mechanism:
A. the synthetic method of annular oligomeric silsesquioxanes (MOSS):The method referred to as metal inducement is self-assembled into around-France.
It is characterized in that the polysiloxanes complexation of the hydrolyzed trialkoxysilanes generation metal ion under transition metal and alkali metal induction
Then the complex and a chlorosilane are reacted, are peeled off in complex by the metal of thing --- three-dimensional oligomerisation-polysiloxanes complex
Metal ion, finally give MOSS.It is PhSi (OR) first in course of reaction3, NaOH, water, alcohol cohydrolysis have obtained saddle
The crystalline complex of shape.The crystalline complex outer layer is phenyl ring-type silicone layer, their negative charge by internal layer copper from
Son and sodium ion neutralization, also contain alcohol and water molecule in crystalline complex.Crystal is reacted with chlorosilane, by copper ion and sodium ion
Peel off and generate CuCl2And NaCl, while generating MOSS.
B. the synthetic method of terminal hydroxy ethylene polysiloxanes:The synthetic method is characterized in that selection potassium hydroxide as anti-
The catalyst answered, from toluene as reaction dissolvent, octamethylcy-clotetrasiloxane D4Enter with methylvinyldimethoxysilane
Row open loop condensation reaction, prepares terminal hydroxy ethylene polysiloxanes.
The curing of c.MOSS modified organic silicon packaging plastics:The method is by silicon hydrogen component annular oligomeric silsesquioxanes
Si―H addition reaction curing reaction between MOSS and vinyl component terminal hydroxy ethylene polysiloxanes, prepares MOSS modified organic silicons
Packaging plastic.
According to above-mentioned reaction mechanism, the present invention is adopted the following technical scheme that:
A kind of annular oligomeric silsesquioxanes, it is characterised in that the structural formula of annular oligomeric silsesquioxanes MOSS is:
A kind of LED encapsulation MOSS modified organic silicon packaging plastics, the packaging plastic is double-component, it is characterised in that described group
A is divided to adopt above-mentioned annular oligomeric silsesquioxanes MOSS, component B is terminal hydroxy ethylene polysiloxanes, during use, by component
A and component B are according to 1:The mass ratio of (1~5) is sufficiently mixed uniformly, and adds chloroplatinic acid catalyst, and its addition is mixed for reaction
The 0.1%~0.3% of compound gross mass, after excluding bubble, solidifies 1~2h at a temperature of 60 DEG C~80 DEG C, or in room temperature
48~72h of lower solidification, can obtain the LED encapsulation MOSS modified organic silicon packaging plastics for solidifying.
The structural formula of above-mentioned component B terminal hydroxy ethylene polysiloxanes is:
Wherein x:Y is 1:1~1:2.
A kind of method for preparing above-mentioned LED encapsulation MOSS modified organic silicon packaging plastics, its levy be the method tool
Body step is as follows:
A. sodium hydrate solid is dissolved in the mixed solvent of n-butyl alcohol and deionized water, heating for dissolving, add with
Sodium hydroxide mass ratio is 2:1~6:1 trimethoxy-benzene base silane, at 100 DEG C~130 DEG C, is heated to reflux 20~60min;
Then will be 1 with sodium hydroxide mass ratio:1~2:1 Copper dichloride dihydrate is dissolved in n-butyl alcohol, by the Copper dichloride dihydrate
Butanol solution is added drop-wise in above-mentioned reaction system, after being added dropwise to complete, and continues 30~60min of backflow.After reaction terminates, will be anti-
Answer solution filtered while hot, concentrating filter liquor, stand still for crystals, filter, obtain blue colored crystal, obtain ten hexichol basic rings, 12 silanol
Copper/sodium complex crystal;
B. by ten hexichol basic ring obtained by step a, 12 silanol copper/sodium complex crystal and pyridine according to mass ratio 1:1~4:
1 is dissolved in normal hexane, and 30~60min of reaction is stirred at room temperature;Then the hexane solution of dimethylchlorosilane is slowly added dropwise, it is described
The mass ratio of ten hexichol basic rings, 12 silanol copper/sodium complex crystal and dimethylchlorosilane be 1:1~3:1, it is stirred at room temperature
