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Most inorganic nucleating agents for poly(ethylene terephthalate) (PET) have limited nucleating ability due to poor compatibility with PET. Polyhedral oligomeric silsesquioxanes (POSS) is a type of cage-shaped organic/inorganic hybrid nanoparticles with three different particle sizes: octameric (T8), decameric (T10), and dodecameric (T12). POSS is considered as a promising nucleating agent for PET because the inorganic moieties contribute to high thermal stability and nucleation and the organic moieties can be tethered to PET chains. In contrast to T8 POSS, the nucleation ability of T12 POSS for PET has been poorly reported. In this study, our newly synthesized aminopropyl functionalized T12 POSS (A-POSS) is proposed as a potential nucleating agent for PET. The amine group of A-POSS is able to be chemically conjugated to PET chains, thereby giving a more homogeneous dispersion of T12 POSS in PET than non-functional T12 Phenyl POSS (N-POSS). Its PET composites gave a ∼1.2 fold higher crystallization temperature and ∼2.7 fold higher shear-induced crystallization rate over pristine PET. Such nucleating effects for PET is more effective than those of non-functional T12 POSS and the more widely studied T8 POSS. This strategy is potentially beneficial for the high-shear melt processes of PET such as spinning and film extrusion.

An investigation into the hydrolysis kinetics of an aqueous base-catalyzed sol-gel reaction yielding ladder-like polysilsesquioxanes was studied using NMR. Under various variables of monomer concentration, water concentration, solvent type, and monomer type, the various effects on molecular weight and degree of condensation were elucidated. Moreover, the various rate orders and rate constants were calculated and compared with previous reports of the hydrolysis of organosilane precursors. Through this study we were able to ascertain the optimal conditions of hydrolysis-polycondensation for obtaining highly condensed, high molecular weight ladder-like polysilsesquioxanes.

Through fine-tuning of the myriad of reaction conditions for an aqueous base-catalyzed hydrolysis–polycondensation reaction, a facile synthesis of structurally controlled polyphenylsilsesquioxanes was developed. Mechanism and kinetic studies indicated that the condensation reaction proceeded through a T1 structured dimer, which was quantitatively and in situ formed through mild hydrolysis of a phenyltrimethoxysilane (PTMS) monomer, to give either the cage-structured polyhedral oligomeric silsesquioxanes (POSS) or the corresponding ladderlike silsesquioxane (LPSQ) with excellent yields. Ladderlike and POSS materials were selectively achieved at higher and lower initial concentrations of PTMS, respectively, and an in-depth spectroscopic analysis of both compounds clearly revealed their structural differences with different molecular weights.

A series of thiol-ene UV-curable inorganic–organic hybrid polysilsesquioxanes of various phenyl:methacryloxypropyl and phenyl:mercaptopropyl copolymer compositions were synthesized in one-batch using a base-catalyzed system. These thermoplastic photocurable ladder-like structured materials were examined as scratch-resistant, hard-coating materials on both glass and PET substrates. The unique fully condensed structure of the hybrid polymers allowed for simplified processing and through variation of the organic functional group, films with high transparency, tunable refractive indices in the range of 1.467–1.546, pencil hardness values of 9H, and high nanoindentation modulus were obtained (7 GPa). These scratch-resistant polysilsesquioxanes may provide insight into the different organic functional group compositions which allow for optimal mechanical properties.

A series of organic–inorganic hybrid spin-on-glass polymethylsilsesquioxanes were synthesized utilizing a cyclic siloxane precursor, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxyl cyclosiloxane (MT4-OH), copolymerized with methyltriethoxysilane (MTES) at various comonomer ratios. By selectively introducing this 2-D cyclic crosslinker, we were able to obtain spin-on-glass hybrimers with low dielectric constant (2.5–2.7), high nanoindentation modulus (5–10.5 GPa), with high thermal stability (>700 °C) without the use of porogens or additives. The use of the cyclic monomer MT4-OH greatly increased the mechanical properties, which allowed for impeccable reliability of a variety of patterns obtained through etching and chemical mechanical planarization processes, while maintaining optimal gap-filling properties. Due to the superior dielectric, mechanical, and integrated processing of these materials, these hybrids derived from MT4-OH may be utilized as next generation spin-on-glass low-dielectric constant materials.

