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JOURNAL OF APPLIED POLYMER SCIENCE · 2019 ·Vol. 136 ·期 32 ·47834 · IF 2.188

A facile route to prepare homogeneous silicone resin doped with titanium

Jianjun Chen,Zien Fu,Hengchao Huang,Zhonghua Chen,Xingrong Zeng

A facile route was introduced to prepare homogeneous silicone resin doped with titanium hybrid with high refractive index (RI). Specifically, the hybrids were obtained from the transesterification of hydroxyl-phenyl-vinyl silicone resin and titanium isopropoxide under anhydrous conditions. The structures of hybrid silicone and their corresponding intermediates (hydroxyl-phenyl-vinyl silicone) were characterized by nuclear magnetic resonance spectroscopy ( 1 H NMR, 29 Si NMR) as well as Fourier transform infrared spectroscopy (FTIR). The hybrids had a transmittance of more than 88% ranging from 450 nm to 800 nm, a high RI of 1.585, and a lower water vapor permeability of 3.58 g /m 2 .24h. Results from FTIR showed intensity of Ti-O-Si bond in hybrid decrease with extended the storage time, but the properties of cured hybrids including optical, mechanical, and gas permeability were not influenced. Compared to chips encapsulated with pure silicone, the luminous efficiency of the chips encapsulated with hybrids was improved from 138.6 lm/W to 156.4 lm/W. The thermal shock and hygrothermal aging test also demonstrated the hybrids had a wide range application in light-emitting diode (LED) packaging. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136 , 47834.

CAS / MDL: 546-68-9
研究领域: 材料科学 · 化学工程
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INTERNATIONAL JOURNAL OF POLYMER ANALYSIS AND CHARACTERIZATION · 2018 · IF 1.333

Direct synthesis of zirconium containing phenyl silicone resin for LED encapsulation

Tiezhu Guo,Xiaodan Lin,Xingsong Hu,Shaowei Cui,Xiaolian Chen

Zirconium containing phenyl silicone resin were synthesized through hydrolysis among zirconium n-propoxide (ZP), diphenyldimethoxysilane, and 3-(trimethoxysily)propyl methacrylate under acidic conditions. The results indicated that the resins have favorable thermal stability for practical usage, and the thermal weightless of all resins are less than 3% under 200°C.The refractive index of the materials is positively correlated with zirconium content, and tunable between 1.57 and 1.59, and light transmittance does not change significantly with the increase of zirconium element. In addition, the resins can be stably stored for more than 6 months without any effect on the application.

CAS / MDL: 5411-14-3
研究领域: 材料科学 · 化学工程
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Silicon · 2020 ·Vol. 12 ·期 12 ·3005-3013 · IF 1.499

A New Dealcoholization Method in the Synthesis of Vinyl Methyl Phenyl Silicone Resins for LED Encapsulation

Pan Zhaoqun,Zeng Kelin,Huang Bingsheng,Zhu Liqiang

The oligosiloxane resins were synthesized through hydrolytic sol-gel reaction and remained many hydroxyl groups, which did great harm to the curing process and resulted in poor performance of the cured products. In previous works, epoxy-modified silicone resins were synthesized by dealcoholization, a reaction between 3-glycidoxypropylmethyldimethoxysilane and terminal hydroxyl groups in phenyl silicone resins. Although this method eliminated the hydroxyl groups, it caused a large loss of vinyl groups inevitably and a poor stability of cured products. In this study, methyltrimethoxysilane (MTMS) was used to eliminate hydroxyl groups containing in vinyl methyl phenyl silicone resins, which were synthesized through hydrolytic sol-gel reaction. Most of residual hydroxyl groups were deleted effectively and the great loss of vinyl groups were avoided in the dealcoholization reaction. Then, the methyl phenyl silicone materials were fabricated by hydrosilylation reaction between the synthesized vinyl methyl phenyl silicone resins and hydrogen-containing ones. The cured silicone materials showed excellent optical performance (~ 89.1% at 450 nm) and good adhesion performance. In addition, due to less vinyl loss in the vinyl methyl phenyl silicone resins, the cured methyl phenyl silicone materials exhibited higher cross-linking density, better thermal resistance (5% mass loss at 435 °C) and better mechanical properties (50 shore D) compared with the epoxy-modified phenyl silicone materials. The lumen depreciation (working 168 h at 50 mA) and reflow soldering tests further demonstrated the methyl phenyl silicone materials possessed good thermal stability. These results indicated that the methyl phenyl silicone materials could be used as a LED encapsulant with a good performance.