After 20~60min, 1.5~3h of back flow reaction, after reaction terminates, is cooled to room temperature, filters, and is washed with deionized, anhydrous
Magnesium sulfate is dried, and removes solvent, obtains colourless viscous liquid and is annular oligomeric silsesquioxanes;
C. by octamethylcy-clotetrasiloxane and methylvinyldimethoxysilane according to 2:1~5:1 mass ratio is dissolved in
In toluene, and add the potassium hydroxide of catalytic amount as the catalyst of reaction, stirring 3~6h of lower back flow reaction, add from
Sub- water, continues to be heated to reflux 1~3h, after reaction terminates, is cooled to room temperature, and it is 7 that deionized water is washed till pH, then micro- with 0.45
The membrane filtration in metre hole footpath, removes solvent, obtains colorless transparent viscous liquid and is terminal hydroxy ethylene polysiloxanes;
During use, by component A and component B according to 1:The mass ratio of (1~5) is sufficiently mixed uniformly, and adds chloroplatinic acid to urge
Agent, its addition for reactant mixture gross mass 0.1%~0.3%, after excluding bubble, at a temperature of 60 DEG C~80 DEG C
1~2h of solidification, or solidify 48~72h at room temperature, the LED encapsulation MOSS modified organic silicons encapsulation for solidifying can be obtained
Glue.
The cubic cage and the higher bond energy of siliconoxygen bond of the annular oligomeric silsesquioxanes of the present invention so that ring itself
The addition that shape oligomeric silsesquioxanes have excellent heat resistance, annular oligomeric silsesquioxanes causes packaging plastic to have very well
Heat stability;At the same time, the phenyl ring with higher Lorentz-Lorenz molar refraction is introduced in annular oligomeric silsesquioxanes so that
Annular oligomeric silsesquioxanes modified organic silicon packaging plastic has higher refractive index, 500nm wavelength light transmittance 90%
More than, the refractive index at a temperature of 25 DEG C is 1.535, and thermal gravimetric analysis results show that the heat decomposition temperature of the packaging plastic is 416 DEG C,
It is 57% in 700 DEG C of residual rates, shows preferable heat resistance, the tensile strength of the packaging plastic and elongation at break difference
For 1.88MPa and 157%, Shore A hardness 36.The inventive method preparation process is simple, synthetic yield are high simultaneously.
Specific embodiment
After now be specified in the specific embodiment of the present invention.
Embodiment one:
1) synthesis of ten hexichol basic rings, 12 silanol copper/sodium complex crystal
Appropriate sodium hydrate solid is weighed first, the heating for dissolving in n-butanol solvent and a small amount of deionized water.To
It is 2 wherein to add with sodium hydroxide mass ratio:Reaction temperature is increased to 100 DEG C, is heated back by 1 trimethoxy-benzene base silane
Stream 60min.Then according to sodium hydroxide mass ratio 1:1 proportioning weighs Copper dichloride dihydrate, and is dissolved in appropriate
In n-butyl alcohol, it is slowly added in above-mentioned reaction system.After being added dropwise to complete, continue backflow 30min.After backflow terminates, will be anti-
Answer solution sucking filtration while hot.After by filtrate, vacuum distillation goes out the n-butanol solvent of half volume at a temperature of 70 DEG C, it is stored in relatively low
At a temperature of stand still for crystals.Finally filter, obtain blue colored crystal, the blue colored crystal is dried to constant weight in 80 DEG C of baking ovens, is obtained
To ten hexichol basic rings, 12 silanol copper/sodium complex crystal.
2) synthesis of component A annular oligomeric silsesquioxanes (MOSS)
By 12 silanol copper of obtained ten hexichol basic ring/sodium complex crystal with pyridine according to mass ratio 1:1 is mixed,
Appropriate normal hexane is being added thereto to as reaction dissolvent, 30min after mixing, is being stirred at room temperature.Then according to ten diphenyl
12 silanol copper of ring/sodium complex crystal mass compares 1:1 weighs dimethylchlorosilane, and is made in being dissolved in normal hexane molten
Liquid, and be slowly added in above-mentioned reaction system, after 30min is stirred at room temperature, temperature is increased to into 70 DEG C of 1.5~3h of backflow.
