Segmented Block Copolymers with Monodisperse Hard Segments: The Influence of H‐Bonding on Various Properties

The properties of segmented‐copolymer‐based H‐bonding and non‐H‐bonding crystallisable segments and poly(tetramethylene oxide) segments were studied. The crystallisable segments were monodisperse in length and the non‐hydrogen‐bonding segments were made of tetraamidepiperazineterephthalamide (TPTPT). The polymers were characterised by DSC, FT‐IR, SAXS and DMTA. The mechanical properties were studied by tensile, compression set and tensile set measurements. The TPTPT segmented copolymers displayed low glass transition temperatures (T_g, ?70 °C), good low‐temperature properties, moderate moduli (G′ ≈ 10–33 MPa) and high melting temperatures (185–220 °C). However, as compared to H‐bonded segments, both the modulus and the yield stress were relatively low.

     

Synthesis and Characterization of Segmented Block Copolymers Based on Hydroxyl‐Terminated Liquid Natural Rubber and α,ω‐Diisocyanato Telechelics

Summary: Segmented block copolymers, consisting of non‐polar soft segments from hydroxyl‐terminated liquid natural rubber (HTNR) and polar hard segments from α,ω‐diisocyanato telechelics obtained by “criss‐cross”‐cycloaddition, have been synthesized. The block copolymer formation took place under relatively mild reaction conditions at 80 °C in dichloroethane in the presence of dibutyltin dilaurate as a catalyst. The resulting block copolymers were characterized by spectroscopic techniques (¹H NMR, FTIR, UV‐vis spectroscopy) as well as GPC for molar mass determination. The block copolymers were compression molded in a hot stage press, and the resulting samples were characterized by DSC and stress‐strain measurement. The solubility and phase morphology of the materials have also been studied.

Segmented block copolymer from HTNR and α,ω‐diisocyanato telechelics     

The Solid State Postcondensation of PET, 2

Summary: A process for the solid state polycondensation of PET is proposed. It is shown that by correctly choosing the prepolymerisation conditions it is possible to crystallise the product and to directly polymerise it in a dispersed phase. This process is significantly faster than the “standard” PET processes, and allows one to obtain high molecular weights directly from a prepolymer without the need to use an intermediate solution polymerisation step.

Reactor set‐up for precursor preparation and dispersed phase prepolymerisation.     

Transcrystallinity in Surface Modified Aramid Fiber Reinforced Nylon 66 Composites

Aramid (kevlar‐49) fibers were surface treated by two different methods to induce roughness and then used to produce unidirectional nylon 66 based composites. The transcrystallinity generated around the treated fibers was characterized by SEM and polarized light microscopy and compared with the regular transcrystalline layers produced by pristine aramid under the same processing conditions. The treated fibers generated a double transcrystalline layer, the inner layer being thinner and more compact than the regular nylon 66 transcrystallinity. In addition, mechanical testing of the composites showed the longitudinal Young's modulus of the treated fiber composites to be significantly higher than the control in a wide range of fiber volume fractions.

Polarized light microscopy picture of double transcrystallinity in Br/NH₃ treated aramid fiber reinforced nylon 66.     

Photoinduced Polymerization in the Wall of Hollow Capsules

Summary: Novel light‐sensitive hollow capsules were fabricated from the small molecule 3‐sulfopropylacrylate potassium (SPA) and poly(allylamine hydrochloride) (PAH). With UV irradiation, SPA could be photopolymerized in the wall of hollow capsules. After photopolymerization the capsule size and surfaces showed pronounced differences. The capsules became much more rigid as indicated by an increase in the modulus of more than a factor of 5.

CLSM image of SPA/PAH hollow capsule emission at 554 nm, from rhodamine B after photopolymerization.     

