Novel Biodegradable Copolymers with a Periodic Sequence Structure Derived from Succinate Butan‐1,4‐diol,and Butan‐1,4‐diamine

Summary: Novel biodegradable copolymers derived from succinate, butan‐1,4‐diol, and butan‐1,4‐diamine were synthesized by two‐step polycondensation reactions. The obtained copolymers had a periodical‐sequence structure consisting of ester and amide units, and the melting temperatures of the periodic copolymers increased with an increase in amide content. The crystalline structure of the periodic copolymers differs from that of butylene succinate homopolymer (PBS), and these results suggest that the periodically introduced amide units are included in the crystalline phase forming a novel crystalline structure.

Periodic copolyester‐amides derived from succinate, butane‐1,4‐diol, and butan‐1,4‐diamine     

Mechanism of Enzymatic Hydrolysis of Poly(butylene succinate) and Poly(butylene succinate‐co‐L‐lactate) with a Lipase from Pseudomonas cepacia

Enzymatic hydrolysis of poly(butylene succinate) (PBS) and poly(butylene succinate‐co‐L ‐lactate) (PBSL) has been studied by using a lipase originated from Pseudomonas cepacia. It has been found that the drawn fibers of PBSL are readily hydrolyzed by the action of the lipase, while those of PBS undergo little enzymatic hydrolysis. Since the polymer films of PBS and PBSL are readily hydrolyzed under the same conditions, the enzymatic hydrolysis should depend not only on the crystallinity but also on the molecular orientation. The molecular weight of the samples gradually decreases with incubation time, because nonspecific hydrolysis occurs on the main chains of both PBS and PBSL even in the absence of lipase. The enzymatic hydrolysis of PBS and PBSL gives 4‐hydroxybutyl succinate (HBS) as the main product with traces of succinic acid and butane‐1,4‐diol together with L ‐lactic acid in the case of PBSL. In addition, the hydrolysis rate of the carboxyl end‐capped PBS is much slower than that of the original or hydroxyl end‐capped PBS. These results imply a hydrolysis mechanism involving the preferential exo‐type chain scission from the carboxyl terminals.

Mass remaining of various PBS and PBSL samples as a function of time.     

Evidence of Branching in Poly(butyl acrylate) Produced in Pulsed‐Laser Polymerization Experiments

Branched poly(butyl acrylate) was obtained from pulsed‐laser polymerizations carried out in bulk and in solution between −16 and 60 °C. The predominantly short branches are formed by backbiting. The Arrhenius temperature dependence of the backbiting rate is calculated, and the activation energy of this process was found to be remarkably higher than that of propagation. Branching thus increases with temperature leading to broader SEC traces and difficulties in the accurate determination of k_p.

Arrhenius plot of k_fp2 versus 1/T determined experimentally.     

Representation of Hydrogen Atoms in Molecular Dynamics Simulations: The Influence on the Computed Properties of Thin Polystyrene Films

The united atoms (UA) and dummy hydrogen atom (DHA) approaches for molecular dynamics simulations of the interface between oxidized atactic polystyrene (aPS) thin films and water are compared. For both oxidized and non‐oxidized aPS films the polymer density profile decays steepest when using the UA model. The surface roughness of the aPS film and the ordering of the phenyl rings near the surface decrease upon changing from vacuum to water for the UA, but not for the DHA model. This also supports the fact that the non‐oxidized aPS films modeled in DHA representation become less hydrophobic. The water structure close to the interface also suggests that the aPS films modeled using UA are more hydrophobic compared to the aPS films modeled with DHA in the phenyl rings.

     

Facile Fabrication of Functional Polypyrrole Nanotubes via a Reactive Self‐Degraded Template

Summary: Polypyrrole nanotubes with high electric conductivity and azo function have been fabricated in high yield via an in‐situ polymerization. During the process fibrillar complex of FeCl₃ and methyl orange (MO), acting as a reactive self‐degraded template, directed the growth of polypyrrole on its surface and promoted the assembly into hollow nanotubular structures.

TEM image of uncompleted PPy nanotubes synthesized in MO solutions after reaction for 40 min.     

