Volume 3, Issue 1

Alternating poly(ester amide)s 6a - e were prepared by polycondensation of α-carboxyl-ω-hydroxyamides 3a - e which were obtained by aminolysis of glutaric anhydride (1) and α,ω-aminoalcohols, H 2 N-(CH 2 ) x -OH (x = 2 - 6) 2a - e. The polycondensation was performed in dimethylformamide solution using a carbodiimide as activating agent, or in bulk with Bu 2 Sn(OMe) 2 , Ti(OBu) 4 and Sn(octoate) 2 as a catalyst. For the polycondensation in bulk, the influence of catalyst and of temperature on the number-average molecular weight was studied. 1 H NMR analyses of the poly(ester amide)s clearly show the alternating microstructure. The poly(ester amide)s from glutaric anhydride and the homologous series of α,ω-aminoalcohols are semicrystalline materials; their melting points show the odd/even effect observed for other poly(ester amide)s.

In the presence of an excess of various alkyl radical scavengers or nitroxide reductants (TEMPO, phenylhydrazine and thiophenol), 31 P NMR monitoring was used to determine the homolysis rate constant (k d ) of β-phosphorylated alkoxyamines. The k d values for a mixture of diastereoisomeric alkoxyamines can be obtained in a single experiment and the formation of reaction products can be followed. The measured values were in good agreement with those obtained with other approaches involving chromatography or electron paramagnetic resonance (EPR).

The synthesis of a novel photochromic dithienylethene-based polyurethane and its characterization by optical spectroscopy and scanning tunneling microscopy are presented. This linear polyurethane builds up perfect free-standing films suited for photonic applications. Moreover it may be extruded to long mechanically stable fibers. The photochromic reactions of the polyurethane, as being the electrocyclic ring-closure and ring-opening reactions of the dithienylethene unit in the polymer backbone, occur in a completely reversible and highly efficient fashion.

This paper describes the preparation of a chiral stationary phase based on a 2-hydroxypropyl-β-cyclodextrin polymer coated on porous silica. This method requires first the synthesis of a water-soluble cyclodextrin polymer carried out by the polycondensation of 2-hydroxypropyl-β-cyclodextrin with epichlorohydrin under controlled conditions. In the second step, the obtained copolymer was immobilised onto the porous silica surface by physisorption. The macromolecular features of the copolymer were investigated by size exclusion chromatography coupled with a multiple angle laser-light scattering detector. The evolution of the structural parameters of the modified silica beads (specific surface area and pore size distribution) was determined using a nitrogen adsorption method. The enantio-separation capability of the coated silica phase was evaluated for different polycyclic molecules. It was found that the enantioselectivity was strongly influenced by the geometry and shape of the solutes under study and the presence of an acidic modifier in the mobile phase.

Copolymers of ethylene with 1-decene, 1-tetradecene and 1-octadecene were prepared using the catalyst system racEt[Ind] 2 ZrCl 2 /MAO and were analysed with regard to chemical heterogeneity using crystallisation analysis fractionation (CRYSTAF), differential scanning calorimetry (DSC) and size exclusion chromatography coupled to FTIR (SEC-FTIR). The melting and crystallisation temperatures from DSC decrease linearly with increasing amount of comonomer, independently of the nature thereof. The decrease in crystallisation temperature from CRYSTAF of copolymers with higher 1-olefin content indicates a small dependence on the length of the side chain. The chemical heterogeneity of the copolymers as analysed by DSC and CRYSTAF broadens with increasing comonomer concentration.

The phase behaviour and optical properties of mixtures based on cholesteric copolymers with 3 - 6 wt.-% of photochromic dithienylethene dopants as well as a cholesteric copolymer containing dithienylethene side groups were studied. It was shown that planar-oriented films of the mixtures and of the copolymer possess a selective light reflection in the visible or near IR regions of the spectrum. UV irradiation of the mixture films leads to the appearance of an intense absorbance peak in the spectral range coinciding with the selective reflection band (λ max ≈ 522 - 615 nm depending on the chemical structure of the photochromic fragment). This process is associated with the photocyclization of dopants and photochromic side groups and the ‘degeneration’ of the selective light reflection. The photoinduced coloured form of dopants and photochromic side groups is thermally stable at room temperature, but subsequent irradiation of the film by visible light (550 or 633 nm) induces a decoloration process. The influence of temperature on the rates of forward and back photoprocesses in such polymeric liquid crystalline films was studied. The potentialities of the use of such type of materials for reversible data recording and storage were demonstrated.

A nitroxide (2,2,6,6-tetramethylpiperidin-1-oxyl, TEMPO) mediated polymerization method was applied to the graft polymerization of styrene (ST)/ n-butyl methacrylate (BMA) to isotactic polypropylene (PP). PP peroxides produced by γ-irradiation in air were used as macroinitiator for grafting. The molecular characteristics of grafted and free poly(ST-r-BMA) chains were analysed by gel permeation chromatography, NMR and IR measurements. The molecular weight of grafted poly(ST-r-BMA) cleaved from PP was slightly higher than that of free poly(ST-r-BMA) generated simultaneously in the reaction system. Polydispersities of these polymers were narrow, indicating that grafting proceeded in a living fashion. The incorporated amount of BMA into grafted poly(ST-r-BMA) was smaller than that of free poly(ST-r-BMA). It is considered that the local concentration of BMA around propagating ends of graft poly(ST-r-BMA) was lower than that around free poly(ST-r-BMA) because PP cannot be dissolved in BMA monomer but in ST monomer at the polymerization temperature.

Blends of polyamide 12 (PA12) with liquid polybutadiene (HTPB) were prepared by melt blending over a composition range varying from 0 to 20% of polybutadiene. A study of the potential reactions led to the conclusion that the system undergoes no chemical reaction under the processing conditions used. Scanning electron micrographs of the blends showed a good dispersibility of HTPB in the PA12 matrix. Charpy impact tests and tensile tests demonstrated that the dispersion of HTPB in PA12 provides a good impact toughness enhancement but leads to a decrease of Young's modulus.

Poly-L-lactide (PLA) fibers were obtained by electrospinning of PLA / dichloromethane solutions. Formation of beaded fibers combined with decreased fiber diameters were observed for low PLA concentrations in solution. Increase of the electrical conductivity by addition of pyridinium formiate (PF) caused a significant reduction of bead formation. The electrospinning of dilute PLA / PF / dichloromethane solutions resulted in PLA nanofibers. Systematic variations clearly identified the solution viscosity and the electrical conductivity at otherwise fixed parameters (surface tension, molecular weight, electrode geometry, electrical field, etc.) as crucial parameters for the formation of beads upon electrospinning of PLA / dichloromethane solutions.

