Synthesis of Functional Inorganic−Organic Hybrid Polymers Based on Poly(silsesquioxanes) and Their Thin Film Properties

New stable and adherent coating materials have been synthesized on the basis of inorganic/organic hybrid polymers. As the inorganic part, different poly(silsesquioxanes) (PSSQ) have been functionalized to act as polymeric chain transfer agents (CTAs) for a reversible addition fragmentation chain transfer polymerization, thereby determining the starting point of a controlled radical polymerization of vinyl-type monomers. Using two different CTAs acrylates, we have successfully polymerized methacrylates and styrene under RAFT polymerization conditions. Different monomers were copolymerized in such an organic block to incorporate multiple functionalities. The variation of the block ratios and …

Substrate-Independent Stable and Adherent Reactive Surface Coatings and their Conversion with Amines

To create stable, adherent and reactive surface coatings, a hybrid polymer composed of poly(methylsilsesquioxane) (PMSSQ) and poly(pentafluorophenyl acrylate) PFPA with a M n of 32000 g/mol was prepared by a RAFT polymerization procedure. These hybrid polymer has been used for coating experiments. The PFPA part enabled a variable functionalization of the coating afterwards. The stability on various substrates (e.g. glass, PMMA, steel) was tested in an ISO tape test. These reactive surface coatings were modified using different amines, such as amino-terminated PEG, dodecyl amine and N-isopropyl amine. The conversion was analyzed by FT-IR and contact angle measurements.

Reactive Coatings in Glass Capillaries: Preparation of Temperature- and Light-Responsive Surfaces and Accurate Determination of Wettability Switching

Reactive surface coatings based on polysilsesquioxanes: defined adjustment of surface wettability.

We have investigated a generally applicable protocol for a substrate-independent reactive polymer coating that offers interesting possibilities for further molecular tailoring via simple wet chemical derivatization reactions. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylate) hybrid polymers have been synthesized by RAFT polymerization, and stable reactive surface coatings have been prepared by spin-coating on the following substrates: Si, glass, gold, PMMA, PDMS, and steel. These coatings have been used for a defined adjustment of surface wettability by surface-analogous reaction with various amines (e.g., glutamic acid to obtain hydrophilic surfaces (Theta(a) = 18 degrees) or per…

Surface coatings based on polysilsesquioxanes: Grafting-from approach starting from organic polymers

AbstractPoly(methylsilsesquioxane) (PMSSQ) based hybrid materials are promising candidates to produce substrate-independent stable and adherent surface coatings. Usually these materials are synthesized by controlled radical polymerization from inorganic precursors. The presented synthetic pathway in here demonstrates how to graft PMSSQ networks from an endgroup-functionalized organic polymer and thus enlarges the range of accessible inorganic/organic hybrid coating materials.

Surface Coatings Based on Polysilsesquioxanes: Solution-Processible Smooth Hole-Injection Layers for Optoelectronic Applications

Optoelectronic devices usually consist of a transparent conductive oxide (TCO) as one electrode. Interfacial engineering between the TCO electrode and the overlying organic layers is an important method for tuning device performance. We introduce poly(methylsilsesquioxane)-poly(N,N-di-4-methylphenylamino styrene) (PMSSQ-PTPA) as a potential hole-injection layer forming material. Spin-coating and thermally induced crosslinking resulted in an effective planarization of the anode interface. HOMO level (-5.6 eV) and hole mobility (1 × 10(-6)  cm(2)  · Vs(-1) ) of the film on ITO substrates were measured by cyclovoltammetry and time-of-flight measurement demonstrating the hole injection capabili…

Temperature-Responsive Surface Coatings Based on Poly(methylsilsesquioxane)-hybrid Polymers

The present paper presents a new method to build up temperature-responsive surfaces. First a poly(silsesquioxane)-block-poly(N-isopropyl-acrylamide) (PMSSQ-b-PNIPAM) was successfully synthesized using RAFT polymerization. Spin-coating or dip-coating of PMSSQ-b-PNIPAM onto glass surfaces resulted in temperature-responsive surfaces. Surface ATR FT-IR measurements proofed the successful surface modification using PMSSQ-b-PNIPAM. IR fine structures of PNIPAM and PMSSQ could be assigned, respectively. In capillary rise experiments a change of the meniscus height measured at temperatures below or above LCST was observed, indicating a different wetting behavior. Thus, a simple spin- or dip-coating…

Questions and controversies in the study of time-varying functional connectivity in resting fMRI.

