Macromol. Chem. Phys. 13/2011

Reactive blending of functionalized polyethylenes (PE) and polyamides (PA) is performed by carefully choosing extrusion conditions and polymeric materials in order to obtain two types of stable morphologies. The first blend type yields a co‐continuous morphology and the second type a dispersion of sub‐micron droplets of the PA phase in a PE matrix. The crystallization kinetics of the PA change from a sigmoidal classical type (for the co‐continuous blend) to first‐order kinetics in the case of the sub‐micron PA droplets. The results demonstrate an intimate relationship between blend morphology and nucleation and crystallization kinetics of the blend components.

     

Cocrystallization of Blends of Ethylene/1‐Olefin Copolymers: An Investigation with Crystallization Analysis Fractionation (Crystaf)

Summary: Crystallization analysis fractionation (Crystaf) is a technique for estimating the chemical composition distribution (CCD) of semi‐crystalline copolymers. Cocrystallization may happen during Crystaf analysis, affecting Crystaf profiles and leading to misinterpretation of the CCD. This study investigates this phenomenon and determines the main factors leading to cocrystallization by analyzing a series of ethylene/1‐olefin copolymers. We considered three factors affecting cocrystallization: comonomer type, cooling rate and chain crystallizability. The results showed that cooling rate and similarity in chain crystallizability are the key factors regulating cocrystallization during Crystaf analysis.

Crystaf analysis of blends of copolymers.     

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.

     

Fabrication of Conjugated Polymer Supramolecules in Electrospun Micro/Nanofibers

A combination of top‐down (electrospinning for fabrication of high surface area micro/nanofibers) and bottom‐up (creation of supramolecular structures through self‐assembly processes in fiber) approaches has enabled the generation of conjugated polymer‐embedded fibers. The efficiency of fiber formation, encapsulated with colorimetric, and fluorogenic conjugated polydiacetylene supramolecules, was dependent on electrospinning conditions, such as concentration, molecular weight, type of matrix polymer, and solvent. In general, electrospinning of a chloroform solution containing 1.6 wt.‐% of a diacetylene monomer and 4 wt.‐% PEO of molecular weight 300 000 g · mol^?1 followed by 254 nm UV irradiation resulted in clean formation of polydiacetylene‐embedded fibers. In addition, UV irradiation during electrospinning can be used for in situ and continuous generation of polydiacetylenes‐encapsulated fibers.

     

Modification of Polyethylene by VUV Irradiation in the Presence of Trimethylsilane and Oxygen

The photoassisted modification of LDPE by VUV irradiation in a reactive trimethylsilane/oxygen atmosphere was investigated. The modified LDPE surface was investigated by FT‐IR, XPS, contact‐angle measurements and electron microscopy. Attachment of alkylsilyl and Si–O units to LDPE was observed. Best results were obtained using an equimolar trimethylsilane/oxygen mixture. Low‐energy surfaces were obtained after a few minutes of irradiation at an intensity of 1.7 mW · cm^?2. After prolonged irradiation, the thickness of the modified polyethylene layer is approximately 700 nm. Surface modifications of this type may be of interest to obtain protective and barrier layers on polyolefins.

     

Synthesis and Dielectric Study of New Liquid‐crystalline Polysiloxanes Presenting a Thioether Spacer

Three new cyanobiphenyl polysiloxanes presenting long thioether spacers have been carried out. This type of spacer leads to very stable liquid‐crystalline polymers at room temperature and remove the crystallinity phenomenon. Dielectric analysis results show that the thioether spacer brings much more molecular flexibility to the system.

Example of an “interdigitated” structure observed by X‐ray analysis.     

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.     

Graft Polymerization of Methacrylamide onto Poly(ethylene terephthalate) Fibers with Benzoyl Peroxide as Initiator and their Characterization

Summary: The effects of polymerization temperature and time, initiator and monomer concentrations, ratio of water and solvent employed on the grafting of methacrylamide onto poly(ethylene terephthalate) fibers by the use of benzoyl peroxide initiator were studied. The graft yield was observed to increase with temperature and monomer concentration. The highest graft yield was obtained with an initiator concentration of 1 × 10^?2 mol/L. The rate of grafting was proportional to the power 0.48 and 1.6 of the methacrylamide and benzoyl peroxide concentrations, respectively. The overall activation energy for grafting calculated was 42.8 kcal/mol. The thermogravimetric data revealed that the thermal stability of poly(ethylene terephthalate) fibers decreased with grafting.

SEM micrographs of ungrafted PET fiber (a) and 44.9% MAAm‐grafted fiber (b).     

Study of Laser‐Induced Photopolymerizations by Optical Pyrometry

Summary: Studies of the 355 nm laser induced free radical and cationic photopolymerization reactions of mono‐ and multifunctional monomers were conducted. These investigations were carried out with the aid of a specially constructed optical pyrometry instrument that provides rapid, reproducible temperature versus time profiles for these fast photopolymerization reactions. Using this technique, the effects of various reaction parameters and monomer structures on the rate and extent of the photopolymerization reactions were examined.

Optical pyrometry instrument for the monitoring of laser‐induced photopolymerizations.     

Radiation‐Induced Reaction of Sulfonamide‐Containing Polymers in the Film State for Color Imaging

A polysulfonamide and copolymers consisting of sulfonamides and amides underwent Fries rearrangement and scission, forming amino groups upon EB irradiation. The EB irradiation of these films with a dose of 500 µC · cm^?2, followed by the color forming reaction provided the color imaging of line/space patterns with a resolution of 300 nm.