After backflow terminates, room temperature is cooled to, filters, and be washed with deionized three times and remove inorganic ionss therein, add suitable
The anhydrous magnesium sulfate of amount is dried, and vacuum distillation after filtration removes solvent, obtains colourless viscous liquid and is annular oligomerisation sesquialter silicon
Oxygen alkane MOSS.
3) synthesis of component B terminal hydroxy ethylene polysiloxanes
Octamethylcy-clotetrasiloxane (D is weighed respectively4) and methylvinyldimethoxysilane (VDMMS), according to quality
Than 2:1 mixing, and add a small amount of potassium hydroxide as the catalyst of reaction, add appropriate toluene and do reaction dissolvent.Room
After warm mix homogeneously, reaction temperature is increased to into 100 DEG C of heated and stirred 4~6h of backflow, appropriate deionized water is added, is continued
It is heated to reflux 2h.After reaction terminates, treat that solution is cooled down, it is 7 that deionized water is washed till pH, then with poly- the four of 0.45 micron pore size
Fluoride film is filtered, then filtrate decompression distillation is removed after solvent and water, is obtained colorless transparent viscous liquid and is terminal hydroxy group
Vinyl polysiloxane.
4) solidification of MOSS modified organic silicons packaging plastic
By component A annular oligomeric silsesquioxanes MOSS and component B terminal hydroxy ethylene polysiloxanes of synthesis according to matter
Amount compares 1:4 are sufficiently mixed and stir, and are subsequently adding a small amount of chloroplatinic acid catalyst and are mixed with, and the addition of catalyst is
The 0.1%~0.3% of mixture gross mass.Decompression excludes bubble, after excluding bubble, at a temperature of 60~80 DEG C solidification 1~
2h, or solidify 48~72h at room temperature.The LED encapsulation MOSS modified organic silicon packaging plastics for solidifying can be obtained.
The MOSS modified organic silicons packaging plastic that the present embodiment is prepared is 90% in the light transmittance of visible light wave range, 25
Refractive index at a temperature of DEG C is 1.516, and thermal gravimetric analysis results show that the heat decomposition temperature of the packaging plastic is 408 DEG C, at 700 DEG C
Residual rate is 53%, shows preferable heat resistance, and the tensile strength and elongation at break of the packaging plastic are respectively 1.87MPa
With 162%, Shore A hardness 32.
Embodiment two:
1) synthesis of ten hexichol basic rings, 12 silanol copper/sodium complex crystal
Appropriate sodium hydrate solid is weighed first, the heating for dissolving in n-butanol solvent and a small amount of deionized water.To
It is 4 wherein to add with sodium hydroxide mass ratio:Reaction temperature is increased to 110 DEG C, is heated back by 1 trimethoxy-benzene base silane
Stream 40min.Then according to sodium hydroxide mass ratio 3:2 proportioning weighs Copper dichloride dihydrate, and is dissolved in appropriate
In n-butyl alcohol, it is slowly added in above-mentioned reaction system.After being added dropwise to complete, continue backflow 40min.After backflow terminates, will be anti-
Answer solution sucking filtration while hot.After by filtrate, vacuum distillation goes out the n-butanol solvent of half volume at a temperature of 80 DEG C, it is stored in relatively low
At a temperature of stand still for crystals.Finally filter, obtain blue colored crystal, the blue colored crystal is dried to constant weight in 90 DEG C of baking ovens, is obtained
To ten hexichol basic rings, 12 silanol copper/sodium complex crystal.
2) synthesis of component A annular oligomeric silsesquioxanes (MOSS)
By 12 silanol copper of obtained ten hexichol basic ring/sodium complex crystal with pyridine according to mass ratio 2:1 is mixed,
Appropriate normal hexane is being added thereto to as reaction dissolvent, 40min after mixing, is being stirred at room temperature.Then according to ten diphenyl
12 silanol copper of ring/sodium complex crystal mass compares 2:1 weighs dimethylchlorosilane, and is made in being dissolved in normal hexane molten
Liquid, and be slowly added in above-mentioned reaction system, after 40min is stirred at room temperature, temperature is increased to into 80 DEG C of 1.5~3h of backflow.
