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POSS related polymer nanocomposites
(2011-12-01)
Kuo, Shiao-Wei
;
Chang, Feng-Chih
;
應用化學系
;
Department of Applied Chemistry
This review describes the syntheses of polyhedral oligomeric silsesquioxane (T(8)-POSS) compounds, the miscibility of PUSS derivatives and polymers, the preparation of both multifunctional and monofunctional monomers and polymers containing PUSS including styryl-POSS, methacrylate-PUSS, norbornyl-PUSS, vinyl-POSS, epoxy-POSS, phenolic-POSS, benzoxazine-PUSS, amine-PUSS, and hydroxyl-POSS. The thermal, dynamic mechanical, electrical, and surface properties of PUSS-related polymeric nanocomposites prepared from both monofunctional and multifunctional PUSS monomers are discussed. In addition, we describe the applications of several high-performance PUSS nanocomposites in such systems as light emitting diodes, liquid crystals, photo-resist materials, low-dielectric constant materials, self-assembled block copolymers, and nano particles. (C) 2011 Elsevier Ltd. All rights reserved.
Synthesis and characterization of polybenzoxazine networks nanocomposites containing multifunctional polyhedral oligomeric silsesquioxane (POSS)
(2006-05-31)
Lee, Yuan-Jyh
;
Kuo, Shiao-Wei
;
Huang, Chih-Feng
;
Chang, Feng-Chih
;
應用化學系
A new class of polybenzoxazine/POSS nanocomposites with network structure is prepared by reacting multifunctional benzoxazine POSS (MBZ-POSS) with benzoxazine monomers (Pa and Ba) at various compositional ratios. Octafunctional cubic silsesquioxane (MBZ-POSS) is used as a curing agent, which is synthesized from eight organic benzoxazine tethers through hydrosilylation of vinyl-terminated benzoxazine monomer (VP-a) with octakis(dimethylsiloxy)silsesquioxane (Q(8)M(8)(H)) using a platinum complex catalyst (Pt-dvs). Incorporation of the silsesquioxane core into polybenzoxazine matrix could significantly hinder the mobility of polymer chains and enhance the thermal stability of these hybrid materials. For these nanocomposites, increasing the POSS content in the hybrids is expected to improve its thermal properties with respect to the neat polybenzoxazine. The morphology feature is useful to explain the thermal property changes (T-g and T-d) and AFM images show that the presence of POSS aggregation in larger scales occurs at higher POSS contents. The reason of the heterogeneous phase separation may be from the less compatibility of the inorganic silsesquioxane core with organic benzoxazine species and the homopolymerization of MBZ-POSS. In the course of the formation of the polybenzoxazine/POSS hybrids, POSS particles were separated from the polybenzoxazine rich region, leading to POSS rich domains in the range of 50-1000 nm. (c) 2006 Elsevier Ltd. All rights reserved.
Novel epoxy nanocomposite of low D-k introduced fluorine-containing POSS structure
(2007-02-15)
Wang, Yen-Zen
;
Chen, Wen-Yi
;
Yang, Chao-Chen
;
Lin, Chen-Lung
;
Chang, Feng-Chih
A nanoporous additives, polyhedral oilgomeric silisesquioxane containing eight functional hexafluorine groups, octakis(dimethylsiloxyhexafluoropropyl ether)silsesquioxane (OF) has been synthesized and blended with the UV-cured epoxy resin. The OF containing (10%) epoxy has significantly lower dielectric constant (2.65) than the plain epoxy (3.71). The incorporation of fluorine containing additives is well-known to reduce dielectric constant due to lower its polarizability. In addition, the presence of the bulky POSS structure is able to create additional free space or pores and further reduces the dielectric constant of the epoxy matrix. (c) 2007 Wiley Periodicals, Inc.
