Dendronized Polymers: Recent Progress in Synthesis

This article divides the synthetic routes leading to dendronized polymers into two main categories (attach‐to and macromonomer) and compares their respective advantages and disadvantages. It gives a comprehensive overview on the kind of structures presently available and also spans the bridge between both polymers and molecular objects, decorated with only a few dendrons, and the structurally related, but less well defined polymers with hyperbranched side chains.

A coiled polymer backbone's stretching through the attachment of increasingly sterically demanding dendrons: a) no dendrons; b) dendrons of the first generation; c) second generation; d) third generation.     

A New Family of High‐Performance Ti Catalysts for Olefin Polymerization

The syntheses, structures and olefin polymerization behavior of Ti complexes containing a pair of chelating aminotropone [O? N] ligands are reported. DFT studies revealed that bis(aminotropone) Ti complexes, when activated, provide a metal alkyl in the cis position to a vacant coordination site for monomer binding, suggesting great potential for the polymerization of olefinic monomers. Unlike Ti‐FI catalysts, bis(aminotropone) Ti complexes do not require the presence of steric bulk in close proximity to the anionic donor. Bis(aminotropone) Ti complexes combined with MAO display high ethylene polymerization activities (max. 27 200 kg polymer per mol catalyst and hour) comparable to those obtained with early group‐four metallocene catalysts under identical conditions.

     

Microwave‐Assisted Synthesis of Poly(L‐lactic acid) via Direct Melt Polycondensation Using Solid Super‐Acids

A microwave‐assisted method of synthesizing high‐molecular‐weight PLA using SSA as green catalyst was developed. Yellowish PLA with above 2.0 × 10⁴ g · mol^?1 was obtained when the reaction was run at 260 °C within 60 min under microwave irradiation with 0.4 wt.‐% SSA. This method used only 10% of the energy consumption necessary for conventional heating, and the catalyst could be used five times without losing catalytic activity. The improvement in and the decrease in the energy consumption under microwave irradiation suggested that selective heating and hot spots effects played a crucial role. The method was shown to be a time‐saving, green and a promising way to lower the cost and spread the application of PLA.

     

Chain‐End and Chain‐Internal Crosslinking in “Latent Reactive” Silicon Elastomers

Summary: Latent reactivity has been employed to create processable elastomers constructed of carbosilane and either carbosiloxane or polyether segments. Two types of latent modes have been introduced: “chain‐internal” and “chain‐end” sites through the use of labile silicon methoxy and trifunctional olefinic functionalities. These latent reactive sites remain inert during formation of the linear copolymer; subsequent exposure to moisture triggers hydrolysis of the methoxy group and formation of a chemically crosslinked thermoset. These “chain‐end” sites limit the formation of dangling chains improving the overall mechanical properties of the material. The thermoset's mechanical response can be potentially varied from plastic to elastic behavior, depending on the ratio of hard and soft monomers employed. The concentration of “chain‐internal” and “chain‐end” crosslink sites enhances strength; modification to the run length and structure of the soft phase enhances elasticity, generating samples having moduli of 6 MPa, tensile strengths of 0.6 MPa and elongations of 400%.

“Latent reactive” silicon elastomer.     

Control of Polyaniline Particle Shapes

Needle‐like poly(aniline p‐toluenesulfonic acid) complex aggregates were synthesized by oxidative polymerization, yielding conductivities of up to 3 S · cm^?1 and maximum aspect ratios of 26. Rod‐like aggregates as precursors to be developed into needle‐like aggregates were obtained with 1 to 2 h APS addition time at 15 °C. Flake‐like polyanilines were prepared at ?2 or +20 °C with 1.9 to 2.5 h of APS addition time, giving aspect ratios of 2 to 10. Plate‐like polyaniline aggregates emerged when xylene was added, and an optimum xylene concentration was 15 vol.‐%, giving 1.3 S · cm^?1 conductivity. The polyanilines were characterized by optical microscopy, SEM and UV‐vis/NIR spectroscopy.

     

Formation Mechanism of Polyaniline Nanotubes by a Simplified Template‐Free Method

PANI nanotubes with diameters of 100–150 nm with conductivities of single nanotubes as high as 30.6 S · cm^?1 were directly oxidized with APS in the absence of hard templates and acidic dopants. The high conductivity was shown to result from protons produced during the polymerization. The pH decreases with increasing polymerization time, and the morphology changes from hollow spheres to short and long tubes. It is proposed that the micelles formed by the aniline monomer in aqueous solution serve as a soft template for forming hollow spheres at the initial stage. As the polymerization proceeds, these hollow spheres are linearly aggregated and elongated to form short and long tubes.