Poly(methyl)silsesquioxane-based spin-on-glass resins incorporating both a cyclic precursor, 1,3,5,7-tetramethyl 1,3,5,7-tetrahydroxyl cyclosiloxane, and incompletely condensed methyl-substituted POSS were synthesized and their thermal, mechanical, and electrical properties were investigated as a function of the POSS loading content. By introducing incompletely condensed methyl-substituted POSS compounds at the molecular level as sol–gel precursors, exceptional thermal stability (>700 °C), good mechanical properties (elastic modulus >4.0 GPa), and an ultra-low dielectric constant (k = 1.8) were obtained. In addition to providing a new route towards fully poly(methyl)silsesquioxane-based spin-on-glass resins with the above properties, the realization of the application of integration circuits was evaluated to show that the ultra low-k, mechanically robust spin-on-glass materials were able to withstand harsh wet chemical and dry etching, as well as chemical mechanical planarization (CMP) processing.

A ladder-like structured poly(mercaptopropyl)silsesquioxane (LPMPSQ) was synthesized in one-bath, under mildly basic conditions at room temperature. Obtained LPMPSQ was utilized as a macroinitiator for thiol-ene graft photopolymerization of various vinyl monomers to give hard, soft, hydrophobic, and hydrophilic graft copolymers with low PDI (

A series of azido-functionalized ladder-like structures was prepared by direct azidation of ladder-like structured poly(p-chloromethylphenyl)silsesquioxane (LPCMPSQ) and poly(chloropropyl)silsesquioxane (LPAPSQ) in excellent yields with perfect substitution of the chloro-compounds. The azido-functionalized silsesquioxanes obtained were then photocured without additional photoinitiator to give highly cross-linked thin films with an exceptionally high modulus (> 12 GPa). Furthermore, these materials were shown to be patterned through photolithography to give impeccable micropatterned microstructures.

Three reactive dichroic dyes with 3,5-dichloro-2,4,6-triazine moiety were synthesized by reaction between dichroic dyes (such as congo red, direct black 22 or direct black 4) and cyanuric chloride. Poly(vinyl alcohol) (PVA) films were dyed with the obtained three reactive dichroic dyes. After 400% drawing of the PVA films, their optical properties were compared with an iodine-doped PVA film prepared in the same condition. Durability test was performed at in 85% of relative humidity for 120 hrs. We found that compared with the iodine-doped PVA polarizing film, the relative durability of the PVA polarizing film dyed with the reactive dichroic dyes was greatly improved.

A novel organic-inorganic hybrid-type ladder-like poly(benzylazide) silsesquioxane (LPBAzSQ) and ladder-like poly(propylazide) silsesquioxane (LPPAzSQ) were synthesized through azidation of ladder-like poly(p-chloromethyl)phenylsilsesquioxane (LPCMPSQ) and ladder-like poly(propylchloro)silsesquioxane (LPPCSQ). The ladder-like structure of the synthesized LPBAzSQ and LPPAzSQ compounds, full substitution of azide groups, and their click chemistry with various functional groups was characterized by 1H NMR, 13C NMR, 29Si NMR, FT-IR, GPC. This new approach for functionalization of ladder-like silsesquioxanes has allowed for insertion of polar functional groups that have yet be examined in silsesquioxane chemistry.

In this study, commercial poly(vinyl alcohol) (PVA) film was dyed with reactive dichroic dyes under mild conditions using organic solvents in stead of strong basic aqueous solution. After drawing of 500% of this PVA film, the polarizing efficiency and the single piece transmittance were measured. The degree of saponification of the commercialized PVA film was determined by using NMR and FT-IR spectromety. The commercial PVA film, with ca. 100% of the degree of saponification determined by NMR spectrometry, was dyed with the reactive dichroic dyes, which have 3,5-dichloro-2,4,6-triazine moiety. As a result, we found that the PVA film dyed with the reactive congo red showed relatively good polarization efficiency, and the PVA film dyed with the reactive direct black 22 exhibited relatively good single piece transmittance.

