以4,4'-二羟基二苯硫醚和9,9-二(4-羟苯基)芴,环氧氯丙烷为原料,在碱性条件下缩聚合成一种含S元素含芴结构的环氧树脂基体;通过溶胶-凝胶法,以四正丁醇锆为前驱体,以KH560为偶联剂,在基体上原位合成无机纳米ZrO2粒子,再经过热固化制备出一种具有高折射率的光学纳米杂化材料。通过红外光谱、1H核磁共振、X射线衍射、纳米粒度仪等手段对杂化材料的结构进行表征,并采用紫外分光光度仪、热重分析仪、椭圆偏振光谱仪对其性能进行了表征与测试。结果表明:ZrO2粒子在聚合物基体中合成,并以纳米粒度均匀分散,杂化材料具有很好的光学性能,在可见光范围内普遍保持90%以上的透过率,随着ZrO2含量的增加,杂化树脂折射率呈线性增加,ZrO2含量在19.33%时,折射率达到1.739。
An epoxy resin matrix containing S element and fluorene structure was synthesized by polycondensation of 4,4'-thiodiphenol,9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin under alkaline conditions.Using four n-butanol zirconium as precursor and KH560 as coupling agent,the inorganic nano ZrO2 particles were in-situ synthesized on the polymer matrix by sol-gel method,and then an optical nano-hybrid material with high refractive index was further prepared by thermal curing.The structure of the hybrid material was characterized by infrared spectroscopy,1H nuclear magnetic resonance,X-ray diffraction,and nanoparticle size analyzer.Its performance was also characterized and tested by ultraviolet spectrophotometer,thermogravimetric analyzer,and Abbe refractometer.The results showed that ZrO2 particles were successfully synthesized in the polymer matrix and uniformly dispersed in nanoparticle size.Hybrid material had good optical properties and generally maintained a transmittance of more than 90% in the visible light range.With the increase of ZrO2 content,the refractive index of the hybrid resin increased linearly.When ZrO2 content was 19.33%,the refractive index reached 1.739.
[1] Kim J S,Yang S C,Bae B S.Thermally stable transparent sol-gel based siloxane hybrid material with high refractive index for light emitting diode (LED) encapsulation[J].Chemistry of Materials,2010,22(11):3549-3555.
[2] Gong T,Lyu P,Palm K J,et al.Emergent opportunities with metallic alloys:from material design to optical devices[J].Advanced Optical Materials,2020,8(23):2001082.
[3] Alim M D,Glugla D J,Mavila S,et al.High dynamic range (Δn) two-stage photopolymers via enhanced solubility of a high refractive index acrylate writing monomer[J].ACS Applied Materials & Interfaces,2018,10(1):1217-1224.
[4] Kleine T S,Glass R S,Lichtenberger D L,et al.100th anniversary of macromolecular science viewpoint:high refractive index polymers from elemental sulfur for infrared thermal imaging and optics[J].ACS Macro Letters,2020,9(2):245-259.
[5] Liu J,Ueda M.High refractive index polymers:fundamental research and practical applications[J].Journal of Materials Chemistry,2009,19(47):8907-8919.
[6] Badur T,Dams C,Hampp N.High refractive index polymers by design[J].Macromolecules,2018,51(11):4220-4228.
[7] Macdonald E K,Shaver M P.Intrinsic high refractive index polymers[J].Polymer International,2015,64(1):6-14.
[8] Lü C,Yang B.High refractive index organic-inorganic nanocomposites:design,synthesis and application[J].Journal of Materials Chemistry,2009,19(19):2884-2901.
[9] 汪洁,尚欣欣,张香兰,等.高折射率有机硅LED封装材料研究进展[J].高分子通报,2016(6):15-22.
[10] Higashihara T,Ueda M.Recent progress in high refractive index polymers[J].Macromolecules,2015,48(7):1915-1929.
[11] Huang D,Qin A,Tang B Z.Thiol-based click polymerizations for sulfur-containing polymers[J].Sulfur-Containing Polymers:From Synthesis to Functional Materials,2021,DOI:10.1002/9783527823819.CH4.
[12] Cheng Yuanrong,Lu Changli,Yang Bai.A review on high refractive index nanocomposites for optical applications[J].Recent Patents on Materials Science,2011,4(1):15-17.
[13] Fang L,Sun J,Chen X,et al.Phosphorus-and sulfur-containing high-refractive-index polymers with high Tg and transparency derived from a bio-based aldehyde[J].Macromolecules,2020,53(1):125-131.
[14] Zhang Y,Liu J,Wu X,et al.Synthesis and characterization of thianthrene-containing preimidized soluble polyimide resins and the derived films with high refractive indices and good optical transparency[J].Journal of Polymer Research,2019,26(1):1-11.
[15] Iino S,Sobu S,Nakabayashi K,et al.Highly transparent and photopatternable spirobifluorene-based polythioethers with high refractive indices via thiol-ene click chemistry[J].Polymer,2021,224:123725.
[16] Shadfan A,Pawlowski M,Wang Y,et al.Design and fabrication of a miniature objective consisting of high refractive index zinc sulfide lenses for laser surgery[J].Optical Engineering,2016,55(2):025107.
[17] Ochi M,Nii D,Suzuki Y,et al.Thermal and optical properties of epoxy/zirconia hybrid materials synthesized via in situ polymerization[J].Journal of Materials Science,2010,45(10):2655-2661.
[18] Noack J,Schmidt L,Glasel H J,et al.Inorganic-organic nanocomposites based on sol-gel derived magnesium fluoride[J].Nanoscale,2011,3:4774-4779.
[19] Xu J,Zhang Y,Zhu W,et al.Synthesis of polymeric nanocomposite hydrogels containing the pendant ZnS nanoparticles:approach to higher refractive index optical polymeric nanocomposites[J].Macromolecules,2018,51(7):2672-2681.
[20] Huang T T,Cheng S W,Tsai C L,et al.Optically isotropic,colorless,and flexible PITEs/TiO 2 and ZrO2 hybrid films with tunable refractive index,abbe number,and memory properties[J].Scientific Reports,2017,7(1):1-10.
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