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The direct solid state polymerization (DSSP) of hexamethylene diammonium dodecanoate (PA 612 salt) was investigated for two different salt grades, fossil-based and bio-based. Aliphatic polyamide salts (such as PA 612 salt) are highly susceptible to solid melt transition (SMT) phenomena, which restrain the industrial application of DSSP. To that end, emphasis was given on reactor design, being the critical parameter influencing byproduct diffusion, amine loss and inherent DSSP kinetics. Experiments took place both at the microscale and the laboratory scale, in which two different reactors were tested in terms of bypassing SMT phenomena. The new reactor designed here proved quite successful in maintaining the solid state during the reaction. Scouting experiments were conducted in order to assess the effect of critical parameters and determine appropriate reaction conditions. Fossil-based PA 612 products proved to have a better end-group imbalance in comparison to bio-based ones, which is critical in terms of achieving high molecular weight. Finally, a real DSSP process was demonstrated, starting from PA 612 salt crystals and ending with PA 612 particles.

The nature-identical engineered polysaccharide α-(1,3) glucan, produced by the enzymatic polymerization of sucrose, was chemically modified by acylation with succinic anhydride. This modification reaction was initially performed at the micro scale in a TGA reactor to access a range of reaction conditions and to study the mechanism of the reaction. Subsequently, the best performing conditions were reproduced at the larger laboratory scale. The reaction products were characterized via coupled TGA/DSC analysis, FT-IR spectroscopy, solution viscosity and pH determination. The acylation path resulted in partially modifying the polysaccharide by altering its behavior in terms of thermal properties and solubility. The acylation in a solvent-free approach was found promising for the development of novel, potentially melt-processable and fully bio-based and biodegradable ester compounds.

Accelerated (artificial) weathering and thermal aging tests were performed to investigate the effectiveness of different formulations in reducing the UV/heat degradation extent for two low-density polyethylene types (LDPE-A, LDPE-T). The two LDPEs differ in the type and extent of branching due to the applied polymerization process, with LDPE-A being produced in an autoclave and LDPE-T in a tubular reactor. Oligomeric or high molecular weight hindered amine light stabilizer (HALS), and two UV absorbers of benzophenone or hydroxyphenyl-triazine types were equally introduced to both the LDPE grades at a total content of 0.2 wt%. The surface morphology, as well as thermal and mechanical properties, were examined during aging showing a significant degradation extent for the neat samples. In particular, a mechanism of chain scission/branch-ing that resulted in crosslinking was assumed for the neat polyethylenes, after combining the decrease of molecular weight observed in the GPC analysis with the increase in Young's modulus after UV exposure. LDPE-T presented higher photo-ox-idation rates due to its comb-like branched structure and its higher possibility of intermolecular reactions between adjacent chains. Little or no degradation was observed for the stabilized grades, confirming the effectiveness of the selected UV/heat systems in improving the weathering resistance of the two LDPE grades and enhancing their useful lifetime. This publication was made possible by the NPRP award (NPRP 9-161-1-030) from the Qatar National Research Fund (a member of The Qatar Foundation). We are also grateful to BASF and Sabo for supplying the additives at no cost. The statements made herein are solely the responsibility of the author(s). Scopus

In the current work, solid-state polymerization (SSP) was studied for the synthesis of poly(butylene terephthalate), PBT-based vitrimers. A two-step process was followed, the first step involved alcoholysis reactions and the incorporation of glycerol in the polymer chains. The second step comprised transesterification reactions in the solid state (SSP) in the presence of zinc(II) catalyst resulting in the formation of a dynamic crosslinked network with glycerol moieties serving as the crosslinkers. The optimum SSP conditions were found to be 3 h at 180 &deg, C under N2 flow (0.5 L/min) to reach high vitrimer insolubility (up to 75%) and melt strength (2.1 times reduction in the melt flow rate) while increasing the crosslinker concentration (from 3.5 to 7 wt.%) improved further the properties. Glass transition temperature (Tg) was almost tripled in vitrimers compared to initial thermoplastic, reaching a maximum of 97 &deg, C, whereas the melting point (Tm) was slightly decreased, due to loss of symmetry perfection under the influence of the crosslinks. Moreover, the effect of the dynamic crosslinked structure on PBT crystallization behavior was investigated in detail by studying the kinetics of non-isothermal crystallization. The calculated effective activation energy using the Kissinger model and the nucleating activity revealed that the higher crosslinker content impeded and slowed down vitrimers melt crystallization, also inducing an alteration in the crystallization mechanism towards sporadic heterogeneous growth.

