Online monitoring of Silicone Network Formation by Means of In‐Situ Mid‐Infrared Spectroscopy

The ReactIR™ reaction analysis system was used to monitor the crosslinking copolymerization of trimethylsilyl methacrylate with α,ω‐methacryloyl‐terminated oligo(dimethylsiloxane). Characteristic infrared bands proved useful to determine the total methacrylate concentration. After less than 12 h at 60 °C using 0.14% 2,2′‐azoisobutyronitrile (AIBN), the methacrylate conversion during the crosslinking reaction exceeded 98%. The comparison of the crosslinking reaction with a methacrylate homopolymerization showed that significant autoacceleration occurred during network formation.

Time‐dependent monomer conversion [M]/[M]₀ for TMSMA homopolymerization (run H in Table 1) and the corresponding crosslinking polymerization (run N) as revealed by the peak at 1 326 cm⁻¹.     

Block Copolymers from Organomodified Siloxane‐Containing Macroinitiators by Atom Transfer Radical Polymerization

Alternating copolymers of 1,3‐diisopropenylbenzene and 1,1,3,3‐tetramethyldisiloxane were synthesized by hydrosilylation–polyaddition. These linear copolymers were functionalized at both ends with 2‐bromoisobutyryl or benzyl chloride moieties. Subsequently, the obtained organomodified siloxane‐containing macroinitiators were successfully used for the preparation of ABA‐type block copolymers by atom transfer radical polymerization (ATRP) of styrene and tert‐butyl acrylate. The high chain‐end functionality of the macroinitiators was confirmed by ¹H NMR analysis of the macroinitiators and GPC measurements of the obtained ABA‐type block copolymers. The macroinitiator peaks disappeared in GPC traces after ATRP, and the obtained block copolymers showed a significantly narrower molecular‐weight distribution than the macroinitiators.

Synthesis of ABA‐type block copolymers by means of ATRP using organomodified siloxane‐containing, benzyl chloride functionalized macroinitiators.     

Electroactive Polymer with Oligoanilines in the Main Chain: Synthesis,Characterization and Dielectric Properties

An electroactive polymer with well‐defined oligoanilines in the main chain has been prepared by oxidative coupling polymerization. The detailed characteristics of the polymer were systematically studied by FT‐IR, ¹H NMR, GPC and XRD. Its electrochemical behavior was explored with UV‐Vis spectra and cyclic voltammetry showing that its intrinsic electroactivity was maintained and exhibited three distinct reversible oxidative states. Its electrical conductivity is about 3.91 × 10^?4 S · cm^?1 in HCl‐doped form at room temperature. Furthermore, the polymer displays a dielectric constant of 48.4 and 13.6 at 10 and 1 MHz, respectively, mainly attributed to the improvement in delocalized charge density and electrical conductivity of the polymer by introduction of the conjugated oligoaniline segments.

     

Evidence of Intramolecular Cyclization in Copolymerization of Ethylene with 1,3‐Butadiene: Thermal Properties of the Resulting Copolymers

Summary: Ethylene and butadiene were copolymerized with a silylene‐bridged bis(fluorenyl) complex {[Me₂Si(C₁₃H₈)₂]NdCl} ( 1 ) in combination with various alkylating agents (BuLi/AlH(iBu)₂, (Bu)MgCl, Mg(Bu)(Oct)). Copolymers have a unique microstructure since they contain 1,2‐cyclohexane rings and unsaturations along the polymer chain. An intramolecular mechanism was proposed for the formation of six‐membered rings. The influence of these cyclic structures on thermal properties of the copolymers has been investigated.

Proposed mechanism for formation of 1,2‐cyclohexane rings.     

Oxidative Coupling Copolymerization of 4‐Methyltriphenylamine with Arenes

A novel synthetic method for the preparation of high‐molecular‐weight conjugated polymers is presented. It consists of the oxidation copolymerization of different arenes with triphenylamine. The structure of the copolymers was characterized by ¹H and ¹³C NMR spectra. The copolymers have good solubility in common organic solvents and are thermally stable. Photoluminescence (PL) spectra (see Figure) showed that the color of emission depends on the type of arene units in the copolymer chain. Cyclic voltammetry (CV) measurements revealed electrochemical activity of the copolymers.

PL spectra of the copolymers.     