After backflow terminates, room temperature is cooled to, filters, and be washed with deionized three times and remove inorganic ionss therein, add suitable
The anhydrous magnesium sulfate of amount is dried, and vacuum distillation after filtration removes solvent, obtains colourless viscous liquid and is annular oligomerisation sesquialter silicon
Oxygen alkane MOSS.
3) synthesis of component B terminal hydroxy ethylene polysiloxanes
Octamethylcy-clotetrasiloxane (D4) and methylvinyldimethoxysilane (VDMMS) are weighed respectively, according to quality
Than 3:1 mixing, and add a small amount of potassium hydroxide as the catalyst of reaction, add appropriate toluene and do reaction dissolvent.Room
After warm mix homogeneously, reaction temperature is increased to into 115 DEG C of heated and stirred 3~5h of backflow, appropriate deionized water is added, is continued
It is heated to reflux 2h.After reaction terminates, treat that solution is cooled down, it is 7 that deionized water is washed till pH, then with poly- the four of 0.45 micron pore size
Fluoride film is filtered, then filtrate decompression distillation is removed after solvent and water, is obtained colorless transparent viscous liquid and is terminal hydroxy group
Vinyl polysiloxane.
4) solidification of MOSS modified organic silicons packaging plastic
By component A annular oligomeric silsesquioxanes MOSS and component B terminal hydroxy ethylene polysiloxanes of synthesis according to matter
Amount compares 1:3 are sufficiently mixed and stir, and are subsequently adding a small amount of chloroplatinic acid catalyst and are mixed with, and the addition of catalyst is
The 0.1%~0.3% of mixture gross mass.Decompression excludes bubble, after excluding bubble, at a temperature of 60~80 DEG C solidification 1~
2h, or solidify 48~72h at room temperature.The LED encapsulation MOSS modified organic silicon packaging plastics for solidifying can be obtained.
The MOSS modified organic silicons packaging plastic that the present embodiment is prepared is 90% in the light transmittance of visible light wave range, 25
Refractive index at a temperature of DEG C is 1.527, and thermal gravimetric analysis results show that the heat decomposition temperature of the packaging plastic is 415 DEG C, at 700 DEG C
Residual rate is 56%, shows preferable heat resistance, and the tensile strength and elongation at break of the packaging plastic are respectively 1.90MPa
With 159%, Shore A hardness 34.
Embodiment three:
1) synthesis of ten hexichol basic rings, 12 silanol copper/sodium complex crystal
Appropriate sodium hydrate solid is weighed first, the heating for dissolving in n-butanol solvent and a small amount of deionized water.To
It is 6 wherein to add with sodium hydroxide mass ratio:Reaction temperature is increased to 130 DEG C, is heated back by 1 trimethoxy-benzene base silane
Stream 30min.Then according to sodium hydroxide mass ratio 2:1 proportioning weighs Copper dichloride dihydrate, and is dissolved in appropriate
In n-butyl alcohol, it is slowly added in above-mentioned reaction system.After being added dropwise to complete, continue backflow 40min.After backflow terminates, will be anti-
Answer solution sucking filtration while hot.After by filtrate, vacuum distillation goes out the n-butanol solvent of half volume at a temperature of 80 DEG C, it is stored in relatively low
At a temperature of stand still for crystals.Finally filter, obtain blue colored crystal, the blue colored crystal is dried to constant weight in 90 DEG C of baking ovens, is obtained
To ten hexichol basic rings, 12 silanol copper/sodium complex crystal.
2) synthesis of component A annular oligomeric silsesquioxanes (MOSS)
By 12 silanol copper of obtained ten hexichol basic ring/sodium complex crystal with pyridine according to mass ratio 3:1 is mixed,
Appropriate normal hexane is being added thereto to as reaction dissolvent, 40min after mixing, is being stirred at room temperature.Then according to ten diphenyl
12 silanol copper of ring/sodium complex crystal mass compares 3:1 weighs dimethylchlorosilane, and is made in being dissolved in normal hexane molten
Liquid, and be slowly added in above-mentioned reaction system, after 40min is stirred at room temperature, temperature is increased to into 90 DEG C of 1.5~3h of backflow.