     

Synthesis and Characterization of Conducting Copolymers of (S)‐2‐Methylbutyl‐2‐(3‐thienyl)acetate with Pyrrole and Thiophene

Polymerization of methylbutyl‐2‐(3‐thienyl)acetate (MBTA) was achieved by constant current electrolysis at low temperature. Subsequently, the syntheses of block copolymers of polyMBTA were accomplished in the presence of either pyrrole or thiophene by constant potential electrolysis. Moreover, the copolymer of MBTA with thiophene was obtained with constant potential electrolysis.

The synthesis of monomer MBTA.     

Impact of Solvent on Electrospinning of Zein and Analysis of Resulting Fibers

Zein fibers have been produced by electrospinning from acetic acid, aqueous methanol, ethanol and isopropyl alcohol. Alcohol solutions produced fibers that were predominantly ribbons. Fibers spun from acetic acid solution have a round morphology with a narrower distribution of diameters when spun under suitable conditions. The IR spectra of electrospun fibers display increased absorbance at 1 650 cm^?1 relative to starting material, indicative of increased α‐helical structure. Raman spectra of fibers spun from acetic acid solution had spectral differences, having increased absorbance at 680, 750 and 860 cm^?1, versus fibers spun from alcoholic solvents suggesting different tertiary structure within the fiber, which may result from different structures in solution. Polarized Raman spectroscopy taken parallel and perpendicular to the fiber axis displayed no differences, suggesting similar secondary and tertiary structures in these directions. All of the fibers had some degree of birefringence demonstrating the presence of orientation. The smaller fibers were highly birefringent throughout the fiber, while the larger fibers had orientation at the surface only. Quality fibers could not be produced from N,N‐dimethylformamide, acetone/water, acetic acid/water, 8 M urea/water or 10% NaOH/water zein solutions.

     

Pinacol rearrangement in the polymer backbone: Synthesis of novel reactive polymers with condensed benzopinacol units in the main chain and their complete rearrangement to poly(benzopinacolone)s

Novel reactive polymers with condensed benzopinacol moieties in the main chain were synthesized and their acid‐catalyzed pinacol rearrangement in the polymer backbone proceeded to afford poly(benzopinacolone)s quantitatively. Since the pinacol rearrangement shows an intramolecular mechanism, no crossover between the polymer chains was observed through the rearrangement. Although the number‐averaged molecular weights and their distributions were not changed, the optical and thermal properties of the poly(benzopinacolone)s were completely different from the parent poly(benzopinacolone)s.

     

Cholesteric Liquid‐Crystalline Side‐on Polysiloxanes: Effects of Biaxiality on the Cholesteric Structure

Summary: Biaxial side‐on cholesteric copolysiloxanes with laterally attached mesogenic groups were investigated in mixtures with a low molar mass liquid crystal. While mixtures with a low concentration of the polymer exhibit the conventional fingerprint texture, for concentrations above about 60 mol‐% characteristic irregularities appear in the cholesteric structure that are obviously due to phase biaxiality. Besides the absence of pseudo‐isotropic lines, irregular patterns perpendicular to the helix axis emerge and the periodic distance of regions with similar optical properties along the helix axis is strongly disturbed. This suggests that the photonic band gap width of a uniaxial cholesteric phase becomes strongly affected when a phase transformation into a biaxial cholesteric phase occurs.

Cholesteric fingerprint texture of a mixture of uniaxial nematic monomer and biaxial cholesteric polymer.     

UV Laser Deposition of SiS/Poly(thiacarbosilane) Composites and their Conversion to SiO/Poly(thiacarbosiloxane) Composites

ArF laser irradiation of gaseous mixtures of carbon disulfide and silane allows efficient deposition of Si? S bond‐containing poly(thiacarbosilanes) incorporating SiS bodies. These SiS/poly(thiacarbosilane) composites are the first example of silicon sulfide/polymer composites. Composite formation is analyzed by GC/MS analysis of volatile products and the structure of the composite as determined by electron microscopy and FT‐IR spectra. The composites undergo reaction with air moisture and methanol vapor, evolve H₂S and evolve to nano‐sized poly(thiacarbosiloxane)s and poly(methoxythiacarbosiloxane)s.

     

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.

     

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.     

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.     

Structural Aspects of Poly(thiodiethylene terephthalate) Investigated by X‐Ray Powder Diffraction

Summary: The full‐profile refinement of X‐ray diffraction patterns was used to investigate two poly(thiodiethylene terephthalate) (PSDET) samples with different thermal history in order to thoroughly analyze their polymorphic aspects. In each sample, a crystalline (α or β) and a microcrystalline (α′ or β′) phase were identified together with an amorphous component. The crystal structures of all the ordered phases were determined. The data indicated an appreciable difference between the two crystalline forms, while the microcrystalline were rather similar. The results reported in this paper agree with the hypothesis that the polymorphic and morphological aspects of PSDET have to be correlated with the order degree and reorganization of crystallites and microcrystallites.

Projection along the a axis and c axis of α‐phase chain arrangement.     

Macromol. Chem. Phys. 24/2009

The behavior of the transmittance self‐oscillation of a polymer chain with a positively charged MAPTAC group is studied. The polymer concentration exerts considerable influence on the behavior and lifetime of the self‐oscillation. The redox potential and transmittance are measured simultaneously showing that the reactivity of the Ru(bpy)₃ moiety is significantly affected by the polymer aggregation state, originating from the solubility of the polymer chain. The behavior and lifetime of the self‐oscillation can be controlled by changing the design of the polymer structure and concentration.