Controlled Radical Polymerization of Vaporized Vinyl Monomers on Solid Surfaces under UV Irradiation

Summary: In order to prepare well‐defined polymers on solid surfaces in the gas phase, a gas phase‐assisted surface polymerization (GASP) of vinyl monomers was carried out on solid surfaces pre‐coated with a photoiniferter, 2‐cyanoprop‐2‐yl N,N′‐dimethyldithiocarbamate, under UV irradiation. The GASP of methyl methacrylate (MMA) resulted in the formation of polymer on the surfaces and showed a proportional relationship between and polymer yield. Consecutive copolymerization of MMA and styrene led to the formation of a block copolymer, which was confirmed by a selective solvent fractionation method. These results demonstrate that controlled radical polymerization of vaporized monomer occurred on the solid surfaces.

Expected mechanism of GASP under UV irradiation.     

Formation of Thermoresponsive Gold Nanoparticle/PNIPAAm Hybrids by Surface‐Initiated,Atom Transfer Radical Polymerization in Aqueous Media

Summary: We investigated the formation of thermoresponsive gold nanoparticle/poly(N‐isopropylacrylamide) (AuNP/PNIPAAm) core/shell hybrid structures by surface‐initiated, atom transfer radical polymerization (SI‐ATRP) in aqueous media and the effect of cross‐linking on the thermoresponsiveness of the AuNP/PNIPAAm hybrids. The disulfide containing an ATRP initiator was attached onto AuNPs and the monomer, NIPAAm, was polymerized from the surface of AuNPs in the absence or presence of a cross‐linker, ethylene diacrylate, in aqueous media at room temperature. The resulting brush‐type and cross‐linked AuNP/PNIPAAm hybrids were characterized by Fourier‐transform infrared spectroscopy, transmission electron microscopy, and variable temperature dynamic light scattering.

     

Miscibility of Carboxy‐Terminated Polystyrene/Poly[2‐(N,N‐dimethylamino)ethyl methacrylate] Blends

The miscibility/immiscibility behavior of CPS/PDMAEMA binary blends were investigated by means of DSC and optical microscopy. CPS was prepared by RAFT polymerization. CPS in a molecular weight range of 5 200–14 400 g · mol^?1 was found to be miscible with PDMAEMA as shown by the existence of a single glass transition, whereas benzyl‐terminated polystyrene with a similar molecular weight was immiscible with PDMAEMA. DSC results suggested that the carboxylic acid terminal groups effectively operated as miscibility enhancers in polystyrene/PDMAEMA blends. Moreover, it was observed that this effect depended on the molecular weight of CPS and the hydrogen bonding function of solvents.

     

Block Copolymers Build‐up of Electron and Hole Transport Materials

Summary: In this article we describe the synthesis of various monomers modified with triphenyl‐1,3,5‐triazine side groups as electron transport moieties. By nitroxide‐mediated polymerization with a TEMPO unimer it was possible to obtain polymers with a narrow polydispersity. Furthermore, by living radical polymerization block copolymers were obtained from these monomers. Therefore, microphase separated structures are accessible which possess hole conducting moieties in one phase and electron conducting moieties in the other phase.

General build‐up of the copolymers consisting of hole and electron conductor.     

Back‐Biting Termination in Methyl Methacrylate/tert‐Butyl Acrylate Anionic Block Copolymerization

The product of spontaneous termination formed after addition of one or two t‐BuA units onto living PMMA chains in the MMA/t‐BuA block copolymerization was isolated and characterized by SEC, UV, FT‐IR, Raman and NMR spectroscopy. It appears as a low‐molecular‐weight peak in SEC eluograms of the copolymers, absorbing at 260 nm; its retention time corresponds to that of the PMMA block. In its FT‐IR and Raman spectra, new bands appeared corresponding to the C?C and C?O vibrations of a conjugated and H‐bonded ester group of the enol form of the cyclic oxoester composed of MMA and t‐BuA units. Experimental support of a back‐biting reaction at the link between PMMA and Pt‐BuA blocks is presented.

     

Synthesis and self‐assembly of polymers containing dicarboximide groups by living ring‐opening metathesis polymerization

Polymers with narrow molecular weight distributions and controlled architectures were generated by living ring‐opening metathesis polymerization of exo‐7‐oxabicyclo[2.2.1]hept‐5‐ene‐2,3‐dicarboximide. The dicarboximide units have been previously shown to exhibit biological activity, can selectively bind to the nucleic acid base adenine by hydrogen‐bonding, and are readily functionalizable. Block copolymers containing these moieties were generated, and underwent self‐assembly into nanoscale spherical aggregates, with surface localized molecular recognition motifs.