Novel nanocomposite of epoxy resin by introduced reactive and nanoporous material
(2007-12-01)
Yang, Chao-Chen
;
Chang, Feng-Chih
;
Wang, Yen-Zen
;
Chan, Chia-Ming
;
Lin, Chen-Lung
A reactive and nanoporous particle (OG) was introduced to UV-cured epoxy resin to form great low D-k material for electronic industrial. We expected the porous cage of OG to decrease the dielectric constant of UV-cured epoxy resin and multiple reactive functional groups (oxirane ring) of OG reacted with photoinitiator to increase the curing density of UV-cured epoxy resin. The glass transition temperatures (T-g) of epoxy increases with the increase of the OG content up to 10 phr due to the increase of crosslinking density. Excessive aggregation at highest OG content of 15 phr results in the reduced crosslinking density and T-g. The char yield of the composite increases with increase of OG content because stable Si and SiO2 are formed after thermal decomposition. The presence of OG results in the higher porosity and thus the lower dielectric constant.
Studies on thermal properties of PS nanocomposites for the effect of intercalated agent with side groups
(2008-03-03)
Fu, Huei-Kuan
;
Huang, Chih-Feng
;
Huang, Jieh-Ming
;
Chang, Feng-Chih
;
應用化學系
Poly styrene-layered silicate nanocomposites were prepared from three new organically modified clays by emulsion polymerization method. These nanocomposites were exfoliated up to 3 wt% content of pristine clay relative to the amount of polystyrene (PS). The intercalated agents C-20, C-20-4VB, and C-20-POSS intercalated into the galleries result in improved compatibility between hydrophobic polymer and hydrophilic clay and facilitate the well dispersion of exfoliated clay in the polymer matrix. Results from X-ray diffraction, TEM and Fourier transform infrared spectroscopy indicate that these intercalated agents are indeed intercalated into the clay galleries successfully and these clay platelets are exfoliated in resultant nanocomposites. Thermal analyses of polystyrene-layered silicate nanocomposites compared with virgin PS indicate that the onset degradation temperature ca. 25 degrees C increased and the maximum reduction in coefficient of thermal expansion (CTE) is ca. 40% for the C-20-POSS/clay nanocomposite. In addition, the glass transition temperatures of all these nanocomposites are higher than the virgin PS. (c) 2008 Elsevier Ltd. All rights reserved.
Polyhedral Oligomeric Silsesquioxane-Encapsulating Amorphous Palladium Nanoclusters as Catalysts for Heck Reactions
(2011-05-01)
Lu, Chu-Hua
;
Chang, Feng-Chih
;
應用化學系
;
Department of Applied Chemistry
Palladium nanoparticles (Pd NPs) capped with a certain protective group possessing stable reactivity of Pd-catalyzed reactions has been quickly and easily synthesized. The thiol-Pd(2+) complexes of C(12)-Pd(2+) and POSS-Pd(2+) are prepared by the ligand exchange of acetate groups on Pd(OAc)(2) with 1-dodecanthiol and SH-POSS (polyhedral oligomeric silsesquioxane), respectively. After thermal treatment at 120 degrees C for 30 min, the C(12)-Pd(2+) and POSS-Pd(2+) turn into C(12)-Pd(0) and POSS-Pd(0) NPs through the reduction of palladium cations with thiol groups. Unlike the well-known metallic Pd NPS with constituent Pd atoms arranged in an orderly repeating pattern, the cores of these thial-Pd(0) NPs are composed of a disordered (amorphous) aggregation of Pd atoms due to the steric hindrance caused by the affinity between in situ Pd atoms and thial groups. The relatively larger gaps between two adjacent POSS moieties, formed by solvent permeation when one isobutyl group approaches another, can be employed as transportation channels for reactants such as iodobenzene (IB). Thus, methyl trans-cinnamate is produced as soon as the reactants of IB and methyl acrylate are added in the POSS-Pd(0) NP-catalyzed Heck coupling. In contrast, an activation time of similar to 1 h is needed for C(12)-Pd(0) NPs to replace these long-alkyl protective groups with iodobenzene.