A series of high molecular weight polymethylsilsesquioxanes (PMSQs) were synthesized through polymerization of an isolated hydroxyl-substituted cyclic siloxane stereoisomer, cis-trans-cis 1,3,5,7 tetramethyl 1,3,5,7 tetrahydroxyl cyclosiloxane, for interlayer dielectric (ILD) application as low dielectric materials. The molecular weights of PMSQs were controlled by varying polycondensation time. Structural analyses of the obtained PMSQs were carried out by gel chromatography (GPC), FTIR, 29Si NMR, static light scattering (SLS), solution X-ray scattering, and X-ray diffraction. The change in molecular shape of the PMSQs went from linear to branched in structure as molecular weight increased. Furthermore, thin film properties were investigated for application as interlayer dielectric materials. As structural branching increased, its properties showed isotropic tendencies, relatively high modulus (5.4 GPa), and low dielectric constant (2.74) with increase in the inter-molecular space.

The stereo cyclic siloxane compounds having tetra hydroxyl and tetra methyl group were synthesized by hydrolysis of tetrahydrido tetramethyl cyclosiloxane consisting of four stereoisomers. Among the stereo cyclic isomers, cis-trans-cis tetrahydroxyl tetramethyl cyclosiloxane (2) was separated by recrystallization and was used as a monomer species for preparation of ladder-like polymethylsilsesquioxane (PMSQ). The isolated isomer was directly polymerized in THF with potassium carbonate (K2CO3) by systematic ring condensation. The hydrolyzed stereoisomers were characterized by 1H and 29Si NMR, and HPLC. The structure of the synthesized PMSQs were characterized by size exclusion chromatography (SEC), MALDI-TOF mass, 29Si NMR, and small angle X-ray scattering (SAXS).

Various ladder-like structured poly(phenyl-co-methacryl silsesquioxane)s (LPMSQ)s with high molecular weight (Mw = 10,000 ∼ 40,000) were synthesized by direct hydrolysis and polymerization in the presence of base catalyst at 25 °C. Synthesized LPMSQs mainly showed ladder-like structure and photo-cure reaction by 100 mW/cm2 (360 nm) for 10 s without any photo-cure initiators. Chemical composition and structural analysis of the obtained LPMSQs were characterized using 1H NMR, 29Si NMR, Fourier transform infrared spectroscopy (FTIR), gel permeation chromatography (GPC), and X-ray diffraction (XRD). Physical properties of LPMSQs before and after photcuring were analyzed by Nanoindentation. Surface modulus increased to 8GPa and hardness of thin films increased from 100 to 400 MPa. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Poly(propyl carbazole silsesquioxane) (PPCSQ) with a high molecular weight (M w = 10,200) was synthesized by the direct hydrolysis of 9-[3-(trimethoxysilyl) propyl]-9H-carbazole with K2CO3, followed by a condensation reaction in an H2O/dimethylformamide (DMF) mixture solvent at 25 °C. The obtained PPCSQ consisted of ladder-like structured siloxane bonds with carbarzole groups as the pendant group, where the distance between two carbarzole pendant groups through the siloxane backbone was 15.6 A and the mean thickness of the siloxane backbone was 4.3 A. This PPCSQ was thermally stable up to 450 °C and the glass transition temperature was ca. 95 °C, showing good film formablity by spin casting.

Six banana‐shaped compounds with a central core based on a 4,6‐dichloro‐1,3‐phenylene group were synthesized by varying the terminal chains (R = OC10H21 or OC11H21) and the lateral substituents (X = H, F or Cl). Their mesophases were characterized by a combination of differential scanning calorimetry, polarizing optical microscopy, triangular wave method, and X‐ray diffractometry. Mesomorphic properties of the banana‐shaped mesogens with an olefinic group (R = OC11H21) as a terminal chain are sensitive to lateral halogen substituents as much as those of the analogues with a saturated group (R = OC10H21). The compounds with X = F showed an antiferroelectric switchable smectic phase, which has been designated a B2 phase. The compounds without a lateral halogen substituent only formed a nematic phase, while the compounds with X = Cl did not exhibit a mesophase in the melt.

Cage dodecaphenylsilsesquioxane (T12-Phenyl) was synthesized in a one batch, mildly basic aqueous solution under room temperature conditions using a trialkoxysilane precursor. Significant improvements in synthetic yield (95%) were observed compared with previous reports. Kinetic studies of the hydrolysis of phenyltrimethoxysilane were conducted and the condensation was monitored by (29)Si NMR which revealed the presence of a transient, intermediary T1 species as the pathway to dodecaphenylsilsesquioxane spherulites, and the tendency for T12 structures over T8, T10, and other substructures was explained through MM2 simulations.