CAS / MDL: 1185-55-3
研究领域: 材料科学 · 化学工程
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RSC Advances · 2021 ·Vol. 11 ·期 30 ·18326-18332 · IF 3.361

Zirconia/phenylsiloxane nano-composite for LED encapsulation with high and stable light extraction efficiency

Ying Lu,Zhihang Zhao,Xianpeng Fan,Xinyu Cao,Mingtan Hai,Zhou Yang,Kun Zheng,Jiaxin Lu,Jingnan Zhang,Yongmei Ma,Rongben Zhang,Shibi Fang

To obtain a rapid processible LED encapsulant that leads to high and stable light extraction efficiency (LEE), UV curable ZrO2/phenyl-siloxane nano-composite (ZSC) double-layer encapsulants were prepared and optimized. The highly crystalline ZrO2 nanoparticles with a diameter of ∼14 nm were synthesized through a modified hydrothermal method at mild conditions, and a UV curable methacryl-diphenyl-polysiloxane (MDPS) with a refractive index (RI) of 1.54 (at 633 nm) was synthesized from self-condensation of diphenylsilanediol and an end-capping reaction. High refractive indexes (RIs) from 1.54–1.61 have been obtained for ZSC composites by adding 0–20 wt% ZrO2. Before and after sulfur vapor erosion, the double-layer encapsulated sample (M-10/M) showed 11.2% and 64.8% higher LEE respectively than that of Dow Corning OE-7662. Meanwhile, the variation of LED light color temperature (Tc) was less than 1%. The effect of the ZrO2 nanoparticle content on LEE of double-layer and single-layer encapsulation were compared and discussed based on Fresnel loss and Rayleigh scattering theories. The double-layered UV curing processing took only 1/6 of the time needed for common thermal curing.

研究领域: 材料科学 · 光学工程
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POLYMER BULLETIN · 2021 ·Vol. 79 ·期 9 ·7177-7192 · IF 2.87

Synthesis and application of cyclotetrasiloxane modified with epoxy resins

Pan Zhaoqun,Chen Mianfeng,Zeng Keling,Kang Yingzi

In this paper, a cyclotetrasiloxane modified with epoxy resin was synthesized via hydrosilylation with 1, 3, 5, 7-tetramethylcyclotetrasiloxane (D4H) and 4-vinyl-1-cyclohexane 1, 2-epoxide (VCHO). The structure of tetramethylcyclotetrasiloxane modified with cyclohexane epoxide (D4H–VCHO) was characterized by Fourier transform infrared (FT-IR), 1H nuclear magnetic resonance (1H-NMR) and gel permeation chromatography (GPC). The effects of feeding methods, feeding ratios, catalyst dosages, reaction temperature and reaction time on the products were investigated. After 4-h reaction with 8 ppm catalyst at 90 °C, D4H–VCHO was obtained with an epoxy value of 0.521 and a refractive index of 1.4920. Then, with 4-methylhexahydrophthalic anhydride as a curing agent and tetrabutylammonium bromide as a catalyst, the obtained D4H–VCHO was cured at 90 °C for 1 h and then 120 °C for another hour. The cured products showed high light transmittance, strong thermal stability, suitable hardness and low water absorption. The glass transition temperature of cured materials was 151.6 °C, indicating the improvement of flexibility. In addition, the introduction of epoxy groups greatly enhanced the adhesion of silicone resins to substrates. The results demonstrated that the epoxy-modified silicone materials could be applied as LED packaging materials.

CAS / MDL: 1643-19-2
研究领域: 材料科学 · 化学工程
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JOURNAL OF APPLIED POLYMER SCIENCE · 2015 ·Vol. 132 ·期 27 · IF 1.768

Synthesis and characterization of vinyl-polyhedral oligomeric silsesquioxanes-reinforced silicone resin with three-dimensional cross-linking structure

Yan Zhang,Yin-wen Li,Jian Zheng,Hui-long Guo,Xiao-xiao Guan,Man-geng Lu,Kun Wu,Li-yan Liang

A novel thermal stability and highly transparent silicone resin-type material was prepared via hydrosilylation of vinyl-polyhedral oligomeric silsesquioxanes (POSS)-grafted methylhydrosilicone oil and vinylmethylsilicone oil in the presence of Karstedt catalyst. The morphology, mechanical property, thermal stability, optical transmittance, thermal-oxidation resistance of the vinyl-POSS-reinforced silicone resins were systematically investigated. Scanning electron microscopy showed that the vinyl-POSS-reinforced silicone resins had good compatibility with polydimethylsiloxane (PDMS) systems. The mechanical analysis and thermo gravimetric analysis indicated that the mechanical properties and thermal stability increased with increasing quantity of vinyl-POSS. However, the optical transmittance increased with the increasing amount of vinyl-POSS rather than decreased. In addition, the incorporation of vinyl-POSS did not improve the thermal resistance of the PDMS polymers. The product has the potential application for LED packaging. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132 , 42187.