Characterization of negative-type photoresists containing polyhedral oligomeric silsesquioxane methacrylate
(2008-07-01)
Lin, Ho-May
;
Hseih, Kuo-Hung
;
Chang, Feng-Chih
;
應用化學系
;
Department of Applied Chemistry
A series of negative-type photoresists made by blending with various contents of polyhedral oligomeric silsesquioxane (POSS) methacrylate were prepared and characterized. These POSS macromers tend to crystallize or aggregate to form their own domains within the photoresist matrix. Sensitivity of the POSS modified photoresist is significantly improved with the increase of the POSS content. Results from photo-DSC analyses indicate that both induction time and peak maximum of heat flux are reduced by blending with POSS macromer. Addition of the proper amount (<13 wt%) of POSS can effectively increase photo-polymerization rate and exothermic heat. Hydrogen bonding interaction between the hydroxyl of photoresist and the siloxane of POSS tends to attract methacrylate double bonds surrounding POSS particles locally and thus enhances the rate of photo-polymerization and sensitivity. (C) 2008 Elsevier B.V. All rights reserved.
Surface Modification of Gold Nanoparticles with Polyhedral Oligomeric Silsesquioxane and Incorporation within Polymer Matrices
(2009-04-15)
Kuo, Shiao-Wei
;
Wu, Yung-Chien
;
Lu, Chu-Hua
;
Chang, Feng-Chih
;
應用化學系
A new approach to achieve polymer-mediated gold ferromagnetic nanocomposites in a polyhedral oligomeric silsesquioxane (POSS)-containing random copolymer matrix has been developed. Stable and narrow distributed gold nanoparticles modified by 3-mercaptopropylisobutyl POSS to form Au-POSS nanoparticles are prepared by two-phase liquid-liquid method. These Au-POSS nanoparticles form partial particle aggregation by blending with poly(n-butyl methacrylate) (PnBMA) homopolymer because of poor miscibility between Au-POSS and PnBMA polymer matrix. The incorporation the POSS moiety into the PnBMA main chain as a random copolymer matrix displays well-dispersed gold nanoparticles because the POSS-POSS interaction enhances miscibility between gold nanoparticles and the PnBMA-POSS copolymer matrix. This gold-containing nanocomposite exhibits ferromagnetic phenomenon at room temperature. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 811-819, 2009
Preparation and Characterization of Epoxy/Polyhedral Oligomeric Silsesquioxane Hybrid Nanocomposites
(2009-10-01)
Huang, Jieh-Ming
;
Huang, Hui-Ju
;
Wang, Yu-Xiang
;
Chen, Wen-Yi
;
Chang, Feng-Chih
We have prepared epoxy/polyhedral oligomeric silsesquioxane (POSS) nanocomposites by photopolymerization from octakis(glycidylsiloxy)octasilsesquioxane (OG) and diglycidyl ether of bisphenol A. We used nuclear magnetic resonance, Raman, and Fourier transform infrared spectroscopies to characterize the chemical structure of the synthetic OG. Differential scanning calorimetry and dynamic mechanical analysis (DMA) revealed that the nanocomposites possessed higher glass transition temperatures than that of the pristine epoxy resin. Furthermore, DMA indicated that all of the nanocomposites exhibited enhanced storage moduli in the rubbery state, a phenomenon that we ascribe to both the nano-reinforcement effect of the POSS cages and the additional degree of crosslinking that resulted from the reactions between the epoxy and OG units. Thermogravimetric analysis revealed that the thermal stability of the nanocomposites was better than that of the pristine epoxy. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1927-1934, 2009
The effect of sulfonic acid groups within a polyhedral oligomeric silsesquioxane containing cross-linked proton exchange membrane
(2010-01-06)
Yen, Ying-Chieh
;
Ye, Yun-Sheng
;
Cheng, Chih-Chia
;
Lu, Chu-Hua
;
Tsai, Li-Duan
In this study, polyhedral oligomeric silsesquioxane (POSS) moieties were incorporated into sulfonated poly(ether ether ketone) (SPEEK) to form a new cross-linked proton exchange membrane (PEM). The distribution of the POSS containing cross-linkers with or without sulfonic acid groups dictates the water behavior and connectivity of hydrophilic domains of the PEM. A PEM formed by incorporating 17.5 wt% of the cross-linker (containing POSS macromer and sulfonic acid groups) into SPEEK exhibits high proton conductivity (0.0153 S/cm), low methanol permeability (1.34 x 10(-7) cm(2)/s), and high selectivity (1.14 x 10(5) Ss/cm(3)). (C) 2009 Elsevier Ltd. All rights reserved.

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