The brain is a complex, multiscale dynamical system composed of many interacting regions. Knowledge of the spatiotemporal organization of these interactions is critical for establishing a solid understanding of the brain’s functional architecture and the relationship between neural dynamics and cognition in health and disease. The possibility of studying these dynamics through careful analysis of neuroimaging data has catalyzed substantial interest in methods that estimate time-resolved fluctuations in functional connectivity (often referred to as “dynamic” or time-varying functional connectivity; TVFC). At the same time, debates have emerged regarding the application of TVFC analyses to re…

Macromol. Chem. Phys. 10/2009

Synthesis of Processable Inorganic‐Organic Hybrid Polymers Based on Poly(silsesquioxanes): Grafting from Polymerization Using ATRP

Inorganic-organic hybrid polymers have been synthesized utilizing atom transfer radical polymerization (ATRP) from a functionalized poly(methylsilsesquioxane) (PMSSQ) macroinitiator. Different polymeric ATRP initiators were prepared by co-condensation of functionalized trichlorosilanes with methyltrimethoxysilane. Various vinyl monomers have been successfully grafted from these macroinitiators, demonstrating a highly variable synthetic concept, which offers the chance to synthesize a wide spectrum of inorganic-organic hybrid polymers. All synthesized polymers were soluble in various organic solvents. Spin-coating these hybrid materials onto various substrates could produce stable and adhere…

A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis

Macromolecules is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Communication to the Editor A Method for Obtaining Defined End Groups of Polymethacrylates Prepared by the RAFT Process during Aminolysis Peter J. Roth, Daniel Kessler, Rudolf Zentel, and Patrick Theato Macromolecules, 2008, 41 (22), 8316-8319 • Publication Date (Web): 01 November 2008 Downloaded from http://pubs.acs.org on November 19, 2008

Versatile Responsive Surfaces via Hybrid Polymers Containing Acetal Side Groups

Two hybrid polymers, poly(methylsilsesquioxane)-poly(2,2-diethoxyethyl acrylate) and poly-(methylsilsesquioxane)-poly(1,3-dioxolan-2-ylmethyl acrylate), were synthesized and used for preparation of stable surface coatings. Their acetal side groups could be functionalized via solution-dipping with different primary amines and hydroxylamines after acidic deprotection and thus allowed for flexible modification of the surface hydrophilicity. Functionalization with a thermo-responsive polymer resulted in a thermo-responsive surface with temperature-dependent contact angles. Further, the two types of acetals showed different stability toward acidic treatment and could be addressed independently.

Reactive Surface Coatings Based on Polysilsesquioxanes: Controlled Functionalization for Specific Protein Immobilization

The key designing in reliable biosensors is the preparation of thin films in which biomolecular functions may be immobilized and addressed in a controlled and reproducible manner. This requires the controlled preparation of specific binding sites on planar surfaces. Poly(methylsilsesquioxane)-poly(pentafluorophenyl acrylates) (PMSSQ-PFPA) are promising materials to produce stable and adherent thin reactive coatings on various substrates. Those reactive surface coatings could be applied onto various materials, for example, gold, polycarbonate (PC), poly(tetrafluoroethylene) (PTFE), and glass. By dipping those substrates in a solution of a desired amine, specific binding sites for protein ads…

Modular approach towards multi-functional surfaces with adjustable and dual-responsive wettability using a hybrid polymer toolbox

Poly(methylsilsesquioxane)-based hybrid polymers carrying orthogonally reactive moieties demonstrate an effective modular approach to creating multi-reactive surface coatings. By a sequential surface-analogous reaction different functions could be immobilized in a defined ratio, resulting in dual- or triple-functionalized surfaces.