A high molecular weight, photocurable inorganic-organic hybrid based on ladder-like poly(phenyl6-co-methacrylate4)silsesquioxanes (LPPMA64) was investigated as a flexible display substrate. Photocured free standing films with 40μm thickness showed high transparency (>95%), excellent thermal stability (Td >450°C), and low coefficient of thermal expansion (38ppm/K) without the use of reinforced glass fibers. Furthermore, these ladder-like structured materials did not require any thermal treatment processes due to the negligible amounts of uncondensed groups, thus simplifying manufacturing processing. These novel hybrid films present an alternative to organic plastics as flexible electronic device substrates due to their excellent optical and thermal properties.

Dielectric cap quantum well disordering (DCQWD) of GaAs/AlGaAs multiple quantum well (MQW) structure was carried out by using SiNx. capping layer grown by plasma enhanced chemical vapor deposition (PECVD). By varying the NH3 flow rate with fixed SiH4 flow rate during the SiNx. growth, the characteristics of the capping film were varied. There was an increase in the energy shift of quantum well photoluminescence (PL) peak after thermal treatment of the samples with rapid thermal annealing (RTA) as the NH3 flow rate was increased, although the thickness of SiNx decreased. This is thought to be due to the increase of hydrogen content in SiNx. film grown at higher NH3 flow rate.

Well-defined hybrid polymers consisting of organic polymers grafted from inorganic backbone were synthesized by atom transfer radical polymerization (ATRP). Ladder-like structured polysilsesquioxane functioned as both ATRP initiator and hard inorganic backbone, while the organic polymers grafted were hard styrene and soft n-butyl acrylate. Ladder-like structured poly(chloromethylphenylsilsesquioxane) (LCMPSQ) was synthesized using sequential two-step reactions with (ρ-chloromethyl)phenyltrimethxysilane as a monomer in one bath in the presence of K2CO3 as a base catalyst (M w = 6,000). Obtained LCMPSQ was then used as a multi-functional macroinitiator for graft polymerization of styrene (St) or/and n-butyl acrylate (nBA) monomers via ATRP using a CuCl catalyzed system, which gave three types of hybrid graft polymers: poly(styrene-g-silsesquioxane) (PS-g-PSQ), poly(nBA-g-silsesquioxane) (PnBA-g-PSQ) and poly(styrene-ran-nBA-g-silsesquioxane) (PS/nBA-g-PSQ). The hybrid graft polymers were prepared with vari...

Polymethylsilsesquioxane(PMSQ)s with photo-curable groups were prepared by copolymerization of alkoxysilanes. Poly(acryloyl-co-methylsilsesquioxane)(PAMSQ)s of various mole ratio acryloyl group (6 mol%, 12 mol%, 24 mol%, 48 mol%, 100 mol%) were obtained from copolymerization of methyltrimethoxylsilane and 3-(trimethoxysilyl)propyl acrylate. Optical and photonic curable properties were studied by near infrared region spectra, prism coupler, UV-visible spectra, and photo-DSC. The optical losses were below 0.002 dB/cm at 830, 1330, and 1550 nm, respectively. Optical loss was found to be independent of a molar ratio of functional group.

A new type of low-k dielectric material, poly(tridecafluoro1,1,2,2,tetrahydrooctyl-co-phenylsilsesquioxane) (PFCPSQ) was synthesized by hydrolysis and condensation reaction of trimethoxysilyl monomers in the presence of a base catalyst in H2O/THF mixture solvent at 25°C. Chemical compositions, molecular weight, and structure of the obtained PFCPSQs were characterized using 1H NMR, 29Si NMR, FT-IR, and GPC. Dielectric values were examined by a HP-4190 system and a dielectric constant k of 1.92 was obtained.

Ladder-like structured polysilsesquioxane with carbazole groups showed unexpected high photo- and electroluminescence efficiencies both in solution and solid states due to its rigid silicone ladder structures, which efficiently isolated the carbazole groups and thus suppressed their excimer formations by inter- and intramolecules.

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