The first part of this series is devoted to the preparation of vinyl functionalized multiblock silicones by the process of anionic ring opening polymerization in miniemulsion. The advantage of working in dispersed media is that different scales of reactivities are found between one-chain reactions, taking place at the interface (propagation, backbiting), and two-chain reactions, located in the bulk of the particles (polycondensation and intermolecular redistribution). First, homopolymerizations of octamethylcyclotetrasiloxane (D 4 ) and tetramethyltetravinylcyclotetrasiloxane (D 4 V) were carried out and compared, focusing specifically on the rates of polymerization, backbiting and polycondensation processes. Copolymerization of D 4 with D 4 V then gave insight into the extent of mixed cycles’ formation and particularly how to avoid these. On this basis, recipes were carefully selected so that homopolymerization and scarce co-polycondensation and redistribution progress at the expense of backbiting reactions and thus multiblock copolymers are formed, the microstructure of which was confirmed with 29 Si NMR.

Using small angle neutron scattering and neutron spin echo spectroscopy, two isotopic blends of low molar mass polydimethylsiloxane (PDMS) and polyethylmethylsiloxane (PEMS), and the corresponding binary blends d-PDMS/ p-PEMS and p-PDMS/d-PEMS (d: deuterated, p: protonated) were studied at the critical composition in the homogeneous regime. From the scattering data it becomes evident that coil dimensions and collective dynamics of these both blend systems behave significantly different. Compared to the isotopic mixtures, which exhibit the expected unperturbed chain dimensions and the typical Rouse relaxation, in the binary blends, which differ by a large shift with respect to the critical temperature, considerable coil expansion and spatially restricted Rouse relaxation occur. Both these structural and dynamic effects are in agreement with the model of droplet formation and chain localization, resulting from the existence of microscopic heterogeneities within the spinodal boundaries of the phase diagram. In addition, the observation of Rouse relaxation, spatially restricted to microscopic length scales, provides a new access to the molecular understanding of the critical slowing down of the mutual diffusion process, observed by photon correlation spectroscopy.

Papers published during 2001 - 2002 on the synthesis and preparation of polymers and polymer-based devices and their applications are reviewed. Polymers for drug and gene delivery, gene therapy, controlled drug release, conjugation with peptides, proteins, and nucleotides, tissue engineering, bone repair and regeneration, coatings, wound dressing, artificial skin and other artificial organs are discussed.

Bench scale performance based cone calorimeter investigations were conducted on glass fibre reinforced polyamide 66 (PA-66) and high impact polystyrene (HIPS) materials. Red phosphorus and magnesium hydroxide were used as fire retardants. Dilution, heat sink, barrier and charring mechanisms are considered to be active in the condensed phase. Dilution, cooling and flame poisoning mechanisms are discussed for the gas phase. Cone calorimeter data are used to give a comprehensive fire behaviour assessment in terms of the propensity to cause a quick growing fire and of the propensity to cause a fire of long duration. The external heat flux is varied between 30 and 75 kW/m 2 so that the results for combustion behaviour and flame retardancy, respectively, are valid for different fire scenarios and fire tests. Results on the intrinsic contribution of the steady heat release rate per unit area reveal information about the flammability behaviour. UL 94 results are predicted in close correspondence to UL 94 experiments.

Synthesizing hyperbranched polyurethanes in a one step process using commercially available raw materials: these were the primary conditions for this work. By taking advantage of intramolecular reactivity differences of isocyanate groups in diisocyanates in combination with reactivity differences of OH and NH groups in alkanolamines, it is possible to generate in situ AB 2 molecules by controlling reactions of specific functional groups towards each other. This AA* + B*B 2 approach works without protecting groups and opens up a simple and versatile strategy towards hyperbranched aromatic as well as aliphatic polyureaurethanes. Preferential diisocyanates for this synthesis were 2,4-toluylene diisocyanate and isophorone diisocyanate, whereas diethanolamine and diisopropanolamine were used as isocyanate-reactive counterparts.

A new method of porous polymer structure formation by means of phase separation of two polymers with different degradation rates is proposed. Aromatic polyesters of oxalic acid as fast degradable polymers were synthesized and their degradation properties under alkaline conditions were studied. Heterogeneous mixtures of poly(phenolphthalein oxalate) with poly(lactic acid) were prepared by solution phase separation and co-precipitation, and porous poly(lactic acid) samples were produced by polyoxalate leaching due to its fast degradation.

Keratin fibers from chicken feathers were modified through graft copolymerization with methyl methacrylate in an aqueous medium, using a KMnO 4 / malic acid redox system. Original and grafted fibers were characterized by IR and Raman spectroscopy and their thermal behavior was studied by both differential scanning calorimetry and thermogravimetric analysis. The grafted fiber surface was characterized by scanning electron microscopy. The characterization results show that grafting was effectively achieved and this was confirmed by a ninhydrin test after acidic hydrolysis of the grafted keratin.

Acrylic copolymers made of a casting syrup (prepared from poly(methyl methacrylate) (PMMA) dissolved in methyl methacrylate) and triethylene glycol dimethacrylate (TEGDMA) were synthesized by promoting the decomposition of benzoyl peroxide (BP) with dimethyl-p-toluidine. In addition, conventional copolymers, made of methyl methacrylate and triethylene glycol dimethacrylate monomers, were synthesized via thermal decomposition of BP. The two types of reaction were carried out as bulk polymerizations. Both types of copolymers were studied applying scanning electron microscopy, IR and micro-Raman spectroscopy, differential scanning calorimetry, and dilatometry. It was found that the conventional polymer is a MMA-TEGDMA copolymer without phase separation, while the phase-separated polymer contains microdomains. The shrinkage of the polymers, as well as their morphology, can be easily controlled through the chemical composition.

A kinetic model of the cure of a polyurethane formulation is determined by the evolution of the conversion calculated during adiabatic experiments. The identified kinetic parameters are validated with two different methods: i) by comparing the simulated and measured evolutions of the conversion rates during these adiabatic reactions, ii) by comparing the simulated and measured (using NIR spectroscopy) evolution of the conversion into a mould during a RIM process.

The degradation of chitosan in the presence of poly(vinyl alcohol) (PVA) or poly(acrylic acid) (PAA) by a crude enzyme complex from Trichoderma viride was studied. It was found that neither PVA nor PAA suppress chitosan hydrolysis. By varying the experimental conditions, the optimal conditions for chitosan degradation in the presence of PVA (37°C, pH 6) or PAA (37°C, pH 4) were found. The biocontrol agent T. viride was embedded in films of chitosan, PVA, chitosan/PVA and chitosan/PAA. Microbiological tests showed that T. viride retained its ability to develop and reproduce in all studied film types. The obtained results imply that the prepared systems are appropriate carriers of biocontrol agents and might be used as novel agropharmaceuticals.