Detailed Molecular Structure Modeling – A Path Forward to Designing Application Properties of ldPE

Summary: This paper describes a step on the ambitious aim to “design” application properties of ldPE by first simulating the detailed molecular structure of a high‐pressure tubular reactor product. The reactor of a certain configuration produces under well‐defined operating conditions. The next step is to correlate the structure with the application properties. Finally, the sequence will be reversed in order to deduce the operating conditions, which lead to the desired product quality. Two‐dimensional distributions, in molecular weight and branching frequency, as well a two compartment models with a core and a shell stream were simulated and compared with experimental results. Therefore, CFD simulations were carried out to discretize the reaction medium. Samples were taken from both pilot and commercial plants. The TREF‐SEC analytical method was successfully applied in order to measure the microscopic structure of the material. The tremendous numerical problems were solved with the help of the software PREDICI .

Detailed MWD for a pilot scale reactor product.     

Viscoelasticity in Polymer Films on Rigid Substrates

The viscoelasticity of two thermally crosslinked polymer coatings was examined in terms of relaxation of the applied stress after a sudden strain. Two different transient methods were utilized: flat‐ended cylindrical indentation testing of a polymer film on a rigid substrate and tensile testing of a corresponding free‐standing polymer film. The correlation between tensile and indentation tests was studied. The mechanical response of a viscoelastic layer deposited on a rigid substrate was investigated as a function of indentation depth. There was good agreement between the results of the tensile and indentation tests for thick film layers at moderate indentation depths. The findings indicate that the substrate influences the coating performance by reducing the viscous contribution to the stress response and amplifying the magnitude of the equilibrium modulus for large indentation depths. The indentation method utilized here was shown to be a potentially suitable tool for the determination of Poisson's ratio of polymer films.

     

Biocomposites Made from Short Abaca Fiber and Biodegradable Polyesters

Natural fiber‐reinforced biodegradable polyester composites were prepared from biodegradable polyesters and surface‐untreated or ‐treated abaca fibers (length ca. 5 mm) by melt mixing and subsequent injection molding. Poly(butylene succinate)(PBS), polyestercarbonate (PEC)/poly(lactic acid)(PLA) blend, and PLA were used as biodegradable polyesters. Esterifications using acetic anhydride and butyric anhydride, alkali treatment, and cyanoethylation were performed as surface treatments on the fiber. The flexural moduli of all the fiber‐reinforced composites increased with fiber content. The effect of the surface treatment on the flexural modulus of the fiber‐reinforced composites was not so pronounced. The flexural strength of PBS composites increased with fiber content, and esterification of the fiber by butyric anhydride gave the best result. For the PEC/PLA composites, flexural strength increased slightly with increased fiber content (0–20 wt.‐%) in the case of using untreated fiber, while it increased considerably in the case of using the fiber esterified by butyric anhydride. For the PLA composite, flexural strength did not increase with the fiber reinforcement. The result of soil‐burial tests showed that the composites using untreated fiber have a higher weight loss than both the neat resin and the composites made using acetylated fiber.

Flexural modulus of PBS composites as a function of fiber content.     

The Anisotropy of Fibrillar Silicate/Rubber Nanocomposites

Summary: Fibrillar silicate (FS)/rubber nanocomposites were successfully prepared by directly mixing modified FS with rubber matrix. It is found that FS could be separated into nano‐fibrils with diameters less than 100 nm by the shear forces during mixing. The stress‐strain characteristics of these composites are similar to those for short micro‐fiber/rubber composites (SFRC). Nevertheless, these FS/rubber composites have some outstanding advantages over the conventional SFRC, even though the reinforcing effect of FS is restricted due to its small shape aspect ratio. More importantly, the differences in mechanical properties of the composites in the two different directions show that SBR/FS and NBR/FS composites both exhibit obvious anisotropy, which strongly depends on the preparation process, FS concentration, and rubber matrix. These factors were thoroughly investigated in this paper, and it can be concluded that the anisotropy of the composites was due to the orientation of nano‐fibrils.

     

The Solid State Postcondensation of PET, 3

Summary: It was demonstrated that it is possible to produce prepolymers with a number‐average degree of polymerisation on the order of 5–40 directly in a liquid‐liquid dispersion in less than three hours. It was also shown that prepolymers made via this route and rapidly crystallised by the addition of a dispersant at ambient temperature are more porous than prepolymers made in an industrial liquid melt process.

