Nylon 6 polymerization in the solid state

The postcondensation of nylon 6 in the solid state was studied. The reactions were carried out on fine powder in a fluidized bed reactor in a stream of dry nitrogen in the temperature range 110-205°C and during 1-24 h. The solid-state polymerization (SSP) did not follow melt kinetics, but was found to be limited by the diffusion of the autocatalyzing acid chain end group. Factors thought to influence SSP were studied, e.g., heat treatment, starting molecular weight, and remelting. Surprisningly, heat treatment had little effect, but the starting molecular weight had a strong effect on the reaction rate. The higher the starting molecular weight, the faster the reaction. This could be explained as a changing concentration distribution of the reactive groups in the solid state on SSP. The kinetics of the SSP had more than one region, and the rate of reaction for conversions of over 30% could be expressed as - dc/dt = k(c/t), where k is a dimensionless constant independent of temperature with a value of 0.28. The integrated form has the form - In(c/co) = k In(t/), where co is the acid end-group concentration at the start, t is the reaction time, and is the induction time. The value of is both dependent on the starting concentration co and the reaction temperature and has an activation energy of 105 kJ/mol

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 (Tg, −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

Thermoplastic Polyurethanes with Poly(butylene terephthalate) as Crystallizable Hard Phase

Polyurethanes were prepared from poly(tetramethylene oxide) end-capped with MDI and PBT extenders. The PBT extenders were random-disperse in length and their length varied from three to seven repeating units. The structure of the polyurethanes was studied by FT-IR and AFM, their thermal and thermomechanical responses were measured by DSC and DMTA, and their elastic behavior was assessed by compression set measurements. The MDI-PBT-MDI hard segments had a ribbon-like crystalline morphology. Increasing the PBT length gave rise to an increase of the storage modulus at room temperature and the melting point. The storage modulus depended strongly on temperature

Crystallization of poly(ethylene terephthalate) and poly (butylene terephthalate) modified by diamides

Poly(ethylene terephthalate) (PET) and poly (butylene terephthalate) have been modified by diamide units (0.1-1 mol%) in an extrusion process and the crystallization behavior studied. The diamides used were: for PET, T2T-dimethyl (N, N-bis(p-carbomethoxybenzoyl)ethanediamine) and for PBT, T4T-dimethyl (N, N-bis(p-carbomethoxybenzoyl)butanediamine). The above materials were compared to talc (0.5 wt%), this being a standard heterogeneous nucleator, and to diamide modified copolymers obtained by a reactor process. Two PET materials were used: a slowly crystallizing recycled grade obtained from soft drink bottles and a rapidly crystallizing injection molding grade. The crystallization was studied by differential scanning calometry (DSC) and under injection molding conditions using wedge shaped specimens; the thermal properties were studied by dynamic mechanical analysis. T2T-dimethyl is effective in increasing the crystallization of PET in both of the extrusion compounds as well as in the reactor materials. It was also found that the crystallization temperature of poly(butylene terephthalate) could be slightly increased by the addition of nucleators