A novel alkoxyamine based on N-tert-butyl-1-diethylphosphono-2,2- dimethylpropyl nitroxide (DEPN) has been designed with a functional group, which promotes the chemisorption of free silanols from silicon surface and organicinorganic hybrid materials by a sol-gel process. This alkoxyamine has been synthesized in high yield from styrene oxide and has been employed for the nitroxide-mediated polymerization of styrene and n-butyl acrylate. The resulting alkoxysilane-containing homo- and copolymer precursors have been shown to have narrow molecular weight distributions.

This paper describes the structural control of polyolefins achieved by using group 4 transition metal complex catalysts featuring a pair of phenoxy-imine chelate ligands (named FI catalysts). FI catalysts can produce very low to ultrahigh molecular weight polymers. For example, a Zr-FI catalyst bearing a cycloalkyl group on the imine-nitrogen with methylaluminoxane (MAO) activation is capable of selectively forming vinyl-terminated low molecular weight polyethylenes (M w < 5000) whereas a Zr-FI catalyst with a triethylsilyl group ortho to the phenoxyoxygen can generate ethylene/propylene amorphous copolymers with ultra-high molecular weights (M w > 10 000 000) when treated with i Bu 3 Al / Ph 3 CB(C 6 F 5 ) 4 . In addition, a Ti-FI catalyst, possessing an o-phenoxytrimethylsilyl group, with MAO can form highly syndiotactic polypropylenes ([rrrr] = 84%, T m = 140°C) via a chainend control mechanism. Conversely, upon activation with i Bu 3 Al / Ph 3 CB(C 6 F 5 ) 4 , a Hf-FI catalyst with a tert-butyl group ortho to the phenoxy-oxygen is able to produce high molecular weight isotactic polypropylenes ([mm] = 69%, T m = 124°C, M w = 412 000) via a site control mechanism. Therefore, FI catalysts have shown the ability to create various polyolefin architectures by simple variation of the central metal, the ligand structure and the co-catalyst.

The compatibilizing effect of pyromellitic anhydride (APy) in blends of PA12 and liquid polybutadiene (HTPB) was investigated. Blends were prepared, with or without APy, and the efficiency of this route of compatibilization was evidenced by observation of their morphologies. The addition of APy led to a finer dispersion of HTPB in the PA12 matrix. The formation of a compatibilizing block copolymer was proven by the evolution of the torque, the amine functionality and the size of the particles during blending, and by extraction of the dispersed phase followed by FTIR analysis. The effect of the mixing procedure was also investigated, and it was shown that the best dispersions were obtained when APy was added to a pre-blend of PA12 and HTPB.

The multiresponse maximum likelihood (MML) method and statistical tests - the F-test, the t-Student test, and the sign changes test - were compared with respect to their power of discrimination between two kinetic models, the terminal and the penultimate model, for the radical copolymerization of the styrene - methyl methacrylate monomer system in bulk. The results indicate that the investigated statistical methods (except the sign changes test) are suitable for kinetic-model discrimination when they are applied to a posteriori data of copolymer composition. Although the MML method was shown to be more demanding in the error estimation of experimental data, it can serve as a proper tool for kinetic-model discrimination in copolymerization, provided the correct estimates of the ratio between errors in measured copolymer composition data are known. The main steps of the calculating scheme are given.

We examined mechanical and morphological properties of fully transcrystalline polypropylene grown from the surface of poly(tetrafluoroethylene) sheets. Comparison of mechanical properties between transcrystalline and spherulitic polypropylenes demonstrated that Young’s modulus is dependent on the crystallinity and independent of the supermolecular structure. On the other hand, the mechanical yielding process was predominantly affected by the supermolecular structure, and the mechanical energy required for yielding of transcrystalline sheets was greater than that of the spherulitic morphology. In addition, it was found that mechanical necking is required for the alignment of lamellae in the stretching direction. This means that the unfolding process of lamellae orienting in the stretching direction is associated with necking and ductility.

The distribution of molecular weight (MW) and composition of diblock copolymers is considered theoretically. Assuming that the chain end of each block is coupled randomly, the weight-average MW of the block copolymers is given by M w = w 1 (M w,1 + M n,2 ) + w 2 (M w,2 + M n,1 ), irrespective of the shape of the distribution of each block, where w i is the weight fraction, and M n,i and M w,i are the number- and weight-average MW of each block. In copolymer chains, the chemical compositions as well as the MWs cannot be identical for all polymers, and there exists a bivariate distribution of MW and composition. When the MW distribution (MWD) of both blocks follows the Schulz-Zimm distribution, the bivariate distribution can be obtained analytically. In addition to the bivariate distribution, the full MWD, the average composition as a function of MW, the composition distribution of copolymers having a specified MW, and the overall composition distribution are obtained. The composition distribution, as well as the average composition, becomes independent of MW under the condition σ 1 /M n,1 = σ 2 /M n,2 , where σ i is a parameter indicating the narrowness of the Schulz-Zimm distribution. The present theoretical analysis provides new insight into the design of diblock copolymers.

A series of polybutadienes (PBs) of different molecular weights (in the range of 3000 to 120 000) but of identical microstructure (1,2-PB content ≈ 80%) was synthesized via anionic polymerization. The adsorption in solution of the various monodisperse PBs on carbon black (CB) was studied for different polymer/ CB ratios as well as for polymer and CB concentrations in the range of 0.1 to 100 g/l. The amount of adsorbed polymer was followed and was found to be essentially governed by the polymer concentration, which determines also the conformation of the polymer chain on the filler surface. CB concentration didn’t prove to be a pertinent parameter, whereas the polymer/filler ratio was found to control the formation of the three-dimensional polymer-filler network on the basis of a percolation process. Results are discussed with respect to the available theories.