CAS / MDL: 68478-92-2
研究领域: 材料科学 · 高分子化学
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JOURNAL OF LUMINESCENCE · 2025 · IF 3.6

Preparation and optical properties of Na-β″-Al2O3: Ce3+ phosphors

Yingnan Dong,Yumeng Jia,Kenan Xu,Xu Sun,Jing Wang,Zhongxiang Shi,Yanchen Liu

In order to expand the multi-scene application of rare earth doped luminescent materials in the field of blue light illumination, a series of Ce 3+ doped Na-β″-Al 2 O 3 phosphors were prepared by solid-state method with Na-β″-Al 2 O 3 as matrix. The crystal structure, micro-morphology, optical properties and thermal stability were investigated systematically. The results show that the activated ion Ce 3+ in the prepared Na-β″-Al 2 O 3 : x Ce 3+ phosphor replaces the Al 3+ (CN = 6) lattice in the crystal, and with a outstanding blue light emission. In addition, the thermal stability of Na-β″-Al 2 O 3 : 0.05Ce 3+ phosphor is analyzed by variable temperature spectrum, and its luminescence intensity at 573K can reach 71.55 % at room temperature. Finally, Na-β″-Al 2 O 3 : 0.05Ce 3+ phosphors are packaged with 330 nm n-UV LED chips to obtain high quality blue LED devices. With its high color rendering index (81.60), low color temperature (2886 K) and good color consistency, it provides a theoretical basis for the application of Na-β″-Al 2 O 3 -based phosphors in blue LED devices, and makes it show great application potential in the field of solid-state blue spectral lighting.

CAS / MDL: 1306-38-3
研究领域: 材料科学 · 固体化学 · 发光材料 · 照明工程 · 无机功能材料
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2018 ·Vol. 34 ·期 2 ·326-332 · IF 1.248

Oligo-fluoropolymer Modified Cycloaliphatic Epoxy Resins with Excellent Compatibility, Waterproof and Mechanical Properties for LED Encapsulation

Sun Yang,Liu Weiqu,Wang Zhengfang,Tan Jianquan

An oligo-fluoropolymer(PFM) with functional cycloaliphatic epoxy and fluorinated groups was obtained via free radical polymerization and applied to the modification of cycloaliphatic epoxy resins(CE). The chemical structure of PFM was characterized by Fourier transform infrared(FTIR) spectroscopy, gel permeation chromatogra-phy(GPC) and nuclear magnetic resonance(NMR) spectroscopy, and the effects of different PFM concentra-tions(0.5%—6%, mass fraction) on the thermal resistance, mechanical properties, surface dewettability, light trans-mission, refractive index and various cured polymer properties were studied in detail. The DSC and TGA results demonstrate that the modified epoxy resins possess a higher thermal resistance than the neat epoxy resin. The im-provements in the surface dewettability and water resistance are caused by the high crosslinking density and the enrichment of the oligo-fluorinated random copolymers dispersed in the matrix. The fracture surface morphologies of the thermosets were investigated by scanning electron microscopy(SEM) and transmission electron microsco-py(TEM). It was observed that the optical transmittance of the composites was maintained even though microphase separation occurred during the curing process. With respect to the corresponding properties of the neat epoxy resins, the 2 phr(parts per hundreds of resin) PFM thermoset exhibited relatively better comprehensive properties, making the cured material a good candidate for light-emitting diode(LED) encapsulation.

CAS / MDL: 78-67-1
研究领域: 材料科学 · 化学工程
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Silicon · 2021 ·Vol. 14 ·期 3 ·1159-1167 · IF 2.67

Synthesis of Epoxy-Modified Methyl Phenyl Silicone Resins for LED Encapsulation

Pan Zhaoqun,Chen Mianfeng,Zeng Keling,Kang Yingzi

The epoxy-modified silicones have the advantages of both epoxy and organic silicon. In this paper, a series of epoxy-modified methyl phenyl silicone resins were synthesized through the hydrosilylation reaction between 1, 2-epoxy-4-vinylcyclohexane and methyl phenyl silicone resins. The effects of catalyst dosage, reaction time and temperature on the products were further discussed to determine optimal reaction conditions. Then, the as-prepared epoxy-modified silicone resins were cured with methylhexahydrophthalic anhydride. The curing kinetics was investigated through differential scanning calorimetry (DSC). The curing conditions were determined as follows: 1-h curing at 80 °C for and subsequent 1-h curing at 110 °C. The as-prepared products exhibited high light transmittance (~ 90% at 450 nm), strong bonding, suitable hardness and sound waterproof performance. In addition, the introduction of methylphenylsiloxane chain significantly improved the heat resistance and UV resistance of cured products. The epoxy-modified silicone resins are ideal LED packaging materials.