After backflow terminates, room temperature is cooled to, filters, and be washed with deionized three times and remove inorganic ionss therein, add suitable
The anhydrous magnesium sulfate of amount is dried, and vacuum distillation after filtration removes solvent, obtains colourless viscous liquid and is annular oligomerisation sesquialter silicon
Oxygen alkane MOSS.
3) synthesis of component B terminal hydroxy ethylene polysiloxanes
Octamethylcy-clotetrasiloxane (D4) and methylvinyldimethoxysilane (VDMMS) are weighed respectively, according to quality
Than 5:1 mixing, and add a small amount of potassium hydroxide as the catalyst of reaction, add appropriate toluene and do reaction dissolvent.Room
After warm mix homogeneously, reaction temperature is increased to into 130 DEG C of heated and stirred 3~5h of backflow, appropriate deionized water is added, is continued
It is heated to reflux 2h.After reaction terminates, treat that solution is cooled down, it is 7 that deionized water is washed till pH, then with poly- the four of 0.45 micron pore size
Fluoride film is filtered, then filtrate decompression distillation is removed after solvent and water, is obtained colorless transparent viscous liquid and is terminal hydroxy group
Vinyl polysiloxane.
4) solidification of MOSS modified organic silicons packaging plastic
By component A annular oligomeric silsesquioxanes MOSS and component B terminal hydroxy ethylene polysiloxanes of synthesis according to matter
Amount compares 1:2 are sufficiently mixed and stir, and are subsequently adding a small amount of chloroplatinic acid catalyst and are mixed with, and the addition of catalyst is
The 0.1%~0.3% of mixture gross mass.Decompression excludes bubble, after excluding bubble, at a temperature of 60~80 DEG C solidification 1~
2h, or solidify 48~72h at room temperature.The LED encapsulation MOSS modified organic silicon packaging plastics for solidifying can be obtained.
The MOSS modified organic silicons packaging plastic that the present embodiment is prepared is 90% in the light transmittance of visible light wave range, 25
Refractive index at a temperature of DEG C is 1.535, and thermal gravimetric analysis results show that the heat decomposition temperature of the packaging plastic is 416 DEG C, at 700 DEG C
Residual rate is 57%, shows preferable heat resistance, and the tensile strength and elongation at break of the packaging plastic are respectively 1.88MPa
With 157%, Shore A hardness 36.
Claims (4)
1. a kind of annular oligomeric silsesquioxanes, it is characterised in that the structural formula of annular oligomeric silsesquioxanes MOSS is:
2. a kind of LED is encapsulated and is used MOSS modified organic silicon packaging plastics, and the packaging plastic is double-component, it is characterised in that described component
A adopts annular oligomeric silsesquioxanes MOSS according to claim 1, and component B is terminal hydroxy ethylene polysiloxanes, is made
Used time, by component A and component B according to 1:The mass ratio of (1~5) is sufficiently mixed uniformly, and adds chloroplatinic acid catalyst, its addition
0.1%~0.3% for reactant mixture gross mass is measured, after excluding bubble, solidifies 1~2h at a temperature of 60 DEG C~80 DEG C,
Or solidify 48~72h at room temperature, the LED encapsulation MOSS modified organic silicon packaging plastics for solidifying can be obtained.
3. LED according to claim 2 is encapsulated with MOSS modified organic silicon packaging plastics, it is characterised in that described component B
The structural formula of terminal hydroxy ethylene polysiloxanes is:
Wherein x:Y is 1:1~1:2.