Poly(butylene terephthalate) (PBT) fibres were obtained by high-speed melt spinning up to a take-up velocity of 8 km/min. Fine structure formation and physical properties of these fibres were investigated. The increase of take-up velocity caused raises in both density and birefringence. In wide-angle X-ray diffraction equatorial profiles, the increase of take-up velocity can be observed in the (010) and (100) reflections of β-crystals; the reflection peaks are the sharpest at a take-up velocity of 6 km/min. The initial modulus of the fibres arises when the fraction of β-crystals is increased, while the tenacity depends more on the fraction of α-crystals, i.e., the total crystallinity. Thermal properties of high-speed spun PBT fibres were measured with differential scanning calorimetry, dynamic mechanical and thermo-mechanical analysis, etc. Endothermic curves become sharper with increasing take-up velocity, and endothermic melting peaks are shifted to higher temperature. Crystal structures are well developed in fibres obtained at higher take-up velocities. The tan δ peaks of PBT fibres tend to shift to higher temperature and the peak intensity is decreased with increasing take-up velocity, i.e., the packing density of PBT fibres is high when the take-up velocity and thus the orientation of amorphous regions is increased. The shrinkage has a tendency to decrease with increasing take-up velocity.

The intrinsic viscosity of polyvinylpyrrolidone (PVP) and various added polymers was investigated by the polymer-solvent method. It has been found that both polymer-polymer interactions and the concentration of the added polymer affect the intrinsic viscosity of PVP. In the ‘polymer-solvent’ system poly(methyl methacrylate) + dimethylformamide (PMMA+DMF), the intrinsic viscosity of PVP decreases as the concentration of PMMA increases, showing that the repulsive interaction between PVP and PMMA originates from the contraction of PVP coils in solution due to the intermolecular excluded volume. However, in the polymersolvent systems poly(vinyl chloride) (PVC) + DMF or poly(vinylidene fluoride) (PVDF) + DMF, the attractive interactions between PVP and PVC or PVDF cause an expansion of PVP coils in solution at high concentrations of PVC or PVDF. The polymer-solvent method allows estimating the compatibility of the used polymers.

Blends of polyamide 12 (PA12) and liquid polybutadiene (HTPB) compatibilized with pyromellitic anhydride (APy) were prepared by melt blending. 10%, 12% and 20% HTPB blends were prepared, with various amounts of APy. The influence of the amount of APy on the morphology of the blends was studied for a wide composition range in the 12% series. Injection moulded tensile and Charpy testing bars were prepared from 10% and 20% binary and compatibilized blends. The deformations of the matrix under room temperature impact and the morphology of the blends were investigated with scanning electron microscopy. Partial miscibilization of HTPB with PA12 due to the addition of APy was postulated to explain the disappearance of polybutadiene in some cases. The mechanical properties of the blends were correlated with morphological parameters. A strong correlation between impact fracture toughness and the amount of non-miscible HTPB was found.

Expressions for the degree of randomness, B, and for the number- and weight-average block lengths of condensation copolymers containing both symmetrical (AA + BB) and unsymmetrical (AB) monomer units are established through an approach based on functional group probabilities. Several parameters introduced in literature to characterize randomness in AA + BB condensation copolymers are also calculated using this approach and compared to B, showing that they are simple linear or rational functions of B. A method for calculating functional group probabilities from the dyad and triad number-fractions determined by NMR spectroscopy is described for poly(ethylene terephthalate)-poly(ε-caprolactone) copolyesters. This method obviously applies to any AA + BB + AB polycondensation and is easily generalizable to other types of condensation copolymers.

Poly(ethyl glyoxylate) (PEtG), a new polyacetal, was synthesized via anionic polymerization in CH 2 Cl 2 . End-capping was achieved using phenyl isocyanate. Average molecular weights in the range of 9000 - 216 000 were obtained. 1 H and 13 C NMR characterization highlight the non-stereoregularity of PEtG. The polymer is quasi-atactic and the polymerization almost followed a Bernoulli process. Compared to its homologue poly(methyl glyoxylate), PEtG exhibits enhanced thermal stability (>200°C) and a lower glass transition temperature, T g . Molecular weight influences T g , but does not affect thermal stability.

The adsorption on carbon black (CB) of a series of monodisperse polybutadienes (PBs) with different molecular weights (M n in the range of 3000 to 120 000) but identical microstructure (1,2-PB content ≈ 80%) was studied in the bulk for different polymer/CB ratios (τ, in the range of 2 to 10 g/g). In this respect we particularly studied the evolution of the amount of polymer, which cannot be extracted from the polymer/filler system upon blending, the so-called bound polymer, and attempted to investigate the conformation of the resulting adsorbed molecules as well as the conditions that control the formation of the polymer/filler network. The conformational transition turned out to depend exclusively on molecular weight, and the networking transition to occur at constant M n 1/2 /τ, essentially through an entanglement process of the adsorbed chains.

A novel polyelectrolyte complex between chitosan and copolymers of 2- acryloylamido-2-methylpropanesulfonic acid (AMPS) and acrylic acid (AA) has been prepared. The formation of the complex has been studied viscometrically, gravimetrically and turbidimetrically in the pH range from 1.2 to 5.8. The stoichiometry and the yield of the complex depend on the copolymer composition and on the pH value of the medium. In the case of copolymers with low content of AMPS units the complexes are enriched in copolymer when formed in the pH range from 1.2 to 4.8. In this pH region mainly AMPS units take part in complex formation. A stoichiometric complex forms only at higher pH values due to the increased number of complexable carboxylate ions of AA units. The stoichiometry of the complexes prepared from copolymers with higher content of AMPS units is close to equimolar and is less sensitive to pH. The obtained complexes are stable up to pH 8. It has been shown that chitosan once included in the complexes remains degradable under the action of a crude enzyme complex produced by the soil fungus Trichoderma viride. The rate of the enzymatic hydrolysis decreases in the order chitosan/PAA > chitosan/P(AMPS-co-AA) > chitosan/PAMPS. Tests on the proliferation of T. viride embedded in chitosan beads have shown that coating the beads with chitosan/P(AMPS-co-AA) complex does not hamper the development of the microorganisms.

The influence of the steric exclusion mechanism on the dependence of the retention on the thickness of the micro-TFFF channel was studied theoretically. A good agreement of theory with experimental data was found. In order to preserve the use of micro-TFFF within an extended range of molar masses and particle sizes, the thickness of the channel cannot be reduced without taking into account a possible deterioration of the separation due to the contribution of steric exclusion to the separation mechanism.

The non-isothermal kinetics of melting and crystallization of gamma-irradiated isotactic polypropylene were investigated by differential scanning calorimetry. At constant temperature the melting rate increased with the dose. During the melting, the average lamellar thickness, the free surface energy and the transport energy through the phase boundary reduced with increasing the dose. The crystallization rate decreased with increasing dose at constant temperature. Mixed α-γ spherulites were grown during crystallization. The non-isothermal crystallization rate expressed, in fact, the rate of secondary nucleation of the lamellae in the spherulites and their growth. Raising the irradiation doses led to a decrease of the crystallization temperature. A critical dose of irradiation of about 200 kGy was found, where the dependences of the calculated kinetic parameters underwent an important change. This change could be successfully connected with the effect of radiation annealing and melting.