     

Synthesis of Laser‐Alignable Liquid Crystalline Conducting Polymers

Summary: The synthetic routes to three series of liquid crystal conducting polymers (based on pyrrole, thiophene, and aniline monomers) are reported and the optimum conditions for polymer preparation are described. These polymers show increased conductivity when laser‐aligned, the greatest effect being shown by the N‐substituted pyrrole‐based system. Information on their liquid crystal and spectroscopic properties and other characteristics are also included.

Structure of the monomers M1, M2, and M3.     

Metathetic Selective Degradation of Polyisoprene: Low‐Molecular‐Weight Telechelic Oligomer Obtained from Both Synthetic and Natural Rubber

Summary: Degradation studies of cis‐1,4‐polyisoprene were carried out using first and second generation Grubbs catalysts to achieve end‐functionalized acetoxy oligomers in both an organic solvent and a latex phase at room temperature. Well‐defined acetoxy telechelic polyisoprene structures were obtained in a selective manner with a range of from 10 000 to 30 000, with a polydispersity index of around 2.5.

Structure produced by the metathetic depolymerization of hydroxy telechelic cis‐1,4‐polyisoprene.     

Cylindrical Polypeptide Brushes

Summary: Cylindrical brushes with poly(L ‐lysine) and poly(L ‐glutamate) side chains were prepared by “grafting through” and “grafting from” techniques. Grafting from is shown to be more successful for the synthesis of cylindrical brushes with high molar mass main and side chains.

AFM height image of polypeptide brushes with protected polylysine side chains spin‐cast from HFIP solution.     

Effects of the Reaction Conditions on the Syndiospecific Polymerization of Propene Promoted by Bis(phenoxyimine) Titanium Catalysts

Summary: The propene polymerization behavior of two typical bis(phenoxyimine) titanium catalysts has been investigated by varying reaction conditions, such as the monomer concentration, the solvent, and the cocatalyst. The experimental results indicate that the stereoregularity and regioregularity of the obtained poly(propylene)s are significantly affected by the reaction conditions. Fractionation of some poly(propylene) samples indicates the formation of macromolecules of different stereoregularity in the same run, suggesting that different active complexes can be generated in situ from these bis(phenoxyimine) titanium precatalysts.

     

Photodeformable Polymers: A New Kind of Promising Smart Material for Micro‐ and Nano‐Applications

Summary: Starting in the 1960s, several kinds of photodeformable polymers have been developed, such as monolayers, polymer gels, solid films and liquid‐crystalline elastomers with different photodeformation mechanisms. This field evolved slowly until recently when significant achievements have been made. Most recently, Lendlein and co‐workers have put forward another new concept – using photo‐crosslinking to prepare deformable polymers with various pre‐determined shapes (Nature 2005 , 434, 879). This highlight gives a general introduction into photodeformable polymers and brings forth future challenges.

A polymer film doped with SCAA molecules where (a) is the permanent shape, (b) is the temporary shape and (c) is the recovered shape.     

Nanoscale Analysis of Polymer Interfaces by Energy‐Filtering Transmission Electron Microscopy

Summary: Energy‐filtering transmission electron microscopy (EFTEM) was employed for the analysis of polymer‐polymer interfaces. To attain imaging and spectral analyses with a spatial resolution of 10 nm, problems arising in the EFTEM analysis for polymer specimens were investigated. Interfaces in poly(methyl methacrylate)/polystyrene‐co‐polyacrylonitrile random copolymer (PMMA/SAN) bilayer films annealed at different temperatures were analyzed by means of elemental mapping and Image‐EELS on EFTEM and the effect of the annealing temperature on the interfacial structures was also investigated.

     

3D Hollow Microspheres Assembled from 1D Polyaniline Nanowires through a Cooperation Reaction

Novel 3D hollow spheres (diameter ≈525 nm, thickness ≈70 nm) self‐assembled from 1D PANI nanofibers (diameter ≈17 nm) with conductivity of 1.11 × 10⁻¹ S · cm⁻¹ are synthesized template‐free by using FeCl₃ and salicylic acid as the oxidant and dopant, respectively. In this method, the reaction of aniline with FeCl₃ and SA to form conductive PANI and the reaction of SA with FeCl₃ to produce a color complex, assigned as Fe(OR)²⁺, wherein OR represents the ionized phenol, coexist. The coexistence of two reactions results in a cooperative effect of the micelle, where aniline/SA acts as as a soft template of the nanofibers and the color complex as a soft‐template of the spheres, to allow the self‐assembly of complex micro/nanostructures via hydrogen bonding as the driving force.