SEM micrograph of prepolymers pLL‐PTA with \overline {DP} _{\rm n} = 28, d_p ∈ 63–125 μm.     

Synthesis and Characterization of Biodegradable Poly(ε‐caprolactone)‐Polyglycolide‐Poly(ethylene glycol) Monomethyl Ether Random Copolymer

Summary: Poly(ε‐caprolactone)‐polyglycolide‐poly(ethylene glycol) monomethyl ether random copolymers were synthesized from ε‐caprolactone (ε‐CL), glycolide (GA) and poly(ethylene glycol) monomethyl ether (MPEG) using stannous octoate as catalyst at 160 °C by bulk polymerization. The copolymers with different composition were synthesized by adjusting the weight ration of reaction mixture. The resultant copolymer with a weight ratio (10:15:75) of MPEG2000, GA, and CL was characterized by IR, ¹H NMR, GPC and DSC. The new biodegradable copolymer has potential for medical applications since it is combined with properties of PCL, PGA and MPEG.

     

Ternary Gels of a Polymer Blend and a Recycled Oil: Their Use as Bitumen Modifiers

A blend of random ethylene‐vinyl acetate copolymer (EVA) and triblock styrene‐butadiene‐styrene copolymer (SBS) was dissolved in a recycled engine oil to obtain ternary thermoreversible gels. As the temperature was increased, first a network associated with EVA disappeared, and a second one associated with SBS dominated, maintaining the elastic response of the system. The principal advantage of these ternary systems is that their mechanical properties and thermal stability are better than that of binary gels. These gels, made from waste, can be used as bitumen modifiers to obtain binders of improved properties and good stability, which are useful for road surfacing.

Temperature sweeps of elastic modulus performed at a frequency of 1 Hz.     

Near Infrared Reflection Spectroscopy: A Versatile Tool for Rapid Characterization of Olefin Copolymers and High‐Throughput Experiments

Near infrared (NIR) spectroscopy was developed as a rapid analytical method for the determination of the composition of olefin copolymers obtained in high‐throughput screening. NIR spectra of ethene/propene and ethene/1‐hexene copolymers, also characterized by means of ¹³C NMR spectroscopy, were recorded and used to design multivariate calibration models. Different methods for the preprocessing of the spectra, including the linearization by non‐linear transformations, were compared. Optimal methods and error estimates were established using crossvalidation. This technique is of particular interest for the rapid on‐line analysis of high‐throughput experiments in the field of polymer and catalyst design employing methods from combinatorial chemistry.

Predicted versus true value of the propene incorporation and standard deviation for ethene/propene copolymers.     

Polydepsipeptides I. Synthesis and Characterization of Copolymers of α-Amino and α-Hydroxy Acids

Copolymers of the type were synthesized and characterized. The syntheses of these copolymers were achieved by copolymerization of an α-amino acid N-carboxy anhydride and an α-hydroxy acid anhydrosulfite in the presence of a catalyst. The copolymers were characterized by spectroscopic methods including infrared, circular dichroism and nuclear magnetic resonance. Specific cleavage of the ester bonds by hydroxylamine in the cold confirmed the A-B block structure where the A represents the poly(amino acid) segment and the B indicates the polyester segment. Measurements by nmr and viscosity indicate that the blocks consist of short chain lengths.     

Exertion of Inhibiting Effect by Aluminosilicate Layers on Swelling of Solution Blended EVA/Clay Nanocomposite

Summary: Ethylene vinyl acetate (EVA) copolymer/dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) nanocomposites were swelled in xylene under atmospheric condition. Swelling index of these nanocomposites decreased with filler loading indicating that the solvent uptake of these nanocomposites was inversely related to the filler contents. The volume fractions of nanocomposites showed an increasing trend with filler concentration because of unswelling effect exerted by aluminosilicate layers. The cross‐link density was determined using the Flory‐Rehner equation and it was observed that the cross‐link density of these nanocomposites also showed an increasing trend with increasing filler loading. Free energy change (ΔG_mix) and the change in entropy (ΔS_mix) on swelling of EVA/12Me‐MMT nanocomposites in xylene were calculated and these values reaffirmed that the interaction between polymer chains and silicate layers was very strong which induced remarkable inhibiting ability on EVA matrix when swelled in xylene.