Dielectric properties of composite materials, polymer - ferroelectric filler, were investigated in wide frequency and temperature ranges. It has been shown that dielectric properties of polymer composites are a function of the size and concentration of ferroelectric filler particles, since these particles contain a defective outer surface layer with dielectric properties significantly different from those of the ferroelectric bulk. Dielectric properties of composites were found to depend on the type and properties of the polymer matrix, as well as on the method and conditions of composite preparation. Composites cured in the measurement cell possess a more porous structure, their dielectric constant ε' being lower compared to compression molded samples. ε' of polypropylene composites in the ferroelectric phase is higher than that of epoxy resin composites.

The optically active photochromic homopolymer deriving from radical polymerization of the monomer (R)-3-methacryloyloxy-1-(4’-nitro-4-azobenzene)- pyrrolidine, containing a chiral group of one prevailing configuration interposed between the methacrylic moiety and the photochromic azoaromatic chromophore, has been synthesized and characterized. Copolymers with the enantiomeric monomer (S)-3-methacryloyloxy-1-(4’-nitro-4-azobenzene)pyrrolidine have also been prepared in order to evaluate the effect on the overall optical activity of side chain chiral groups of opposite configuration in various ratios. The spectroscopic and chiroptical properties in solution of the polymeric derivatives have been assessed.

Thermoelastic measurements of synthetic rubber/organoclay nanocomposites provided the first experimental evidence for the dramatic dependence on interfacial interactions of the scale of nanoparticle displacements within filler aggregates of synthetic rubber/organoclay nanocomposites at high uniaxial extensions.

We report on the electrochemical synthesis of two novel soluble PPV-like polymers, poly(2-decyloxy-4,4'-biphenylenevinylene), DOPBV, and poly(2-decylsulfonyl- 4,4'-biphenylenevinylene), DSPBV, their spectroscopic and thermal characterization as well as their electrical properties. We also report on the use of sandwich devices Au/DOPBV/Al and Ni/DSPBV/Al to investigate the charge injection and transport characteristics, besides other important parameters such as the optical energy gap and the HOMO energy level, leading to an estimate of the ionization potential and electron affinity of these polymers.

Blends of polystyrene and high-density or linear low-density polyethylene have been prepared in an internal mixer and studied in a wide range of compositions. Phase inversion compositions have been determined using selective extraction and scanning electron microscopy. It appears that phase inversion can occur in a domain of compositions rather than at a single point. The existing models of phase inversion are not complete enough to explain the entire phenomenon, and percolation of each component may be considered to describe the formation of co-continuity.

Natural muscles have mechanical properties that conventional actuators do not possess. These natural machines show large strain, moderate stress, high efficiency and stability, fast response time, high power/weight ratio, long lifetime, etc. In the last years a great interest has arisen to develop materials that mimic natural mechanisms. Conducting polymers have an array of potential applications as artificial muscles since they are capable to produce a moderate displacement when submitted to an electrochemical reaction. This property has been used to fabricate actuator devices that imitate and even improve the performance of natural muscles. For example, conducting polymers show stresses 15 times higher than those generated by mammalian muscles, a high power/weight ratio and a high degree of compliance. However, there are also several responses that need improvement in the actuators based on conducting polymers. Strains are still c. 50% lower than in natural muscles. Most of this kind of actuators only work in liquid media. It is necessary to increase the response time and obtain more durable actuators with longer lifetime and higher stability. In spite of these disadvantages, the first actuators based on conducting polymers are being commercialized. This paper presents a brief summary of some of the actuators based on these polymers, focusing on their design, performance and actuation mechanism.

In order to obtain temperature-responsive hydrogel networks, poly- (glycidol-block-ethylene oxide-block-glycidol) copolymers were chemically crosslinked by using glutaraldehyde and tetraethoxysilane in a sol-gel reaction. The crystallinity of copolymer networks prepared has been estimated by differential scanning calorimetry. Thermo-responsive properties were evaluated by measuring the equilibrium swelling degree for a series of copolymer hydrogels as a function of temperature.

The reversible addition-fragmentation chain transfer (RAFT) bulk polymerization of styrene was studied using 2-cyanoprop-2-yl dithionaphthalate (CPDN) as RAFT agent in the presence or absence of 2,2’-azoisobutyronitrile (AIBN). The results of both thermally and AIBN-initiated styrene (St) polymerizations show that St can be polymerized in a controlled way using CPDN as RAFT agent; i.e., the polymerization rate is first order with respect to monomer concentration, and molecular weight increases linearly with monomer conversion. The molecular weights obtained from gel permeation chromatography are close to the theoretical values and molecular weight distributions are relatively narrow (M w /M n < 1.2). It is confirmed by chain extension reaction that the polymer prepared via RAFT polymerization can be used as a macroRAFT agent. The effects of reaction temperature and mole ratios [St] 0 /[CPDN] 0 /[AIBN] 0 on the polymerization were investigated. The results indicate that the reaction temperature has a positive effect on the polymerization rate, but little effect on molecular weight and molecular weight distribution, and the optimum mole ratios were found to be [CPDN] 0 /[AIBN] 0 > 4/3 and [St] 0 /[CPDN] 0 < 800.

Frontal polymerization (FP) has been successfully applied to the preparation of a polyurethane (PU) having practical interest. By comparing the classical PU synthetic route with FP, the latter allowed for the obtainment of both higher molecular weights and yields. Furthermore, reaction times have been significantly reduced. Eventually, FP materials are characterized by higher glass transition temperature and lower melting point than their batch counterparts.

Differently N-substituted maleimides were copolymerized with styrene to yield alternating styrene-maleimide copolymers (SMI-R) with different chain diameters. The polymers were obtained by free radical polymerization and characterized by NMR and size exclusion chromatography / differential viscometry. Glass transition temperatures were measured by differential scanning calorimetry. An increase in chain diameter and chain stiffness is accompanied by a decrease in the entanglement density, reflected in lower values of the plateau modulus, which were corrected for the low molecular weight portion using the Wasserman/Graessley model. Increasing the chain diameter by a factor of two results in a decrease of the entanglement density to one third. SMI-Me showed a much lower entanglement density than polystyrene (PS) although they have the same chain diameter. SMIMe however is more rigid than PS because of the maleimide five-membered ring structure in the main chain. SMI-Me and SMI-PhOPh show the same glass transition temperature. However, because of the larger chain diameter of SMIPhOPh, it has a much lower entanglement density. Thus, both the chain flexibility and the chain diameter, two parameters that are strongly related, affect the entanglement density.