Poly(amidoamine)s with 2‐Dithiopyridine Side Substituents as Intermediates to Peptide–Polymer Conjugates

Cystamine, when employed as a cross‐linking agent, leads to poly(amidoamine) networks, which on reaction with 2,2′‐dithiodipyridine turn into linear poly(amidoamine)s with side dithiopyridyl groups that easily undergo exchange reactions with reduced L ‐glutathione, a model thiol‐containing biologically active peptide. The resultant products represent the first examples of soluble poly(amidoamine)–peptide conjugates in which the peptide moieties are linked to the polymer chain by S S bonds stable in blood, but cleavable inside cells.

     

The Effect of Substrate on the Annealing of Poly(butylene succinate) Single Crystals

The morphological evolution of poly(butylene succinate) (PBS) solution‐grown single crystals during annealing was studied using hot‐stage atomic force microscopy. Their morphology changed with increasing temperature and annealing time. The annealing behavior and melting temperature were found to be affected by the substrate. Morphological changes occurred at a much lower temperature on an amorphous carbon film than that on a mica surface. Moreover, the pattern of morphological evolution of the single crystals on a carbon film was different from that on a mica surface. Since the PBS melt had a larger contact angle on the mica surface, these differences in the melting behavior were ascribed to the different interfacial interactions between the chain‐folded surface of the single crystal and the substrate.

     

Reaction of Boranes with TMS Diazomethane and Dimethylsulfoxonium Methylide. Synthesis of Poly(methylidene‐co‐TMSmethylidene) Random Copolymers

Summary: Borane reacts with TDM by a sequence of insertion and disproportionation reactions to yield tris‐(trimethylsilylmethyl)borane. No further addition of TDM occurs. Triallylborane and tris‐(4‐methoxyphenylethyl)borane initiate the copolymerization of TDM and dimethylsulfoxonium methylide. The reactions afford TMS‐substituted polymethylene oligomers. The resultant poly(methylidene‐co‐TMSmethylidene) random copolymers arise from incorporation of TMSmethylidene (CHSiMe₃) and methylidene (CH₂) groups into the growing polymer chain one carbon at a time.

Trialkylborane‐catalyzed copolymerization of trimethylsilyl diazomethane and dimethylsulfoxonium methylide.     

Surface Fixing Effect of Vacuum Evaporated Particles on Polyethylene Single Crystals

Summary: The recrystallization behavior of high density polyethylene (HDPE) single crystals with vacuum evaporated metal chromium or carbon on their surface has been investigated by transmission electron microscopy (TEM) and electron diffraction (ED) techniques. The results indicate that the particle‐coated HDPE single crystals can retain their single crystal structure after complete melting and subsequent recrystallization, with the heat‐treated temperature as high as 200 °C. This phenomenon is attributed to a surface fixing effect of vacuum evaporated Cr or carbon on the single crystals.

A bright‐field electron micrograph and the corresponding electron diffraction pattern of recrystallized Cr‐coated HDPE single crystals.     

Ordered Microporous Surface Films Formed by Core‐Shell‐Type Nanospheres

Summary: Polymer nanospheres are synthesized by free‐radical dispersion copolymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) with a methacryloyl‐terminated polystyrene (PS‐MC) macromonomer in cyclohexane. Such polymer nanospheres are stabilized sterically with polystyrene (PS)‐grafted chains in cyclohexane at temperatures greater than 34 °C (the Θ temperature for PS). Ordered microporous surface films are constructed by casting these core‐shell‐type nanospheres from hot cyclohexane solution at 20 °C. The results indicate the possibility of fixation or encapsulation of functional materials after microporous patterning of the core‐shell‐type nanospheres.

SEM photograph of a vertical section of a hexagonal micropore film obtained here.     

Kinetic Modeling as a Tool to Understand and Improve the Nitroxide Mediated Polymerization of Styrene

Kinetic modeling is used to obtain insight in the complex interplay between reaction rates and obtained polymer properties in the SG1 and the TEMPO mediated bulk polymerization of styrene at 396 K. The increase of the viscosity during NMP is accounted for. At higher targeted chain lengths, chain transfer to dimer and transfer from nitroxide to dimer are shown to cause the experimentally observed reduced control over the average polymer properties and to result in a clear fronting of the polymer chain length distribution. The potential of kinetic modeling to design tailor‐made synthesis strategies is illustrated. Simulations indicate that careful control of the polymerization conditions allows to obtain an important improvement of the polymer properties. The approach is also applicable for NMP mediated by other alkoxyamines/nitroxides and allows to expand the application range of NMP for styrene polymerization in particular to synthesize complex polymer architectures by assembly of functionalized polymers.