TEM photograph of EVA/12Me‐MMT nanocomposite containing 8 wt.‐% 12Me‐MMT.     

Improved Design of Shearing Sections with New Calculation Models Based on 3D Finite‐Element Simulations

New models for the Maddock and spiral shearing sections have been developed, employing three‐dimensional finite element analysis (3D FEA). These models describe the pressure‐throughput and power consumption behavior of the shearing sections for both the extrusion and the injection molding process and have been implemented in the REX 6.0 and PSI 4.0 simulation software. As a consequence it is now possible to describe the process behavior of these shearing sections within just a few seconds with the accuracy of FEA calculations.

Actual Maddock shearing section (left) and actual spiral shearing section (right).     

Cover Picture: Macromol. Mater. Eng. 8/2005

Summary: Poly(butylene succinate‐co‐adipate) (PBSA) and organically modified montmorillonite (OMMT) nanocomposites of three different compositions were prepared by melt‐extrusion in a batch mixer. The structure of the nanocomposites was studied using X‐ray diffraction (XRD) and transmission electron microscopy (TEM) that revealed a coexistence of exfoliated and intercalated silicate layers dispersed in the PBSA matrix, regardless of the silicate loading. The degree of crystallinity of PBSA decreases with the addition of OMMT platelets. Dynamic mechanical analysis revealed remarkable increase in flexural storage modulus when compared with that of neat PBSA. Tensile property measurements exhibit substantial increase in stiffness with simultaneous increase in elongation at break of nanocomposites as compared to that of neat PBSA. The effect of clay loading on the melt‐state linear viscoelastic behavior of mixed intercalated/exfoliated nanocomposites was also investigated.

Elongation at break of compression molded annealed samples of neat PBSA and various PBSACNs.     

Synthesis of Fluorinated Hyperbranched Polymers and Their Use as Additives in Cationic Photopolymerization

Summary: A fluorine containing hyperbranched polymer was synthesized by modifying an aromatic‐aliphatic hyperbranched polyester with a semifluorinated alcohol via a Mitsunobu reaction and was subsequently used as an additive in cationic photopolymerization of an epoxy resin. The remaining OH groups of the fluorinated hyperbranched polymer interact with the polymeric carbocation through a chain‐transfer mechanism inducing an increase in the final epoxy conversion. The fluorinated HBP induces modification of bulk and surface properties, with an increase in T_g and surface hydrophobicity already reached at very low concentration. The HBFP additive can, therefore, protect the coatings from aggressive solvents, increases hardness, and allows the preparation of a low energy surface coating.

Synthesis of fluorinated hyperbranched polyester.     

Polymerization Catalysis in Liquid Propylene: High Activities and Molecular Weights in Propylene/CO Copolymerization Reactions

Summary: The dicationic [(dppp)Pd(NCCH₃)₂](BF₄)₂ catalyst (dppp = 1,3‐bis(diphenylphosphino)propane) was applied in a liquid monomer, two phase process for the CO/propene copolymerization reaction. For the first time it was possible to synthesize propene/CO copolymers with an activity up to 7 500 g/(mol · h) and molecular weights of 500 000 g/mol. Activities up to 40 000 g/(mol · h) could be obtained with the use of the unsymmetric catalyst [(CF₃‐dppp)Pd(NCCH₃)](BF₄)₂ (CF₃‐dppp = 1‐diphenylphosphino‐3‐bis[3,5‐di(trifluormethyl)phenyl]phosphinopropane) in homogeneous liquid propene solution.

Granules found after copolymerization.     

Thermal decomposition of uranyl chloride hydrate

The thermal decomposition of uranyl chloride hydrate has been investigated by thermal analyses, X-ray diffraction and infrared spectroscopy. From the results it is concluded that uranyl chloride hydrate decomposes thermally as follows: .