Carboxyl-terminated polystyrene was esterified with 2,2,2-trifluoroethanol using a carbodiimide-mediated room temperature reaction, and hydroxyl-terminated polystyrene was fluoro-derivatized with trifluoroacetic anhydride. The soformed fluorine-containing esters were then quantitatively determined with 19 F NMR, using α,α,α-trifluorotoluene as secondary standard. This provides a technique for the reliable determination of carboxylic acid and hydroxyl groups in small samples of polymers.

Microhardness (H) has been used to quantitatively characterize the quality of the interphase boundary of blends of atactic polystyrene (PS) with natural rubber (NR) and the compatibilizer styrene-butadiene-styrene (SBS) block copolymer. Qualitative conclusions are drawn for the same purpose from scanning electron microscopy (SEM) observations on surface indentation. Cast films of neat PS and the blends PS/NR, PS/SBS and PS/NR/SBS were prepared from a common solvent (toluene). While neat PS shows a constant H = 175 MPa, the PS/SBS blend exhibits a gradual decrease starting from H = 130 - 140 MPa at a distance of about 100 μm from the phase boundary up to the final value of 25 MPa. For the PS/NR blend this decrease starts at about 50 μm, reaching the same final value. Owing to the elastic recovery, no indentations on the NR or SBS particles surface can be detected as confirmed by SEM. The compatibilized blend PS/NR/SBS is characterized by the thinnest phase boundary (about 25 μm) and a final H value of 75 MPa which demonstrates that the compatibilizer SBS is distributed just on the phase boundary between PS and NR. Results confirm previous findings in incompatible blends of poly(methyl methacrylate)/NR, highlighting that microindentation is a sensitive tool for studying the breadth and quality of the interphase boundary in compatibilized or non-compatibilized polymer blends and other non-homogeneous materials. This technique allows, in addition, the localization of the compatibilizer in the polymer blends.

This study examines the compatibilization of the polyetherimide Ultem 1000 with the thermotropic liquid crystalline polymer Vectra A 950 by using an epoxy resin (PKFE) as compatibilizer. IR spectroscopy and electron-microscopic morphological analysis indicate the grafting of PKFE molecules on fibrillar domains of Vectra during melt mixing. Moreover, morphological analysis shows that the addition of PKFE improves the dispersion and decreases the size of Vectra fibrils. Both Vectra and PKFE significantly reduce the glass transition temperature of Ultem in ternary blends. The tensile modulus and the ultimate strength of the blends are improved with respect to those of neat Ultem. However, the final materials are very fragile. The roles of Vectra and PKFE are discussed.

4-Vinylpyridine monomer was mixed with organically modified montmorillonite (MMT) and polymerized in the presence of 2,2’-azoisobutyronitrile as radical initiator. Organophilic montmorillonite was obtained by using a block copolymer of poly(methyl methacrylate) and quaternized poly(4-vinylpyridine) (P4VP) in different compositions. X-ray diffraction (XRD) and thermogravimetric analysis confirmed that the block copolymer is inserted between MMT layers while the interlayer distance is expanded. The P4VP nanocomposites obtained from the block copolymer with the longer P4VP block exhibited no XRD peak, suggesting an exfoliated structure. These composites showed increased storage modulus and thermal stability at a very low loading of 1 - 2 wt.-%, compared to neat P4VP. Scanning electron microscopy and atomic force microscopy analyses were also conducted for selected nanocomposites.

This paper presents the latest improvements, in terms of reactivity and molar masses, of the process of cationic polymerisation of p-methoxystyrene in miniemulsion, which was published previously [Cauvin et al., Macromolecules 2002, 35, 7919]. The formulation was adapted to change dramatically the specific surface and the polarity of the interface where the polymerisation takes place. Adding hexadecane permits to significantly decrease the particle diameter and thus to favour a faster polymerisation rate. In addition, droplets generated by sonication are ideally covered by the INISURF (initiator/surfactant) dodecylbenzenesulfonic acid and nucleate quantitatively (true miniemulsion polymerisation). Hexadecane addition finally ensures a better stability of the polymerised dispersion. A more hydrophobic acidic surfactant, though used at much smaller concentrations, again allowed increasing the polymerisation rate. Both systems, however, show no improvements in terms of molar masses compared to those observed previously. By separating the initiating agent (a super acid such as triflic acid) from the surfactant (a non-ionic one) an increase of molar masses is obtained but accompanied by an important drop of the polymerisation rate.

Morphological features and the melting behaviour of truncated lozenge crystals have been studied. For the crystals investigated, the heights of the (110) and the (200) sectors were measured to be 14.5 and 12.7 nm, respectively, using atomic force microscopy (AFM) in contact and non-contact mode. Moreover, melting temperatures of 123°C for the (110) sector and of 120°C for the (200) sector have been measured using real-time AFM during annealing experiments. Applying atomic force acoustic microscopy and the n-alkane decoration technique, no difference in the surface fold organisation of (110) and (200) sectors could be detected. For similar stem lengths, variations in stem tilt angle within the sectors might cause the thickness difference observed. However, a very high tilt angle difference above 20° is required. More likely, a shorter stem length within the (200) sector may cause its lower melting temperature.

Copolymers of 2-acryloylamido-2-methylpropanesulfonic acid (AMPS) and acrylic acid (AA), as well as the corresponding homopolymers PAMPS and PAA, were studied in vitro on human pool plasma for their anticoagulant activity. The values of the haemostatic parameters - prothrombin time, activated partial thromboplastin time and thrombin time - depend on the composition and the concentration of the (co)polymers. Reptilase time remains unchanged on adding the (co)polymers. A broad concentration range from 16 μg/ml to 3 mg/ml was studied. The copolymers possess anticoagulant activity, which is higher at higher content of AMPS units. It was found that, at certain concentrations, the haemostatic parameters of PAMPS are close to that of heparin. PAA has the lowest anticoagulant activity.

Terpolymers based on poly(methyl methacrylate), containing terpyridinemoieties as well as epoxide groups, were synthesized via free-radical polymerization. The products were cross-linked non-covalently with iron(II) ions and covalently by treatment with AlCl 3 . Both steps could be combined in different order. The non-covalent cross-linking could be reversed by applying a strong competing ligand. The swelling behaviour of the polymers was investigated.

