One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with Pendant Acryloyl Functionalities by Chain Walking Copolymerizations

Chain walking copolymerization of ethylene with 1,4‐butanediol diacrylate at elevated concentrations for the synthesis of low‐viscosity hyperbranched polyethylenes tethered with a controllable amount of acryloyl functionality is reported. At concentrations much higher than the critical gelation concentrations, the diacrylate comonomer is copolymerized predominantly following the mono‐insertion pattern. A range of hyperbranched polyethylenes tethered with acryloyl functionality (1.3–4.8 mol‐%) and having low melt viscosity (ca. 25 Pa · s at 25 °C) and low glass transition temperature (T_g = ?69 °C) has been synthesized. This unique method is specific to the Pd‐diimine‐catalyzed chain‐walking copolymerization system.

     

On the Mechanism of the Ring‐Expansion Polymerization of Thiiranes

Ring polymers are synthesized using a cyclic bifunctional thioester as initiator for REP of thiiranes. PMT yields satisfactory results, whereas polymerization with MT appears to develop dead polymeric material as by‐product and TBMT gives only negligible conversion rates. The process produces high yields and high conversion rates. The corresponding molecular weight distributions show increasing broadening and multimodal character with increasing reaction time due to thermodynamically controlled ring‐merging reactions between macrocycles. The polymerization rate of PMT obeys a pseudo first‐order kinetics with an activation energy of 38.8 kJ mol^?1. ¹H NMR, ESI‐MS, and glass transition temperatures independent of the molecular weight demonstrate the presence of cyclic polymer.

     

Control of the radical polymerization by 2,2,15,15‐tetramethyl‐1‐aza‐4,7,10,13‐tetraoxacyclopentadecan‐1‐oxyl and its sodium salt

The control of the radical polymerization of styrene by 2,2,15,15‐tetramethyl‐1‐aza‐4,7,10,13‐tetraoxacyclopentadecan‐1‐oxyl is reported here in bulk at 90 °C, 120 °C and in miniemulsion. Similarly, the control by its sodium complex is reported in bulk at 90 °C.

M _n vs. conversion for 3 , 3Na , and TEMPO.     

A Poly(vinyl alcohol)‐graft‐Copolyester: Synthesis of a Novel Graft Copolymer Containing Adamantane Moieties as Guest for Cyclodextrin

A novel graft copolymer is synthesized from commercially available poly(vinyl alcohol) using ring‐opening polymerization. For the polymerization reaction of novel brush‐like poly(vinyl alcohol)‐graft‐poly(?‐caprolactone‐co‐(3‐/7‐(prop‐2‐ynyl)oxepan‐2‐one) 5 Sn(Oct)₂ is used as a catalyst. The formation of the graft copolymer is confirmed by ¹H NMR, ¹³C NMR, and Fourier transform infrared (FTIR) spectroscopy. Furthermore, the modification of the novel synthesized graft copolymer via a “click” reaction to implement adamantane groups is described. The success of the “click” reaction is proven by ¹H NMR spectroscopy and visualized by decomplexation of cyclodextrin with included phenolphthalein.

     

Monolayer Assemblies of Comb Polymers Containing Different Kinds of Fluorocarbon Side‐Chains

Summary: Langmuir monolayers and organized molecular films of comb polymers containing different kinds of fluorocarbon side‐chains with various chain lengths and substituted atoms at the ω‐position were characterized by surface pressure‐area isotherms as well as Brewster angle microscopy on a water surface and by scanning probe microscopies (AFM and FFM) and the out‐of and in‐plane X‐ray diffractions on the solid substrates, respectively. When compared with monolayers of fluorinated amphiphilic vinyl monomers, those of the corresponding comb polymers were significantly stabilized. The nanostructures of these organized molecular films changed considerably with the film fabrication method used (such as mixed monolayers with hydrogenated amphiphiles) and the deposition conditions as well as with minor chemical modification of the fluorinated comb polymers with different hydrophilic esters and fluorocarbon side‐chains. The characteristic friction behavior for films built up of the fluorinated amphiphiles and comb polymers was found to depend strongly on the chemical constituents of the outermost layer of the film surface.

