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.     

Preparation of Core–Shell‐Type Poly(ethylene glycol)‐Grafted Polystyrene Resins and Their Characteristics in Solid‐Phase Peptide Synthesis

By suspension polymerization using styrene, divinylbenzene, and synthetic poly(ethylene glycol) (PEG) macromonomers, we have prepared core–shell‐type resins that have a highly crosslinked polystyrene core and a PEG shell. The PEG macromonomer, which has a vinyl group and an amino group at each terminal, plays a role as a stabilizer in the suspension polymerization system. All the resins were of the bead type with a diameter of 38–150 μm. The loading capacities of the amino groups were 0.1–0.2 mmol · (g resin)⁻¹ and the thickness of the PEG shell 2–4 μm, which was verified by cross‐sectioned views of the fluorescamine‐coupled beads. During coupling of amino acids in solid‐phase peptide synthesis, the resin showed better yields than TentaGel resin, especially during the first coupling step. In the enzymatic cleavage reaction, the resin‐bound peptides were shaved about 5–10 times more than TentaGel resin.

SEM micrograph of CutiCore resin (×200).     

Characterization of Carbon Monoxide Centered Triads in Poly[ethylene‐co‐(butyl acrylate)‐co‐(13C‐carbon monoxide)] by Isotopic Labeling and Two‐Dimensional NMR

Summary: Poly[ethylene‐co‐(butyl acrylate)‐co‐(carbon monoxide)] (polyEBC) samples, prepared from ¹³C‐labeled carbon monoxide, were characterized using two dimensional (2D) pulsed field gradient (PFG) 750 MHz NMR spectroscopy. To elucidate the complex mixture of structures present in this terpolymer, 2D ¹H/¹³C‐heteronuclear multiple bond correlation (HMBC) experiments were conducted by selectively exciting the enhanced peaks resulting from ¹³C‐labeling. High resolution 2D NMR combined with ¹³C‐labeling of the polymer greatly simplifies the 2D NMR spectra, selectively enhances the weak peaks from low occurrence C‐centered triad structures and aids in their resonance assignments.

     

Synthesis of Ethylene/Acrylonitrile Composite Elastomers with Nanosized Polyacrylonitrile Domains Using α‐Dimine‐[N,N] Nickel Dichloride/EASC

A series of ethylene and acrylonitrile composite elastomers were prepared using (1,4‐bis(2,6diisopropylphenyl)‐acenaphtenediimine‐nickel(II))‐dichloride/ethylaluminum sesquichloride (EASC). The xylene‐soluble polymer fraction showed nitrile bands in infrared spectroscopy at 2 245 and 2 214 cm^?1 and polyacrylonitrile‐enriched structures were detected in the xylene‐insoluble fraction by¹H and ¹³C NMR. In addition, TEM detected nanosized polyacrylonitrile domains dispersed in the polyethylene matrix. Differential scanning calorimetry scans conducted from ?70 to 350 °C measured exothermic bands corresponding to the cyclization and aromatization of the nitrile groups dispersed in the polyethylene matrix.

     

Synthesis and Photovoltaic Properties of a Poly(2,7‐carbazole) Derivative Based on Dithienosilole and Benzothiadiazole

A low bandgap poly(2,7‐carbazole) derivative PCDSBT containing dithienosilole and benzothiadiazole is synthesized by Stille polymerization. The incorporation of dithienosilole and carbazole causes PCDSBT to have a broad absorption from 350 to 800 nm and a relatively low HOMO level. Solar cell devices fabricated by blending PCDSBT with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) at a 1:2 weight ratio in a mixed solvent of 3% (by volume), 1,8‐diiodooctane, and 97% dichlorobenzene lead to a power conversion efficiency of 1.65% under the illumination of AM 1.5G (100 mW · cm^?2).

     

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.

     

An Easy Strategy for the Synthesis of Well‐Defined Aliphatic‐Aromatic Hyperbranched Polyesters

A one‐pot solution polymerization under mild conditions was adapted for the synthesis of well‐defined aliphatic‐aromatic polyesters with different degrees of branching. The esterification was performed at room temperature using 4,4‐bis(4′‐hydroxyphenyl)valeric acid (AB₂) and 3‐(4‐hydroxyphenyl)propionic acid (AB) as monomers. DPTS was used as a catalyst and DCC as a coupling agent. Polyesters with statistical, dendritic topology, controlled degree of branching and > 35 000 g · mol^?1 were obtained. The polymers were characterized by ¹H and ¹³C NMR, SEC, DSC, and TGA. A strong dependence of the degree of branching and the thermal properties of the polymers depending on the AB/AB₂ monomer ratio was observed.

