Reactivity of 2,3-Dichloropropene in free-radical copolymerization reactions

The copolymers of 2,3-Dichloropropene with vinyl chloride, methyl methacrylate, and styrene of different compositions were obtained via free-radical copolymerization. The copolymerization constants for the comonomers were found from the dependence of the copolymer composition on the initial mixture content. An increase in the content of 2,3-Dichloropropene in the initial mixture was found to decrease the yield and intrinsic viscosity of the copolymer for all systems. The reactivity of 2,3-Dichloropropene in copolymerization reactions was assessed according to the reciprocals of the copolymerization constants of vinyl chloride, methyl methacrylate, and styrene, which indicate the reactivity of the dichlorinated monomer when interacting with comonomer radicals. It was found that 2,3-dichloropropene is the most active in the reaction with a styrene radical. However, its reactivity with a methyl methacrylate radical decreases by a factor of 0.88 as compared to the styrene radical. The lowest reactivity of 2,3-Dichloropropene is observed when interacting with a vinyl chloride radical. The synthesized copolymers can be further modified by replacing chlorine atoms with functional groups.

The effect of isothermal crystallization on mechanical properties of poly(ethylene 2,5-furandicarboxylate)

The effects of isothermal crystallization temperature/time on mechanical properties of bio-based polyester poly(ethylene 2,5-furandicarboxylate) (PEF) were investigated. The intrinsic viscosity, crystallization properties, thermal properties, and microstructure of PEF were characterized using ubbelohde viscometer, X-ray diffraction, polarizing optical microscope, differential scanning calorimetry, and scanning electron microscopy. The PEF sample isothermal crystallized at various temperatures for various times was denoted as PEF-T-t. The results showed that the isothermal crystallization temperature affected the mechanical properties of PEF-T-30 by simultaneously affecting its crystallization properties and intrinsic viscosity. The isothermal crystallization time only affected the crystallization properties of PEF-110-t. The crystallinity of PEF-110-40 was 17.1%. With small crystal size, poor regularity, and α′-crystal, PEF-110-40 can absorb the energy generated in the tensile process to the maximum extent. Therefore, the best mechanical properties can be obtained for PEF-110-40 with the tensile strength of 43.55 MPa, the tensile modulus of 1,296 MPa, and the elongation at a break of 13.36%.

Novel Polyimide-block-poly(dimethyl siloxane) copolymers: Effect of time on the synthesis and thermal properties

Polyimide-block-poly(dimethyl siloxane) copolymer was synthesized by a two-step process, initiated by coupling anhydride terminated poly(amic acid), AT-PAA with amino terminated poly(dimethyl siloxane), (NH2)2-PDMS to form poly(amic acid)-block-poly(dimethyl siloxane). The resulting copolymer is then thermally treated to produce polyimide-block-poly(dimethyl siloxane), PI-PDMS. Because of the high glass transition temperature, Tg of polyimide, it is usually cured at a high temperature of about 300°C for over 2.5 h. Copolymerization of polyimide with polysiloxane, reduces the imidization temperature while maintaining high thermomechanical properties. A series of instruments were used to monitor the progress of copolymerization. The time-based analysis of the product of copolymerization enables the optimization of the structure and properties of the copolymers. The chemical structure and composition of the copolymer were studied by Fourier Transform Infrared Spectroscopy, (FT-IR). The incorporation of PDMS blocks into the copolymer and the degree of imidization of the polyimide block increased with increasing reaction time. The change in the viscosity of the copolymerizing solution was monitored by simple shear viscometry conducted with the Brookfield Viscometer. The reported increase in solution viscosity with increasing copolymerization time is associated with increasing molecular weight of the copolymer. The intrinsic viscosity of the copolymer solution was measured as a function of copolymerization time and it was found that the intrinsic viscosity of the copolymer solution increased with increasing reaction time. The glass transition temperature (Tg) and the thermal stability of the copolymer were determined by differential scanning calorimetry, DSC and thermogravimetric analysis, and TGA, respectively. Between 25°C and 420°C, the copolymers synthesized in this study show two glass transition temperatures due to the polyimide, PI block at around 380°C and another peak associated with PDMS plasticized polyimide at about 290–300°C. The two Tg peaks observed in the DSC thermogram are believed to be indicative of the structure of a block copolymer. TGA analysis shows that the thermoxidative stability of the copolymers increased with increasing reaction time, due to the incorporation of increased amount of PDMS unit into the copolymer. The combination of increasing molecular weight of copolymer, higher degree of imidization of polyimide blocks and enhanced thermoxidative stability may translate into improved flame retardancy of copolymers. This suggested enhancement in flame retardancy in air atmosphere, is believed to be due the incorporated PDMS blocks, which can be converted into silica, SiO2, a recognized thermally stable material.

Degradation of a mechanically recycled polylactide/halloysite nanocomposite in an ethanolic food simulant

<p class="JARTEAbstract">This work aims to study the effect of immersion in a ethanolic food simulant in mechanically recycled poly(lactic acid) (PLAR) and its nanocomposites reinforced with halloysite nanotubes (HNT). PLAR was obtained by subjecting PLA to an accelerated ageing process, which includes photochemical, thermal and hydrothermal ageing steps, followed by a final demanding washing step. PLAR was further reinforced with 4 %wt. HNT to improve the properties of the PLAR films. The materials were melt compounded by melt extrusion and processed into films by compression molding. The resulting films were exposed to food simulant D1 (50 %vol. ethanol solution) for 10 days at 40 °C. The intrinsic viscosity, crystallization behavior, thermal stability as well as the mechanical performance were analyzed before and after the contact with the food simulant. The swelling, plasticizing and hydrolyzing effect of the food simulant led to an important decrease of the intrinsic viscosity of all the samples, along with a significant increase of the crystallinity. Thermal stability was negatively affected by the decrease of the molecular weight, while the high crystallinity values resulted in materials with higher Vickers hardness values after the immersion in the food simulant.</p>

Parameter Estimation of Mark-Houwink Equation of Polyethylene Glycol (PEG) Using Molecular Mass and Intrinsic Viscosity in Water

Polyethylene glycol (PEG) is an ingredient for approved drug products by the Food & Drug Administration. PEG is mostly used as a pharmaceutical adjuvant, ophthalmic and oral acts as an encapsulating agent, plasticizing agent in food packages, modified and/or functionalized materials, among other applications. It is important to know the molecular mass of PEG because it will bring the product configuration for these applications. The use of instrumental techniques is often infeasible due to high investment and operational costs. The viscosimetry by capillary, in the case of a classical technique, simple and inexpensive, allows significant results for the determination of the molecular mass of polymers from the intrinsic viscosity. The objective of the present study was to determine the parameters of the Mark-Houwink equation for PEG using molecular mass and intrinsic viscosity in water at different temperatures. The parameters resulting in “K” between 0.046828 x 10-3 and 0.298291 x 10-3 cm3.g-1 and “α” between 0.40 and 0.70. The viscosimeter by the capillary allowed to obtain significant results for the estimation of the parameters "K" and "α", with a correlation coefficient greater than 98%.