     

Synthesis of a Polyphenol with a Mesoionic 6‐Oxo‐1,6‐dihydropyrimidin‐3‐ium‐4‐olate as Pendant Group and Its Photochemical Behavior

This study deals with the synthesis of a polyphenol bearing photosensitive groups, and its photochemical behavior upon UV irradiation. Mesoionic 5‐(4‐hydroxybenzyl)‐6‐oxo‐1,2,3‐triphenyl‐1,6‐dihydropyrimidin‐3‐ium‐4‐olate was prepared by condensation of 4‐benzyloxybenzylmalonic acid with N,N′‐diphenylbenzamidine using dicyclohexylcarbodiimide as condensing agent, followed by deprotection of the benzyl group. The monomer was polymerized by an iron‐salen complex to give a polymer with a mesoionic 6‐oxo‐1,6‐dihydropyrimidin‐3‐ium‐4‐olate moiety as the pendant group. Spin coated polymer films were prepared and characterized. It was shown by IR spectroscopy that irradiation with UV light converted the mesoionic structure to a bis(β‐lactam) structure. Waveguide spectroscopy showed a large decrease in the film thickness without refractive index changes during irradiation.

Time development of the refractive index and the film thickness measured with p‐polarized light.     

Dielectric Response of Aramid Fiber‐Reinforced PEEK

Dielectric spectroscopy was applied for the first time to aramid fiber‐reinforced PEEK, wherein the effect of the fiber on the dielectric response was examined for both amorphous and crystalline poly(ether ether ketone) (PEEK) over wide temperature and frequency ranges. Whereas the temperature behavior of the dielectric losses of the materials exhibited the typical α and β processes of PEEK, the specific effect of the fibers in the crystalline PEEK was revealed in shifting the α process to a higher temperature. The unique effect of the fibers was expressed by a significantly higher activation energy and lower dielectric strength for the α relaxation, reflecting a higher constraint level that is imposed by the fiber. It is proposed that this additional constraint is associated with fiber generated transcrystallinity.

Scanning electron micrograph of transverse fracture surface of crystallized unidirectional aramid fiber‐reinforced PEEK.     

The Development of Stereoerrors During the Homo‐ and Copolymerization of Propylene Using C2‐Symmetric Metallocene Catalysts – A Cautionary Note

Summary: A recent paper described the development of atactic sequences during the copolymerization of propylene and 1‐pentene using the C₂‐symmetric metallocene catalyst rac‐dimethylsilyl‐bis(2‐methylbenz(e)indenyl) zirconium dichloride. We have found similar stereoerrors, and showed that atactic material could in fact be extracted from the material, indicating that the catalyst in question had probably isomerized in solution, leading to a mixture of isotactic and atactic polymers.

     

Synthesis and aqueous phase behavior of thermoresponsive biodegradable poly(D,L‐3‐methylglycolide)‐block‐poly(ethylene glycol)‐block‐poly(D,L‐3‐methylglycolide) triblock copolymers

Novel biodegradable thermosensitive triblock copolymers of poly(D ,L ‐3‐methylglycolide)‐block‐poly(ethylene glycol)‐block‐poly(D ,L ‐3‐methylglycolide) (PMG‐PEG‐PMG) have been synthesized. Ring‐opening polymerization of D ,L ‐3‐methyl‐glycolide (MG) initiated with poly(ethylene glycol) (PEG) and Ca[N(SiMe₃)₂]₂(THF)₂ provided triblock copolymers with alternating lactyl/glycolyl sequences of controlled molecular weight, low polydispersity index and uniform chain structure. At relatively low temperatures (≈ 10 °C) these copolymers formed clear solutions in water up to high concentrations (50 wt.‐%). Depending on molecular mass ratios of PMG and PEG blocks, a sol‐gel transition or an increase in viscosity without gel formation was observed upon increasing the temperature of the aqueous solutions. The temperature‐induced gelation was ascertained by rheology and dynamic differential scanning calorimetry (DDSC).

Phase diagram of PMG‐PEG‐PMG 1 400‐1 450‐1 400 in an aqueous solution.     

Crystallization and Ring‐Banded Spherulite Morphology of Poly(ethylene oxide)‐block‐Poly(ε‐caprolactone) Diblock Copolymer

Summary: The crystallization behavior of crystalline‐crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(ε‐caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring‐banded spherulite morphology for the PEO‐b‐PCL diblock copolymer.