     

Modification of Oligomeric Cyanate Ester Polymer Properties with Multi‐Walled Carbon Nanotube‐Containing Particles

The properties of an oligomeric cyanate ester polymer were modified by the addition of 0.01–3 wt.‐% multi‐walled carbon nanotube (MWNT) containing particles. The dynamic mechanical behavior and thermal properties of the cyanate ester/MWNT nanocomposites were evaluated. The storage modulus, G′, of the nanocomposite with 1 wt.‐% MWNT particles was nearly 60 and 600% higher than the neat polymer at 100 and 200 °C, respectively. The glass transition temperature of the nanocomposite was also raised by 30 °C and its thermal stability in air and nitrogen was increased by 58 and 25 °C, respectively. The property improvements are attributed to reinforcement of the cyanate ester as a result of good nanotube dispersion and effective polymer‐MWNT interaction.

     

A Facile One‐Pot Synthesis to Dextran‐Based Nanoparticles with Carboxy Functional Groups

Summary: Stabilized nanoparticles functionalized with carboxy groups were synthesized directly from dextran and acrylic acid (AA), without using any organic solvent and surfactant. The composition and morphology of these dextran‐based nanoparticles, as well as the mechanism of this one‐pot synthesis, were also investigated in this paper. This approach is anticipated to be applicable to various water‐soluble polysaccharides to fabricate nanoparticles facilely.

Facile synthesis of stabilized nanoparticles functionalized with carboxy groups from dextran and AA.     

Branched and Functionalized Polybutadienes by a Facile Two‐Step Synthesis

Anionic polymerization was used to prepare silane‐endfunctionalized polybutadiene macromonomers with different molecular weights ranging from 9 000 to 34 000 g · mol^?1. These were polymerized by a hydrosilylation reaction in bulk to obtain branched polymers, using Karstedt's catalyst. Surprisingly, the addition of monofunctional silanes during the polymerization showed only a minimal effect concerning the degree of polymerization. Furthermore, it was possible to introduce a variety of functional silanes without increasing the overall number of reaction steps by a convenient AB₂ + A type “pseudocopolymerization” method. All branched polymers were analyzed by SEC, SEC‐MALLS, SEC‐viscosimetry. ¹H NMR spectroscopy, and DSC concerning their branching ratio. The branching parameters for the branched polymers exhibited similar characteristics as for hyperbranched polymers obtained from conventional AB₂ monomers. Detailed kinetic studies showed that the polymerization occurred very rapidly in comparison to the hydrosilylation polymerization of classical AB₂ type carbosilane monomers.

     

Radical Polymerization of MMA Co‐initiated by 2‐Phenyloxazoline

The subject of this work is the study of a new type of radical polymerization that occurs at elevated temperatures (80–100 °C) in mixtures of acrylates or (meth)acrylates and imine baes (IBA polymerization). The radical character of this polymerization is proven by the determination of copolymerization ratios and the reaction kinetics. On the basis of these facts and the hypothesis that the vinyl monomer acts as a co‐initiator, calculations reveal the concentration of the initiating species to be very low (K_eq < 10^?6). Furthermore, the choice of the reaction medium plays a crucial role on reaction kinetics and the average molecular weight of the resulting polymer. In combination with computational methodologies on the initiation, the multistep nature of this reaction is indicated.

     

Catalytic Chain Transfer Copolymerization of Methyl Methacrylate and Butyl Acrylate

In this work it is shown that catalytic chain transfer is a very efficient way of controlling molecular weight in the copolymerization of methyl methacrylate (MMA) and butyl acrylate (BA). The experimental data are compared to a previously developed model based on copolymerization kinetics and the mechanisms for catalytic chain transfer and for cobalt‐mediated living radical polymerization that can describe the observed transfer constants. Secondly, it is shown that the presence of a catalytic chain transfer agent does not affect the reactivity ratios within the concentration range studied. Finally, the effect of conversion and therewith composition drift on the catalytic chain transfer polymerization of MMA and BA is investigated and it is shown that under the conditions employed in the experiments a certain degree of macromer copolymerization is present at high partial conversions of MMA.