Crystallization kinetics and melting behaviour of poly(propylene terephthalate) (PPT) were investigated by means of differential scanning calorimetry and hot-stage optical microscopy. Isothermal crystallization kinetics was analysed according to the Avrami treatment. The effects of temperature and duration of melting on the overall rate of isothermal crystallization were studied: the rate was found to decrease with increasing melting temperature and melting time. This result was discussed on the basis of the gradual destruction of predetermined athermal nuclei. Values of the Avrami exponent close to 3 were obtained, regardless of the adopted thermal treatment and the crystallization temperature, T c , in agreement with a crystallization process originating from predetermined nuclei and characterized by three-dimensional spherulitic growth. As a matter of fact, spacefilling spherulites were observed by optical microscopy at all T c ’s, independent of the applied thermal treatments. For each of them, the rate of crystallization became lower as T c increased, as usual at low undercooling where the crystallization process is controlled by nucleation. The observed multiple endotherms, which are commonly displayed by polyesters, were influenced by T c and ascribed to melting and recrystallization processes. Linear and non-linear treatments were applied in order to estimate the equilibrium melting temperature for PPT, by using the corrected melting temperatures. The non-linear estimation yielded an about 33°C higher value with respect to the one obtained by means of the linear approach. Through the analysis of secondary nucleation theory, the classical II→III transition was found to occur at a temperature of 194°C. The average work of chain folding for nucleation was determined to be c. 5.2 kcal/mol. The heat of fusion was correlated to the specific heat increment for samples with different degree of crystallinity and the results were interpreted on the basis of the existence of an interphase, whose amount was found to depend on the thermal treatment the polymer was subjected to.

Aromatic polyamide (aramid) copolymers having a highly branched architecture were prepared by direct polycondensation of an AB 2 monomer (5-(4-aminobenzoylamino) isophthalic acid) with an AB monomer (N-(4-aminophenyl)terephthalamic acid). Two synthetic routes have been followed for copolymer preparation, differing from each other in the overall monomer content and the type of salts added to the reaction medium (LiCl or LiCl + CaCl 2 ). Otherwise, both methods used the same conditions and the same condensing agent (triphenyl phosphite). The feed ratio of the monomers affected the copolymer solubility in aprotic polar solvents such as N,N-dimethylformamide, N-methylpyrrolidone and dimethyl sulfoxide. Only high AB 2 /AB monomer ratios allowed obtaining completely soluble polymers in the above media. Also copolymer intrinsic viscosity was influenced by that ratio as well as by the polymerisation routes. IR measurements gave an indication of polymer structure evolution as a function of the monomer feed ratio, while 1 H NMR experiments verified the actual monomer composition in the synthesized polymers. The monomer feed ratio turned out to influence polymer properties, such as degree of crystallinity, thermal degradation temperature and liquid crystalline behaviour. Some of the characterisation techniques we used ( 1 H and 31 P NMR, IR, SEM-EDS) revealed the presence of phosphorus derivatives in the copolymers, despite extensive sample purification. This presence is coming from derivatives of the condensing agent, and is directly related to the content of AB 2 -type structures present in the copolymers.

New electro-conjugated diazine-based oligo(phenylene vinylene) derivatives with some interesting optical and thermal properties have been synthesised and characterised. These conjugated systems are built up on two benzenic cycles linked to a central diazine, either pyrimidine or pyrazine, through a carbon-carbon double bond. Both benzenic rings are substituted by one or two alkoxy chains. The length, the position and the number of alkoxy chains per benzenic ring have been varied and have proved to modulate both optical and thermal properties. Optical properties have been studied by UV-visible absorption spectroscopy as well as emission spectroscopy. Differential scanning calorimetry, wide-angle X-ray scattering and optical microscopy under crossed polarizers have been applied for characterising the thermal transitions and crystalline changes occurring in these conjugated systems.

Folded chains of syndiotactic polystyrene located on the surface of its solution-grown crystals (SGCs) have been observed on nano scale by use of atomic force microscopy (AFM). Transmission electron micrographs of the SGCs on the mesoscopic scale exhibited truncated-lozenge platelets accompanied by a sharp electron diffraction pattern of the β”-form. AFM images of selected areas on the SGC surface indicated folded chains existing periodically on the surface with c. 1.3 to 1.4 nm spacing, suggesting that the polymer chains are aligned in parallel with the {230} growth faces of SGC.

The electrochemical and photoelectrochemical characteristics of conducting polymer bilayers composed by polypyrrole, PPy, and poly(3-methylthiophene), PMeT, are described. The bilayers were produced by galvanostatic deposition of the polymers using different charge densities. Scanning electron micrographs indicate that the sequence of polymerization affects the surface morphology of the bilayers and, while PMeT polymerizes into the pores of the PPy film, a PPy film is formed over the PMeT film. Cyclic voltammetry of the bilayers shows the peaks corresponding to PPy and PMeT, regardless of the sequence of deposition; however, the potentials of redox processes are slightly shifted. The sequence of polymer deposition also affects the photoelectrochemical properties of the bilayers. The results show that, for a bilayer with PMeT as inner polymer and PPy as outer polymer, an enhanced photocurrent can be obtained by controlling polymer film thickness.

The direct synthesis of poly(p-phenyleneterephthalamide) has been successfully performed by polymerizing its dimer, N-(4-aminophenyl)terephthalamic acid, instead of p-phenylenediamine and terephthaloyl chloride or terephthalic acid, as commonly carried out. An intrinsic viscosity much higher than those typical of the commercial fibres (Kevlar ® ) has been obtained. The procedure and the advantages of the method are highlighted.

The first frontal atom transfer radical polymerization (FATRP) has been successfully carried out using tri(ethylene glycol) dimethacrylate as a monomer. The effect of the catalyst/initiator ratio has been investigated and related to the front velocity and its maximum temperature. By comparing this new approach with classical radical polymerization routes and with conventional frontal polymerization, it was found that the so-obtained polymer is characterized by higher conversion, shorter reaction times, higher degradation temperature, and does not contain entrapped bubbles.

The melting and crystallization behaviour of random copolymers of propene with 1-butene, 1-pentene and 1-hexene synthesized with the catalyst system (CH 3 ) 2 Si(2-methylbenz[e]indenyl) 2 ZrCl 2 /methylaluminoxane (MAO) were investigated by differential scanning calorimetry and crystallization analysis fractionation (CRYSTAF). The melting and crystallization temperatures decreased linearly with increasing comonomer content. The depressions of the melting and crystallization temperatures are strongly dependent on the nature of the monomer and are more pronounced for copolymers of propene with 1-hexene than with 1-butene. In comparison to 1-hexene and 1-butene, the incorporation of 1-pentene leads to an intermediate behaviour. This is in contrast to the behaviour of copolymers of propene with longer chain 1-olefins, where the melting and crystallization temperatures are independent of the comonomer type. The depressant effects of the amount of comonomer incorporated on the melting and the crystallization temperatures are equal.