DSC heating curve for the PEO‐b‐PCL block copolymer.     

Synthesis of Poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)]‐Poly(propylene oxide) Block Copolyester by Direct Polyesterification of Reactive Oligomers

Summary: The objective of this study was to synthesize thermoplastic elastomers by the direct copolyesterification of reactive oligomers of poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)] (PET) and poly(propylene oxide) (PPO). The synthesis of hard segment oligomers was achieved in two steps. The first step consisted of the glycolysis of PET leading to α,ω‐hydroxyl functionalized oligomers. The second step corresponded to the ring opening polymerization of ε‐caprolactone onto the hydroxyl end groups of the PET oligomers. Commercially available hydroxytelechelic poly(propylene oxide) was modified to obtain carboxytelechelic poly(propylene oxide). The chemical structure of the product was investigated by ¹H NMR and size exclusion chromatography (SEC). Multiblock poly(ester‐ether) was then synthesized by polyesterification of hydroxytelechelic poly[(ethylene terephthalate)‐co‐(ε‐caprolactone)] with carboxytelechelic poly(propylene oxide) oligomers, using different catalysts and reaction conditions. The best stoichiometric ratio for the reaction was determined in order to obtain the highest possible . The chemical structure of the synthesized poly(ester‐ether) was investigated by size exclusion chromatography and ¹H NMR. The thermal and thermomechanical behavior of the synthesized poly(ester‐ether) was investigated by differential scanning calorimetry and dynamic mechanical analysis, which showed that the poly(ester‐ether) behaved as a thermoplastic elastomer. This product could also be an interesting way for chemical recycling of PET waste.

Synthesis of multiblock co‐poly(ester‐ether).     

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.

     

Poly(N‐hexyl‐cyclopenta[c]pyrrole) – A Novel 1,3,4‐Alkyl‐substituted Polypyrrole Soluble in Organic Solvents and Redox Conducting

Summary: N‐Hexyl‐cyclopenta[c]pyrrole was synthesized and electrochemically and chemically polymerized to a novel 1,3,4‐alkyl‐substituted polypyrrole. The polymer was characterized in solution and as thin solid film by cyclic voltammetry, UV‐vis, FTIR and NMR spectroscopy, MALDI mass spectroscopy, GPC analysis, electrochemical quartz crystal microbalance, ESR spectroscopy and in situ conductivity. The polymer, with a defect‐free structure and an average degree of polymerization of 13 (electrochemically prepared) and 24 (chemically prepared), is soluble (>1%) in acetone, acetonitrile and chlorinated solvents. Its in situ conductivity as a function of potential and doping charge has the typical features of redox conductivity with a maximum value of ca 1 × 10^?3 S · cm^?1.

Structure of poly(N‐hexyl‐cyclopenta[c]pyrrole).     

Gas‐Phase Assisted Surface Polymerization of Vinyl Monomers with Fe‐Based Initiating Systems

Summary: Gas‐phase assisted surface polymerization (GASP) of methyl methacrylate (MMA) and styrene (St) was investigated with Fe‐based radical initiating systems, FeCl₂/2,2′‐bipyridine (Bpy)/methyl α‐bromophenylacetate (MBPA), etc. GASP with these initiating systems proceeded to produce corresponding polymers on substrate surfaces. The resulting PMMA had very high PDI values, suggesting an uncontrolled reaction. In an attempt to control the GASP, polymerization with a simple initiating system, Fe(0)/MBPA, was examined on Fe(0)‐metal surfaces, resulting in significant polymerization activity to produce high‐molecular‐weight PMMA. The results of time‐course tests on GASP of MMA and St suggested that a change had taken place to produce physically controlled propagation sites on the Fe(0) powder surfaces.

GASP schemes with a simple initiating system Fe(0)/MBPA.     