     

Synthesis of Di‐block Copolymers Containing Regioregular Poly(3‐hexylthiophene) and Poly(tetrahydrofuran) by a Combination of Grignard Metathesis and Cationic Polymerizations

Poly(3‐hexylthiophene)‐block‐poly(tetrahydrofuran) was synthesized by cationic ring‐opening polymerization of tetrahydrofuran (THF) using a poly(3‐hexylthiophene) macroinitiator. Poly(3‐hexylthiophene) macroinitiator used for the ring‐opening polymerization of THF was synthesized by reacting the hydroxypropyl end‐group with trifluoromethanesulfonic anhydride in the presence of 2,6‐di‐tert‐butylpyridine. ¹H NMR spectroscopy and SEC data confirmed the formation of the di‐block copolymers. Field‐effect mobility of poly(3‐hexylthiophene)‐block‐poly(tetrahydrofuran) was measured in a thin‐film transistor configuration and was found to be 0.009 cm² · V^?1 · s^?1.

     

Polyrotaxanes of Pyrene–Triazole Conjugated Azomethine and α‐Cyclodextrin with High Fluorescence Properties

The paper reports on the preparation of a new 2‐rotaxane monomer through an acid coupling reaction between 1‐pyrenecarboxaldehyde and α‐CD/3,5‐diamino‐1,2,4‐triazole inclusion complex. Pyrenyl groups are large enough to provide a blocking effect toward cyclodextrin de‐threading. The oxidative C? C coupling of 2‐rotaxane in the presence of RuCl₃ catalyst afforded conjugated azomethine polyrotaxanes. The expected modifications of the solubility, morphology, film forming ability for rotaxane polymer were proved. As shown by fluorescence and UV‐vis spectroscopy, a material with optical properties appropriate for use in photonics was obtained.

     

Polymerisation of Norbornene Catalysed by Highly Active Tetradentate Chelated α‐Diimine Nickel Complexes

A series of three recently synthesised tetradentate chelated α‐diimine nickel complexes of the type [NiBr₂(Ar‐BIAN)] (where Ar = 2‐(1‐R‐1H‐1,2,3‐triazol‐4‐yl)phenyl; R = benzyl 1 , 1‐phenylethyl 2 , phenyl 3 ) are used as precatalysts for the polymerisation of norbornene. When activated with MAO, 1 – 3 are highly active catalysts for the production of high molecular weight polynorbornene (e.g., 1.39 × 10⁷ g PNB mol Ni^?1 · h^?1). The catalytic activity and polymer molecular weight increase markedly with the initial concentration of norbornene, but both parameters decrease with the reaction time. The characterisation of the polynorbornenes by NMR, GPC/SEC, X‐ray diffraction, and DSC/TGA leads to the assignment of a structure typical of a polynorbornene originated by a coordination vinyl addition mechanism.

     

Synthesis of poly(fluorenevinylene‐co‐phenylenevinylene) by suzuki coupling

Suzuki coupling modified by adding Ag₂O instead of the Na₂CO₃ used in the original reaction protocol, was used as a synthetic tool for the synthesis of a copolymer in which 9,9‐dialkylfluorene moieties were coupled to unsubstituted poly(p‐phenylenevinylene) (PPV) units. The possibility of performing the polymerisations at moderate temperatures appears to be an advantage related to the use of Ag₂O. The copolymer shows a M _w of 21 000 and M _w/M _n = 2.1 and is suitable for the construction of electroluminescent devices. Monolayer organic light‐emitting diodes (OLEDs) have been built which emit greenish light.

Synthesis of poly(fluorenevinylene‐co‐phenylenevinylene).     

Photocurable Shape‐Memory Copolymers of ε‐Caprolactone and L‐Lactide

Biodegradable and photocurable block copolymers of ε‐caprolactone and L ‐lactide were synthesized by polycondensation of PLLA diol ( = 10 000 g · mol^?1), PCL diol ( = 10 000 g · mol^?1), and a chain extender bearing a coumarin group. The effect of copolymer composition on the thermal and mechanical properties of the photocured copolymers was studied by means of DSC and cyclic tensile tests. An increase in Young's modulus and a decrease in the tensile strain with increasing PLLA content was observed for the block copolymers. Block copolymers with high PCL content showed good to excellent shape‐memory properties. Random copolymers exhibited R_f and R_r values above 90% at 45 °C for an extremely large tensile strain of 1 000%.