CAS / MDL: 1643-19-2 101-02-0
研究领域: 材料科学 · 化学工程
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POLYMERS FOR ADVANCED TECHNOLOGIES · 2018 ·Vol. 29 ·期 8 ·2245-2252 · IF 2.137

High refractive index adamantane-based silicone resins for the encapsulation of light-emitting diodes

Lin Tong,Yakai Feng,Xujun Sun,Ying Han,Dongshun Jiao,Xiaohua Tan

The encapsulation of high power light emitting diode (LED) needs the silicone resins to have relative high refractive index and thermal-aging properties. Herein, high refractive index adamantane-based phenyl epoxy-silicone (APES) resins for LED encapsulation were synthesized by the sol-gel condensation of 1-adamantane methanol propyltrimethoxysilane-3-urethane, γ-(2,3-epoxypropoxy)propytrimethoxysilane and diphenylsilanediol. These adamantane-based silicone resins have multifunctional groups including adamantyl group, phenyl group, and epoxy group in order to meet the various requirements for LED encapsulation. Importantly, the adamantane group in the silicone resins benefits for high refractive index and anti-thermal properties. These APES resins were characterized by proton nuclear magnetic resonance and Fourier transform infrared spectroscopy. When APES resins were cured by methylhexahydrophthalic anhydride, they showed relatively high refractive index of 1.56, high hardness, and high thermal resistance. The encapsulated LED demonstrated high adhesion properties by red-ink tests. These merits make adamantane-based silicone resins promising candidates as LED encapsulation materials.

CAS / MDL: 1119-94-4 301-10-0
研究领域: 材料科学 · 光学工程
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APPLIED SURFACE SCIENCE · 2018 · IF 4.439

Preparation and origin of thermally resistant biobased epoxy resin with low internal stress and good UV resistance based on SiO2 hybridized cellulose for light emitting diode encapsulation

Xuelin Fan,Jia-Tao Miao,Li Yuan,Qingbao Guan,Aijuan Gu,Guozheng Liang

Big internal stress and poor UV resistance are two bottlenecks of epoxy resins for light emitting diode (LED) encapsulation, and how to solve them with a green method is still a great challenge. Herein, a unique hybrid was synthesized by forming SiO 2 particles on surface of cellulose, the hybridized cellulose (mCNC@SiO 2 ) was then used to develop new high performance epoxy resin (mCNC@SiO 2 /EP) for LED encapsulation. The effect of the content of mCNC@SiO 2 on the comprehensive performances of mCNC@SiO 2 /EP resins was studied. Results show that the presence of mCNC@SiO 2 not only greatly reduces the internal stress and improves UV resistance, but also increases moisture resistance while maintaining high heat resistance. When the content of mCNC@SiO 2 is only 2.0 wt%, the internal stress is reduced by 62%, thanking to the significant decrease in thermal expansion coefficient, and curing stress derived from the flexibility of Si-O-Si segment in mCNC@SiO 2 . In addition, mCNC@SiO 2 /EP resin has good transmittance, proving that the presence of mCNC@SiO 2 can effectively alleviate yellowing and improve UV resistance. These excellent comprehensive properties of mCNC@SiO 2 /EP resin demonstrate that mCNC@SiO 2 is a green and multifunctional modifier of epoxy resin for high performance LED encapsulation.

研究领域: 材料科学 · 绿色化学
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PROGRESS IN ORGANIC COATINGS · 2021 · IF 5.161

Facile thiol-epoxy click chemistry for transparent and aging-resistant silicone/epoxy composite as LED encapsulant

Guanghong Lin,Jingfeng Yin,Ziqian Lin,Yuwei Zhu,Weijian Li,Huizi Li,Zhu Liu,Hongping Xiang,Xiaoxuan Liu

The thiol-epoxy click chemistry is promising for microelectronic packaging due to its outstanding properties, while there is little knowledge on silicone/epoxy composite fabricated via this approach. Herein, a thiol-functionalized silicone resin (MDT-SH) is synthesized and compounded with epoxy resin to form silicone/epoxy composite. The thermal-curing behaviors, mechanical properties and LED encapsulation of the developed composite are studied detailedly. The thermal-curing kinetics indicate that the thiol-epoxy polymerization in silicone/epoxy composite tends more to the first-order reaction and its active energy is about 60.3 kJ/mol. The mechanical properties of the composite are varied with the molecular structure of MDT-SH and thiol/epoxy ratio. Moreover, the composite has excellent transparency in visible region, and its transparency is little affected by thermal and UV ageing. More importantly, the transparency is only slightly decreased after the composite is serviced at normal temperature and pressure for 2 years. The light output power of LEDs encapsulated by this composite is comparable to the commercial counterparts like Dow Corning OE-6550, but its thermal-curing time and temperature are much lower than the latter, contributing to cost reduction. Therefore, this silicone/epoxy composite based on thiol–epoxy click chemistry would greatly improve the microelectronic packaging.

CAS / MDL: 6674-22-2
研究领域: 材料科学 · 微电子封装
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