Aniline‐Based Disulfide/Aniline Copolymers as a High Energy‐Storage Material

Aniline‐based disulfide, 5‐amino‐1,4‐dihydrobenzo[d]‐1′,2′‐dithiadiene (DTAn), was synthesized through a new route. The DTAn/aniline copolymers [P(DTAn‐co‐An)] were prepared by chemical oxidative polymerization. The results show that the polymerization activity of the DTAn is obviously lower than that of aniline, and the degree of polymerization increases with the increasing feed ratio of aniline and oxidant dosage. The cyclic voltammograms of the copolymers indicate that intramolecular self‐catalyzed effects occurred between the conducting backbone and the S‐S side chain. The charge–discharge tests of Li/P(DTAn‐co‐An) cell show an initial specific capacity of 262 mAh · g⁻¹, which suggests that P(DTAn‐co‐An) may be a promising cathode material in secondary lithium batteries.

     

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 of New Blue Anthracene‐based Conjugated Polymers and Their Applications in Polymer Light‐Emitting Diodes

A series of anthracene‐based conjugated copolymers containing 9,10‐bis(6‐bromonaphthalen‐2‐yl)‐2‐tert‐butylanthracene (BNA) and 2,7‐diphenyl substituted fluorene (DPPF) moieties are prepared via a palladium‐catalyzed Suzuki polymerization. All of the synthesized polymers emit blue light at around 450 nm and show good thermal and color stability. Their electroluminescence spectra remain unchanged at high driving voltage. The double‐layer polymer light‐emitting diode (PLED) fabricated with ITO/PEDOT:PSS/DPPFBNA3/CsF/Al, produces a maximum brightness of 1 650 cd · m^?2 and has a luminance efficiency of 0.39 cd · A^?1. The ITO/PEDOT:PSS/TFB/DPPFBNA3/CsF/Al multilayer PLED, incorporating a TFB layer to facilitate hole transportation, produces a maximum brightness of 5 371 cd · m^?2 and a luminance efficiency of 1.18 cd · A^?1.

     

Allyl End‐Functionalized Poly(ethylene oxide)‐block‐poly(methylidene malonate 2.1.2) Block Copolymers: Synthesis,Characterization, and Chemical Modification

Summary: Poly(ethylene oxide)‐block‐poly(methylidene malonate 2.1.2) block copolymer (PEO‐b‐PMM 2.1.2) bearing an allyl moiety at the poly(ethylene oxide) chain end was synthesized by sequential anionic polymerization of ethylene oxide (EO) and methylidene malonate 2.1.2 (MM 2.1.2). This allyl functional group was subsequently modified by reaction with thiol‐bearing functional groups to generate carboxyl and amino functionalized biodegradable block copolymers. These end‐group reactions, performed in good yields both in organic media and in aqueous micellar solutions, lead to functionalized PEO‐b‐PMM 2.1.2 copolymers which are of interest for cell targeting purposes.

Synthetic route to α‐allyl functionalized PEO‐b‐PMM 2.1.2 copolymers.     

Controlled Ring‐Opening Polymerization of Lactones and Lactide Initiated by Lanthanum Isopropoxide, 2. Mechanistic Studies

The mechanism of ring‐opening polymerization of some lactones and lactide initiated by lanthanum isopropoxide has been comprehensively investigated. NMR and viscosity analyses demonstrated that three active polymer chains grow per lanthanum atom and that, depending on the coordinating ability of the monomer, propagation proceeds on aggregated or unaggregated active species. It is also demonstrated that inter‐ and intramolecular side reactions are limited and that lanthanum‐based initiator selectivity in ring‐opening polymerization is analogous to that of aluminum ones.

Part of the proposed mechanism for the lanthanum alkoxide initiated polymerization of ε‐caprolactone.     

Towards Highly Substituted Starburst Macromolecular Semiconductors: Microwave Synthesis,Spectroscopy and Electrochemical Properties

As part of a strategy to explore highly functionalized macromolecular semiconductors, a series of highly substituted twelve‐armed macromolecules F1CzTr‐F3CzTr consisting of truxene, 9‐phenylcarbazole and oligofluorene units were synthesized. To accomplish the synthesis of twelve‐armed targets, a high yield microwave enhanced synthesis method for direct twelve‐fold Suzuki couplings was developed. The resulting materials exhibited high purity and good monodispersity (PDI 1.01–1.03). The molecular weight of the compound F3CzTr achieved 14 266 g · mol^?1, representing one of the largest well‐defined starburst conjugated molecules. The thermal, photophysical and electrochemical properties were investigated.