     

Cyclic Ladder Polymers by Polycondensation of Silylated Tetrahydroxy‐tetramethylspirobisindane with 1,4‐Dicyanotetrafluorobenzene

Summary: 5,5′,6,6′‐Tetra(trimethylsiloxy)‐4,4,4,4′‐tetramethyl‐1,1‐spirobisindane was polycondensed with 1,4‐dicyanotetrafluorobenzene under variation of solvent temperature, time, and feed ratio. Under optimized reaction conditions, all products detectable by MALDI‐TOF mass spectrometry (up to masses around 8 000 Da) proved to be cyclic ladder oligomers and polymers. In N‐methylpyrrolidone and dimethylsulfoxide odd‐numbered cycles were formed in addition to the prevailing even‐numbered ones. However, in sulfolane exclusively even‐numbered cycles were obtained (detectable up to masses around 10 000 Da), together with even‐numbered linear chains. Temperatures above 100 °C enhanced the molecular weights by side reactions. With the less reactive cyano‐2,3,5,6‐tetrafluorobenzene (CTB) again cycles were formed, but their content and the conversions were lower. Polycondensation of CTB up to 160 °C and all polycondensations of cyanopentafluorobenzene gave crosslinked products.

Synthesis of cyclic ladder polymers.     

Novel Phosphorous‐Containing Aromatic Polyethers – Synthesis and Characterization

Summary: The synthesis of novel phosphorous‐containing aromatic polyethers P‐PEEK and P‐PSU, based on poly(ether ether ketone)s (PEEK) and poly(ether sulfone)s (PSU) was carried out successfully by using phosphorous‐containing aromatic diols instead of bisphenol A in the usual synthesis procedure. The molecular weights of the P‐PEEKs and P‐PSUs obtained reflect both the influence of the different halogen components used and the lower thermal stabilities of the phosphorous‐containing diols compared to bisphenol A. However, polymers with sufficient molecular weights could be obtained, having interestingly high T_gs, high thermal stabilities as well as modified flame retardance properties depending on the diol type incorporated.

Comparison of the molecular weights of the synthesized P‐polyethers.     

Synthesis and Characterization of Hyperbranched Polyethylenes Made with Nickel‐α‐Diimine Catalysts

The polymerization of ethylene in the presence of 1,4‐bis(2,6‐diisopropylphenyl)acenaphthenediiminenickel(II) dichloride ( 1 ) and methylaluminoxane (MAO) gives hyperbranched polyethylene (HBPE) in appropriate reaction conditions. The system 1 /MAO is active in solvents like toluene or hexane at temperatures as high as 80 °C and ethylene pressures ranging from 1 to 15 atm. The polyethylenes obtained show high molecular weights (up to 467 kg · mol^?1) and more than 218 branches per 1 000 backbone carbon atoms, qualifying these materials as hyperbranched. Dynamic‐mechanical thermal analysis (DMTA) of these materials shows high β‐transitions, directly related to the branch content of these polyethylenes.

DMTA analysis of polyethylenes obtained with 1 /MAO at 0, 30, and 50 °C (corresponding to entries 1, 2 and 3).     

Insights into the Ring‐Expansion Polymerization of Thiiranes with 2,4‐Thiazolidinedione

The behavior of the ring‐expansion homopolymerization of 2 (phenoxymethyl)thiirane (PMT) and propylene sulfide (PS), respectively, with thiazolidine‐2,4‐dione (TZD) as a cyclic initiator is investigated. The polymerizations show steadily growing molar masses with increasing monomer conversions. In addition, reversible merging reactions between rings are observed, with up to six merged macrocycles formed. The degree of merging is strongly dependent on the initial monomer concentration, whereas temperature has only a small impact. Under optimized conditions, ring‐poly(PMT) polymer with values of M _n up to 50 250 g mol^?1 and dispersities down to 1.11 can be synthesized. DSC and ESI‐MS measurements of the novel ring‐poly(PS) prove the formation of ring polymer having topological purity above 95%.