Double Thermoresponsive Block Copolymers Featuring a Biotin End Group

A poly(oligo(ethylene glycol) monomethyl ether methacrylate)-block-poly(N-isopropyl methacrylamide) (POEGMA-b-PNIPMAM) block copolymer with a biotin end group on the PNIPMAM block as a biotarget was synthesized as a model system for temperature-controlled polymer immobilization. The synthesis was based on RAFT polymerization followed by postpolymerization modification of an activated ester precursor block and an exchange of the dithioester end group within one step. NMR, differential scanning calorimetry (DSC), dynamic light scattering (DLS), and turbidimetry measurements were performed to investigate the stimulus-responsive properties. The double thermoresponsive POEGMA-b-PNIPMAM with biot…

Functional templates for hybrid materials with orthogonal functionality.

We demonstrate an integrated approach to prepare a nanostructured, multifunctional material with mutually exclusive, orthogonal properties. The hybrid material was obtained within a single step via self-assembly in solution. It consists of TiO(2) as a functional metal oxide and an amphiphilic block copolymer, poly(ethylene oxide)-b-poly(triphenylamine) (PEO-PTPA). Within the materials' synthesis, the block copolymer not only acts as a templating agent but also adds an electronic functionality to the resulting hybrid material. During the synthesis, a variety of self-assembled morphologies, ranging from spheres to wires, can be created. The obtained morphology depends on the weight fraction o…

Versatile ω-end group functionalization of RAFT polymers using functional methane thiosulfonates

Five different polymers, poly[methyl methacrylate] (PMMA), poly[lauryl methacrylate] (PLMA), poly[diethylene glycol methacrylate] (PDEGMA), poly[N-iso-propylacrylamide] (PNIPA), and poly[styrene] (PS) prepared by the RAFT process and thus terminated with dithioesters were aminolyzed in the presence of S-3-butynyl methane thiosulfonate (MTS), which was synthesized in two steps. Analysis of the polymers by 2D NMR, UV–vis absorbance, and gel permeation chromatogra-phy revealed them to quantitatively carry acetylene end groups connected with disul-fide bridges, indicating that functional MTS reagents can be employed for end group functionalization of RAFT polymers. This versatile method is of ad…

Reactive surface coatings based on polysilsesquioxanes: universal method toward light-responsive surfaces.

Reactive surface coatings were used as an ideal precursor coating for the fabrication of three different photoswitchable surface coatings in parallel. Different light-responsive moieties, such as azobenzene, salicylideneaniline, and spiropyran, were immobilized on glass, polycarbonate, and steel surfaces. Independent from the underlying substrate, wettability could be switched reversibly by UV irradiation. The maximum switching range was obtained after functionalization of the reactive coating with spiropyran, resulting in a contact angle difference between the two isomeric states of almost 30°.

Comparison of Hybrid Blends for Solar Cell Application

In blended hybrid systems distinct micro- or nanostructured materials can be formed by phase separation. Network structures of particles or rods in a polymer matrix can be developed via self-assembly. We use this blending approach to compare active materials for application in solar cell devices. Blends were fabricated from either poly(hexylthiophene) P3HT or poly(triphenylamine) PTPA mixed with nanocrystalline TiO 2 rods. In this manner, we compare two different hole conducting polymers in their performance in photovoltaic devices, while experimental conditions are kept identical. We find that the choice of solvent and photovoltaic characterization conducted in inert atmosphere is of impor…

Macromol. Chem. Phys. 14/2008

Synthesis of Defined Poly(silsesquioxane)s: Fast Polycondensation of Trialkoxysilanes in a Continuous-Flow Microreactor

The polycondensation of trialkoxysilanes to PSSQs in a microreactor setup is demonstrated. While continuous-flow processes involving microreactors found various applications in chain growth polymerization, their influence on step-growth polymerization is less explored, and the polycondensation of multifunctional monomers has not been studied in detail. We found significantly increased yields and a decreased polydispersity of the obtained polymers in comparison to the batch process. By variation of the residence time molecular weights could be adjusted reproducibly ranging from M n =1900 to 11000 g · mol -1 . Thus, the microreactor setup offers for the first time the possibility to synthesiz…