     

Alternating Diene Metathesis Polycondensation (ALTMET) – A Versatile Tool for the Preparation of Perfectly Alternating AB Copolymers

Perfectly alternating copolymers can be synthesised by reacting diacrylates with terminal dienes using alternating diene metathesis polycondensation (ALTMET). This novel method is very versatile and allows preparation of diverse structures of polymers, including main‐chain liquid crystalline polymers.

Main‐chain liquid crystalline polymer obtained by ALTMET.     

Stabilization of Polymer Bilayers by Introducing Crosslinking at the Interface

Summary: Bisphenol A solid epoxy serves as an effective reaction compatibilizer to the bisphenol A polycarbonate (PC)/PMMA bilayer systems. Addition of epoxy to the bottom PMMA layer can retard or even prevent the dewetting of PC films by introducing crosslinking between both components at the interface. This is the first investigation of polymer bilayers stabilized by chemical reactions.

AFM topographic image of a representative dewetting hole.     

Construction of a Hexameric Zn(II)‐metallomacrocycle and its Photo‐ and Electroluminescence Properties: [Zn6(O‐hexyl‐3,5‐bis(2,2′:6′,2″‐terpyridine)phenol)6(BF4)12]

Summary: An O‐hexyl‐3,5‐bis(terpyridine)phenol ligand has been synthesized and transformed into a hexagonal Zn(II)‐metallomacrocycle by a facile self‐assembly procedure capitalizing on terpyridine‐Zn(II)‐terpyridine connectivity. The structural composition was confirmed by NMR and mass spectral techniques; photo‐ and electroluminescence properties were also investigated. The OLED device shows green electroluminescent emission at 515 nm with a maximum luminance of 39 cd · m⁻² and maximum efficiency of 0.16 cd · A⁻¹.

Structure and electroluminescent properties of the metallomacrocycle investigated.     

Graphene Enhances the Shape Memory of Poly (acrylamide‐co‐acrylic acid) Grafted on Graphene

Acrylamide and acrylic acid are grafted on graphene by free‐radical polymerization to produce a series of graphene–poly(acrylamide‐co‐acrylic acid) hybrid materials with different contents of graphene. The materials demonstrate shape memory effect and self‐healing ability when the content of graphene is in the range of 10%–30% even though poly(acrylamide‐co‐acrylic acid) itself had poor shape memory ability. The permanent shape of the materials can be recovered well after 20 cycles of cut and self‐healing. The result is attributed to the hard–soft design that can combine nonreversible “cross‐link” by grafting copolymer on graphene and reversible “cross‐link” utilizing the “zipper effect” of poly(acrylamide‐co‐acrylic acid) to form or dissociate the hydrogen‐bond network stimulated by external heating.

     

Aqueous RAFT Polymerization of Acrylamide and N,N‐Dimethylacrylamide at Room Temperature

Summary: The first example of a room temperature reversible addition‐fragmentation chain transfer polymerization conducted directly in aqueous media is detailed. Under these conditions acrylamide and N,N‐dimethylacrylamide may be polymerized in a controlled fashion to near quantitative conversions employing a difunctional trithiocarbonate chain transfer agent (CTA). Hydrolysis studies conducted at pH 5.5 suggest that the CTA is stable up to approximately 50 °C.

     

Diversified Applications of Chemically Modified 1,2‐Polybutadiene

Commercially available 1,2‐PB was transformed into a well‐defined reactive intermediate by quantitative bromination. The brominated polymer was used as a polyfunctional macroinitiator for the cationic ring‐opening polymerization of 2‐ethyl‐2‐oxazoline to yield a water‐soluble brush polymer. Nucleophilic substitution of bromide by 1‐methyl imidazole resulted in the formation of polyelectrolyte copolymers consisting of mixed units of imidazolium, bromo, and double bond. These copolymers, which were soluble in water without forming aggregates, were used as stabilizers in the heterophase polymerization of styrene and were also studied for their ionic conducting properties.