     

Determination of Polyisoprene‐block‐poly(methyl methacrylate) Domain Sizes Using 1H Spin Diffusion

The microphase structure of polyisoprene‐block‐poly(methyl methacrylate) diblock copolymers was studied using solid‐state NMR techniques. Wideline separation spectroscopy reveals a narrow interphase between the two polymers. The domain sizes of a lamellar sample and a sample with hexagonally ordered cylinders were determined using ¹H spin diffusion. The lamellar sample shows a domain size of 16 ± 2 nm for the minor polyisoprene phase and a long period of 33 ± 4 nm. The cylindrical structure has a long period of 38 ± 7 nm, the diameter of the PMMA cylinders is 21 ± 4 nm. These results are about 20% below the estimates obtained from theoretical calculations according to Helfand and Wasserman.

Morphologies of an a) lamellar, and b) hexagonally ordered cylindrical sample (schematic). The triangle in (b) indicates the symmetry that can be used to calculate the d_L.     

Can the First Addition of Alkyl Radicals Play a Role in the Fate of NMP?

Values of k_d for the C? ON bond homolysis were measured for alkoxyamines based on imidazoline and imidazole nitroxides. They were analyzed in terms of polar/stabilization, steric, and entropic effects. k_d decreased with increasing electron‐withdrawing capacities of the groups attached to the nitroxide, but increasing with both the bulkiness of the group attached to the nitroxide and the presence of substituents on the ring. With three alkoxyamines, it was shown that the fate of the NMP of styrene depended on the type of initiating alkyl radical: successful for initiating 1‐phenylethyl radicals and unsuccessful for initiating p‐nitrophenyloxycarbonyl‐2‐prop‐2‐yl radicals.

     

Blue‐Green Light Emitting Poly(phenylenevinylene) Derivatives as Candidates for Polymer LEDs: Synthesis and Characterization

Summary: Alkoxy substituted derivatives of poly‐ and oligo[(m‐phenylenevinylene)‐alt‐(p‐phenylenevinylene)] were synthesized via the Wittig ( P1 , OPV1 , OPV2 ) and the Wittig‐Horner ( P2 , OPV3 , OPV4 ) condensation routes. The polymers were characterized by ¹³C NMR, ¹H NMR, FT‐IR spectroscopy and GPC. ¹H NMR was a convenient tool to distinguish between the cis and trans double bonds in the compounds. Poly[(4‐decyloxy‐1,3‐phenylenevinylene)‐alt‐(1,4‐phenylenevinylene)] ( P1 ) contained cis and trans double bonds in significant amounts, the vinylene configuration of poly[(4‐decyloxy‐1,3‐phenylenevinylene)‐alt‐(2,5‐dipentyloxy‐1,4‐phenylenevinylene)] ( P2 ) was nearly exclusively trans. Model compounds ( OPV1–4 ) were also synthesized to support the structural and optical characterization. UV‐vis absorption, photoluminescence (PL) and cyclic voltammetry measurements have been performed to investigate the influence of the positions and the number of substituents on electronic levels. The polymers exhibited an intensive solid‐state emission in the blue‐green ( P1 ) and the green ( P2 ) region of the spectrum. Light emitting diodes have been fabricated consisting of ITO, PEDOT:PSS, P2 and Ca/Al. They exhibited high luminance of 100 cd · m^?2 at 5.9 V and low onset voltages (4.3 V) for the electroluminescence (EL).

Schematic representation of a light emitting diode fabricated by use of an alkoxy substituted derivative of poly[(m‐phenylenevinylene)‐alt‐(p‐phenylenevinylene)] ( P2 ).     

Synthesis of Propylene/1‐Butene Copolymers with Ziegler‐Natta Catalyst in Gas‐Phase Copolymerizations, 1

Summary: The appropriate choice of comonomers can be used to create a wide range of polymer properties, leading to considerable improvement of product performance. Experimental runs were performed to evaluate the effect of 1‐butene on the crystallinity, the melt temperature and the molecular weight distribution (MWD) of the final propylene/1‐butene copolymer resins. According to the results obtained, the melt temperature of the copolymer material can be reduced significantly compared to that of the polypropylene homopolymer. The incorporation of 1‐butene into the copolymer chain leads to a decrease of the sealing initiation temperatures of propylene polymer resins. GPC analyses of copolymer samples showed that 1‐butene concentration does not seem to significantly influence either the shape of the MWD or the polydispersity indexes for a given set of reaction conditions. Therefore, a family of propylene/1‐butene random copolymers grades can be successfully developed for gas phase processes for packaging and film applications.