Evolution of MWD with conversion for the CCT copolymerization of MMA and BA in toluene at 60 °C, [AIBN] = 6 × 10^?3 mol · L^?1.     

Synthesis and Electroluminescent Properties of Disubstituted Polyacetylene Derivatives Containing Multi‐Fluorophenyl and Cyclohexylphenyl Side Groups

A new series of disubstituted polyacetylene derivatives that contain multi‐fluorine atoms on the pendent phenyl ring have been synthesized and characterized. The results reveal a greater red‐shift in UV‐vis absorption and PL emission upon incorporating more fluorine atoms on the pendent phenyl ring. Among them, disubstituted polyacetylene with a difluorophenyl group ( PDPA‐2F ) showed the highest luminescent efficiency. The device performance can be promoted by blending a hole‐transporting material TM‐TPD into PDPA‐2F as the active layer or by using a light‐emitting copolymer in which PDPA‐2F was copolymerized with a carbazole group ( PDPA‐2Fcab ). A light‐emitting diode of ITO/PEDOT/ PDPA‐2Fcab /Ca/Al revealed a maximum luminescence of 4230 cd · m^?2 at 14 V and a maximum current efficiency of 3.37 cd · A^?1 at 7 V.

     

Nitroxide‐Mediated Radical Polymerization of N‐tert‐Butylacrylamide

The nitroxide‐mediated polymerization of N‐tert‐butylacrylamide (TBAM) in DMF at 120 °C using SG1/DEPN and AIBN has been investigated. Linear growth in number‐average molecular weight ( ) versus conversion and narrow molecular weight distributions (MWDs) with high livingness were obtained up to ≈8 000 g · mol^?1. For higher molecular weights, the MWDs gradually became broader with low molecular weight tailing, and deviated downwards from theoretical values. Quantitative analyses of MWDs, along with specifically designed conventional radical polymerizations at 120 °C, were consistent with chain transfer to monomer limiting the attainable . This finding can be equally applied to existing literature polymerizations of TBAM.

     

Semicontinuous Emulsion Polymerization of Butyl Methacrylate and 1, 3‐Butadiene in the Presence of Cyclodextrins and Cytocompatibility of Dicarboxylic Acid Telechelic Oligo(butyl Methacrylate)s Derived from Ozonolysis of the Latexes

Ozonolysis of unsaturated polymers produced useful telechelic oligomers that can form building blocks for networks and block copolymers. The unsaturated polymers can be prepared by semicontinuous emulsion polymerization with dienes, and here it is shown that the addition of cyclodextrins enhanced the incorporation of these comonomers. Both α‐ and β‐cyclodextrin provide copolymers with higher fractions of butadiene (BD) incorporated into the chain but α‐cyclodextrin had the highest levels of incorporation. Oxidative work up after ozonolysis produced latexes of carboxylic acid oligomers of different molar masses. A clear effect of polymer size on toxicity was observed with the oligomers with < 2 700 g · mol.^?1 proving to have similar cytotoxic effects to lactic acid. However, oligomers with above 2 700 g · mol.^?1 were cytocompatible and gave similar results to a polylactide control material.

     

Nickel‐Mediated Surface Grafting From Polymerization of α‐Amino Acid‐N‐Carboxyanhydrides

Summary: The feasibility of a living grafting from polymerization of α‐amino acid‐N‐carboxyanhydrides (NCA) from a surface using nickel initiators was shown. The polymerization has been carried out on commercially available polystyrene resins as spherical substrates in two different ways. Firstly L ‐glutamic acid was bound to the surface as γ‐ester via a UV‐labile linker and transferred into the NCA by treatment with triphosgene. The grafting from polymerization was then carried out as a “block copolymerization” by reaction of the surface bound NCA with an excess of the Ni amido‐amidate complex initiator and subsequent addition of free NCA to grow the polymer chain. By this procedure polymer was formed at the surface and can be isolated after photolysis of the linker. The characterization of the polymer by size exclusion chromatography indicates a living polymerization at the surface. The second approach employs N‐alloc‐amides at the surface to prepare an initiating Ni amido‐amidate complex directly at the surface. It can be shown that the latter approach is much more straightforward and gives smaller quantities of non‐tethered polypeptide.

Surface bound polypeptides were obtained by ring opening polymerization of α‐amino acid‐N‐carboxyanhydrides initiated by nickel amido‐amidate complexes installed at surfaces of commercially available polystyrene resins.