The occurrence of nematic liquid-crystalline ordering in semidilute and concentrated solutions of semiflexible macromolecules has been studied by means of grand canonical Monte Carlo computer simulations using the bond fluctuation model and the configurational bias scheme. Chain length was equal to 20 monomer units, while the persistence length was about 5 monomer units. We used an intramolecular stiffness potential depending on the angle between successive bonds along the chain and on the bond length, and an attractive interaction between monomer units to model variable solvent quality. We have monitored the processes of appearance and destruction of monodomain and multidomain nematic configurations. Our findings are that the first stages of both the ordering and disordering processes occur upon sufficient oversaturation through the spinodal ordering scenario. Possible screening of nucleation processes and the applicability of our model to real kinetics are discussed. Results of our simulations are visualized in six movies.

The kinetics of interchain exchange reactions proceeding via end-group mechanism in homogeneous polymer blends is studied theoretically. A set of kinetic equations describing the evolution of the block weight distribution is derived. It is demonstrated that the process may be divided into a fast and a slow stage. The fast stage is characterized by alteration in the fractions of end sequences of different type. At the same time most of the homopolymer chains transform into copolymer with block weight distribution close to the Flory distribution. In the course of the subsequent slow stage, the distribution shape is preserved, with average block lengths gradually decreasing to the values typical of the completely random copolymer. The copolymer composition is found to change mostly in the course of the fast stage of the process. The possibilities of using kinetic data for the discrimination between end-group and direct interchange mechanisms are discussed.

Functional segmented polymer networks (FSPNs) were synthesised via free radical initiated copolymerisation of polytetrahydrofuran (PTHF) bis-macromonomers with vinylbenzyl chloride (VBCl). The purpose of this work was to create FSPNs, providing supports with a functional group that can be substituted and may serve to immobilise other reagents such as catalysts. After the preparation and detailed characterisation of several PTHF bis-macromonomers, FSPNs were prepared with varying molecular weight of the PTHF chain and varying PTHF/ PVBCl ratio. Measurements of the soluble fraction and elemental analyses demonstrated that FSPNs with a wide composition range could be prepared. From dynamic-mechanical and thermal analyses, it could be concluded that most FSPNs showed some degree of compatibility and complete absence of crystallinity. The mechanical properties of the FSPNs are directly related to their composition. The degree of substitution of all networks is close to quantitative.

Separation of blends of styrene-butadiene rubber and butyl rubber was accomplished by gradient HPLC. Using a polar stationary phase and chloroformcyclohexane as eluent, the blends were separated with regard to chemical composition, irrespective of the molar masses of the components. The exact chemical structure of the blend components was analysed by coupling the chromatographic separation to FTIR detection. FTIR spectra of the components reveal information on styrene and butadiene contents and the conformation of the butadiene units (1,2-, 1,4-cis and 1,4-trans units). Complete separation of the blends with respect to chemical composition and molar mass was achieved by two-dimensional liquid chromatography. Combining gradient HPLC and size exclusion chromatography in a fully automated 2D chromatography set-up, the complex distributions of chemical composition and molar mass were fingerprinted simultaneously.

An efficient method is described for the simultaneous introduction of 4-ferrocenylbutyl and n-hexyl side groups into cellulose. For this purpose, cellulose triacetate is treated in dimethyl sulfoxide/NaOH solution with mixtures of 4-bromobutylferrocene and n-hexyl bromide. An almost quantitative conversion of the cellulose hydroxyl groups was reached when less than one ferrocene substituent was attached to the cellulose repeating units on average. At higher degrees of ferrocene substitution, some of the cellulose hydroxyl groups seem to remain unsubstituted. This conclusion has been drawn on the basis of size exclusion chromatography (SEC) with online light-scattering detector where coil contraction was observed with increasing ferrocene content in the cellulose sample. This finding was further supported by IR spectroscopy, viscometry, and conventional SEC investigations. We assume that steric hindrance of the bulky side groups is responsible for incomplete conversion.

An efficient method is described for the simultaneous introduction of 4’-p-benzyl-2,2’:6’,2’’-terpyridine and benzyl side groups into cellulose. For this purpose, cellulose triacetate was treated in dimethyl sulfoxide/NaOH solution with mixtures of 4’-p-bromomethylphenyl-2,2’:6’,2’’-terpyridine and benzyl bromide. An almost quantitative conversion of the cellulose hydroxyl groups was reached when less than one terpyridine substituent was attached to the cellulose repeating units on average. At higher degrees of terpyridine substitution, some of the cellulose hydroxyl groups seem to remain unsubstituted. This conclusion has been drawn on the basis of NMR, IR and solubility measurements. We assume that steric hindrance of the bulky side groups is responsible for incomplete conversion. In a final step, the terpyridine substituents of the cellulose derivatives could be converted quantitatively into ruthenium(II) complexes via treatment with activated [Ru(tpy)Cl 3 ] in N,N-dimethylacetamide/1-butanol (tpy: 2,2’:6’,2’’-terpyridine).

Alternating poly(amide urea)s from ε-caprolactam, diamines H 2 N-(CH 2 ) x - NH 2 (x = 2 - 4), and diphenyl carbonate were prepared in two steps. The microstructure of the poly(amide urea)s, as determined by means of 1 H NMR spectroscopy, reveals a strictly alternating sequence of the building blocks. The molecular weights and polydispersities obtained were 7500 < M n < 10 000 and 1.48 < M w /M n < 1.56, respectively. Thermal properties were determined by means of differential scanning calorimetry (DSC) (163.9°C < T m < 197.2°C; 55.5°C < T g (2 nd heating) < 72.2°C), and thermogravimetric analysis (TGA). TGA shows a three-step decomposition at 200, 350, and 450°C, which was attributed to the cleavage of O-phenyl urethane end groups, as well as urea and amide linkages. These assignments were made by comparison with model compounds. Furthermore, alternating poly- (amide urethane urethane)s from ε-caprolactam, diamines, and ethylene carbonate were prepared in three steps. The microstructure of the poly(amide urethane urethane)s, as determined by means of 1 H NMR spectroscopy, reveals imperfections. The molecular weights and polydispersities obtained were 5400 < M n < 17 000 and 2.08 < M w /M n < 2.99, respectively. Thermal properties were determined by means of DSC (155.9°C < T m < 159.0°C; 35.5°C < T g (2 nd heating) < 39.0°C) and TGA. TGA shows a complex decomposition due to the formation of ethylene carbonate by cleavage of the urethane groups (at approx. 230°C) and formation of poly(amide urea)s. The newly formed poly(amide urea)s decompose in a similar way as the poly(amide urea)s.