     

Synthesis of Novel Monomers and Copolymers from 1‐Vinylpyrrolidin‐2‐one: Attractive Materials for Drug Delivery Systems?

Summary: Polyvinylpyrrolidone (PVP) is a synthetic, non‐toxic, water‐soluble polymer commonly used in a wide range of applications including several pharmaceutical applications. One example of an important application is the controlled release and delivery of therapeutic agents into sites of inflammation or tumours. However, PVP lacks reactive groups, which limits the possibility of adding new functions to the polymer in order to modify its physical and chemical properties. Furthermore, large differences in radical reactivity between 1‐vinylpyrrolidin‐2‐one (NVP) and most other monomers lead to compositional drift during copolymerization. This complicates the introduction of reactive groups into the polymer using this method. Monomers that are derivatives of NVP itself are expected to show smaller differences in radical reactivity and therefore provide a way of preparing PVP with adjustable properties. Here we present the synthesis of five NVP‐based monomers and their use in the preparation of functional PVP with adjustable properties in terms of solubility, loading of functional groups, and molar mass. The results show the possibility of tailoring PVP for different biomedical applications e.g. drug delivery systems.

Copolymers from 1‐vinylpyrrolidin‐2‐one.     

Quantitative Analysis of Dielectric Constants from EFM Images of Multicomponent Polymer Blends

Summary: A simple quantitative model for the analysis of EFM images of three‐ or more‐component polymer blends is applied to determine the dielectric constants of the blend constituents. The value of the dielectric constant of PIPA calculated from the EFM images of POMA‐PIPA‐APP blend is determined in good agreement with the literature value.

     

Linear Terpyridine‐Ruthenium(II) Poly(ethylene glycol) Coordination Polymers

In the present contribution, we synthesized linear coordination polymers based on oligo(ethylene glycol)s as well as poly(ethylene glycol)s and terpyridine ruthenium(II) complexes. The reaction conditions, e.g., solvent, concentration, were varied to obtain well‐soluble, high molecular weight polymers. The resulting compounds were characterized by UV‐vis and NMR spectroscopy. The viscosity of the materials was also investigated with and without salt addition. Finally, the polymers were characterized with DSC and AFM. AFM revealed a lamellar morphology.

     

Morphology and Phase Characteristics of High‐Density Polyethylene Probed by NMR Spin Diffusion and Second Moment Analysis

Summary: A dipolar filter pulse sequence combined with cross‐polarization‐MAS is applied to characterize the phase distribution, morphology, and spin diffusion within a high‐density polyethylene sample. A new method to obtain quantitative ¹³C NMR by combining cross‐polarization‐MAS and spin diffusion NMR is presented. The derived crystallinity is consistent with the corresponding crystallinity obtained by ¹H NMR.

Illustration of the pulse sequence(s) applied in the present work.     

Synthesis and Photovoltaic Properties of Conjugated Copolymers with Benzo[1,2‐b:4,5‐b′]dithiophene and Bis(thiophene)phthalimide Units

Two new donor/acceptor copolymers PBDTPhBT1 and PBDTPhBT2 with alternating benzodithiophene ( BDT ) and bisthiophene‐phthalimide ( PhBT ) units were synthesized by Stille coupling reaction. The copolymers showed identical optical bandgaps of 1.98 eV. The HOMO energy levels are ?5.35 and ?5.32 eV for PBDTPhBT1 and PBDTPhBT2 , respectively. The bulk heterojunction solar cell devices based on these copolymers as donors and PC₇₁BM as acceptor displayed high open‐circuit voltages of 0.90–0.93 V and achieved power conversion efficiency of 1.54% under the illumination of AM 1.5, 100 mW · cm^?2.

     

Shape‐Memory Natural Rubber: An Exceptional Material for Strain and Energy Storage

Shape‐memory polymers (SMPs) are smart, responsive materials with numerous potential applications. Based on previously introduced shape‐memory natural rubber (SMNR), which shows exceptional properties such as strain storage of 1000%, cold storage, cold programmability, and mechanical and thermal triggers tunable both during and after programming, different SMNRs regarding their shape‐memory parameters are investigated. Furthermore, their energy‐storage capability and their mechanical properties are explored. SMNRs show fixity ratios of up to 94% and excellent recovery ratios of up to 100% whereas strains even above 1000% can be stored. Energies of up to 4.88 J g^?1 can be stored with efficiencies of up to 53.30%. Further, the Young's modulus of SMNR can be switched by two orders of magnitude upon triggering or programming.