4. a kind of method of the LED encapsulation MOSS modified organic silicon packaging plastics prepared described in Claims 2 or 3, which is levied and is
The method is comprised the following steps that:
A. sodium hydrate solid is dissolved in the mixed solvent of n-butyl alcohol and deionized water, heating for dissolving is added and hydrogen-oxygen
It is 2 to change sodium mass ratio:1~6:1 trimethoxy-benzene base silane, at 100 DEG C~130 DEG C, is heated to reflux 20~60min;Then
To be 1 with sodium hydroxide mass ratio:1~2:1 Copper dichloride dihydrate is dissolved in n-butyl alcohol, by the positive fourth of the Copper dichloride dihydrate
Alcoholic solution is added drop-wise in above-mentioned reaction system, after being added dropwise to complete, and continues 30~60min of backflow.After reaction terminates, will react molten
Liquid filtered while hot, concentrating filter liquor, stands still for crystals, filters, and obtains blue colored crystal, obtains ten hexichol basic rings, 12 silanol copper/sodium
Complex Crystal;
B. by ten hexichol basic ring obtained by step a, 12 silanol copper/sodium complex crystal and pyridine according to mass ratio 1:1~4:1 is molten
In normal hexane, 30~60min of reaction is stirred at room temperature;Then the hexane solution of dimethylchlorosilane is slowly added dropwise, it is described
Ten hexichol basic rings, 12 silanol copper/sodium complex crystal is 1 with the mass ratio of dimethylchlorosilane:1~3:1, it is stirred at room temperature 20
After~60min, 1.5~3h of back flow reaction, after reaction terminates, is cooled to room temperature, filters, and is washed with deionized, anhydrous sulfur
Sour magnesium is dried, and removes solvent, obtains colourless viscous liquid and is annular oligomeric silsesquioxanes;
C. by octamethylcy-clotetrasiloxane and methylvinyldimethoxysilane according to 2:1~5:1 mass ratio is dissolved in toluene
In, and the potassium hydroxide of catalytic amount is added as the catalyst of reaction, the lower 3~6h of back flow reaction of stirring adds deionized water,
Continue to be heated to reflux 1~3h, after reaction terminates, be cooled to room temperature, it is 7 that deionized water is washed till pH, then uses 0.45 micron openings
The membrane filtration in footpath, removes solvent, obtains colorless transparent viscous liquid and is terminal hydroxy ethylene polysiloxanes;
During use, by component A and component B according to 1:The mass ratio of (1~5) is sufficiently mixed uniformly, and adds chloroplatinic acid catalyst,
Its addition for reactant mixture gross mass 0.1%~0.3%, after excluding bubble, solidifies 1 at a temperature of 60 DEG C~80 DEG C
~2h, or solidify 48~72h at room temperature, the LED encapsulation MOSS modified organic silicon packaging plastics for solidifying can be obtained.
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CN102634027A (en) * | 2012-03-20 | 2012-08-15 | 上海交通大学 | Preparation method of MOSS (macrocyclic oligomeric silsesquioxanes) containing 12-epoxy group |
CN102827477A (en) * | 2011-06-16 | 2012-12-19 | 日东电工株式会社 | Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device |
CN104893310A (en) * | 2015-06-29 | 2015-09-09 | 山东东岳有机硅材料有限公司 | Polysilsesquioxane-contained liquid silicone rubber for LED packaging and preparation method of polysilsesquioxane-contained liquid silicone rubber |
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CN102827477A (en) * | 2011-06-16 | 2012-12-19 | 日东电工株式会社 | Silicone resin composition, encapsulating layer, reflector, and optical semiconductor device |
CN102634027A (en) * | 2012-03-20 | 2012-08-15 | 上海交通大学 | Preparation method of MOSS (macrocyclic oligomeric silsesquioxanes) containing 12-epoxy group |
CN104893310A (en) * | 2015-06-29 | 2015-09-09 | 山东东岳有机硅材料有限公司 | Polysilsesquioxane-contained liquid silicone rubber for LED packaging and preparation method of polysilsesquioxane-contained liquid silicone rubber |
Non-Patent Citations (1)
Title |
---|
韩金: "含环形齐聚倍半硅氧烷聚合物的合成及其结构与性能研究", 《中国博士学位论文全文数据库》 * |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110194946A (en) * | 2019-05-16 | 2019-09-03 | 上海大学 | Organic silicon packaging glue and preparation method thereof |
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