In the current paper, a comparative study on the direct solid state polycondensation (DSSP) reaction of different terephthalate based semi-aromatic salts (XT salts, X = 4–18) in the TGA micro-reactor is reported. High purity XT salts were prepared in solution and were used as starting materials for DSSP. The reaction temperature (TDSSP) for each salt was suitably selected as 20 °C–30 °C below the melting point Tm of the respective salt. The PAXT products were characterized by TGA/DSC, liquid 1H-NMR, and SEM. In the DSSP of XT salts, some diamine is always lost to the gas phase and as a consequence, the attainable molecular weight of the polymer formed gets limited by the unbalance of acid and amine end-groups. The TGA curves show that as the diamine length increases and its volatility decreases, higher molecular weights are obtained. SEM pictures of the products reveal true solid character during the polymerization reaction up to and including PA10T, whereas PA5T, PA12T, and PA18T reveal stickiness and agglomeration during reaction. A possible mechanism explaining such behaviour is also provided. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 2493–2506

The current article deals with the development of different novel, tailor-made polyolefin formulations exhibiting both low flammability and high weathering resistance, so as to provide value-added polyethylene grades with extended service lifetime. Two low-density (LDPE) and one linear low-density (LLDPE) polyethylene grades were modified via melt compounding with an additive system comprising: (a) a nitrogen-phosphorous intumescent system for flame retardance and (b) a hindered amine light stabilizer and a benzophenone-type UV absorber for UV/heat stabilization, at a total loading of 30-35 wt%. The target was to reach V0 classification in UL94V flammability tests, while to a large extent maintaining the mechanical properties, such as, tensile and impact strength of the investigated polymers, thus ensuring that the additives do not interfere significantly with the material quality. Subsequently, the compounds were subjected to separate artificial UV and heat aging at 100 C for 1500 h; the formulations showed good flame retardance, even after prolonged artificial weathering, but there was an observable, although acceptable, decrease in the mechanical properties. Nevertheless, all the results show that the developed polyethylene compounds are very promising for outdoor applications, such as, irrigation piping and profiles, where long-term weathering stability is important, and where flame retardance is important for safety during storage. This publication was made possible by the NPRP award (NPRP 9-161-1-030) from the Qatar National Research Fund (a member of The Qatar Foundation). We are also grateful to BASF and Sabo for supplying the additives at no cost. We further express our gratitude to Dr. Mabrouk Ouederni from QAPCO for providing us with the three polyethylene grades. The statements made herein are solely the responsibility of the author(s). Scopus

The effect of six halogen-free flame retardant (FR) formulations was investigated on the thermal stability of two low-density polyethylenes (LDPE) and one linear low-density polyethylene (LLDPE), by means of thermogravimetric analysis (TGA) under nitrogen and air atmosphere. The relative data were combined with flammability properties and the overall performance of the FRs was correlated with the type of branching in the polyethylene grades and to their processing behavior. The thermal degradation kinetics was further determined based on the Kissinger and Coats-Redfern methods. In terms of flammability, the addition of a triazine derivative and ammonium polyphosphate at a loading of 35 wt. %. was found to be the most efficient, leading to UL 94 V0 ranking in the case of the LDPE grade produced in an autoclave reactor. - 2019 by the authors. Funding: This publication was made possible by the NPRP award [NPRP 9-161-1-030] from the Qatar National Research Fund (a member of The Qatar Foundation). The statements made herein are solely the responsibility of the author(s). Scopus

The aim of this work was to develop and optimize a direct solid state polymerization (DSSP) process on a micro scale for alkyldiammonium-terephthalate salts. This was successfully demonstrated for the first time by the case of tetramethylenediammonium-terepththalate salt (4T salt). The derived polymer (PA4T) presents interesting properties, but the temperature-favored acid catalyzed cyclization of tetramethylenediamine (TMD) to mono-functional pyrrolidine and ammonia inhibits a high polymerization conversion. DSSP was performed in a thermogravimetrical analysis (TGA) chamber, and the continuously monitored weight loss was correlated to polymerization conversion via the release of water, excluding any mass and heat transfer limitations. It was found that the conditions under which the DSSP is performed and the morphology of the starting material affect both the reaction rate and the product quality. The effect of the critical process parameters, namely vent size, heating rate to reach SSP temperature, and reaction temperature were quantified by the observed mass loss and by 1H NMR analysis. It was noticed that, besides the water formed by amidation, other volatile compounds were also released during the DSSP reaction, with main component, the TMD. In particular, it was observed that conditions favoring the evaporation of TMD also favored a higher reaction rate. The TMD loss was minimized by optimization of the aforementioned process conditions, leading to a more thermally stable and a higher molecular weight final product. The thermal stability of the PA4T was found to be inversely correlated to the concentration of carboxylic end groups present in the formed polymer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43271.

In the current article, the effect of different techniques was investigated on the preparation of tetramethylenediammonium terephthalate (4T salt), which consists of an industrially important precursor of high-performance polyamides. In particular, 4T salt was synthesized through solution, slurry, and solvent-free techniques. In each case the salt was isolated as a solid, correlating for the first time the salt preparation/isolation method with attained properties and morphology. This correlation led to a generalized comparison between all synthesized 4T salt grades, aiming at understanding the preparation mechanism of 4T salt. Accordingly, highly pure 4T salt, free of any unreacted diacid traces, can be only obtained from a clear salt solution either by cooling or by nonsolvent addition. Furthermore, by altering the crystallization conditions of the salt, thermal and morphological properties can be significantly affected, which further result in a qualitative correlation with the rate of subsequent direct solid-state polymerization (DSSP). The DSSP reactions were carried out in the microscale of a thermogravimetric chamber, where the different 4T salt grades were heated isothermally until full conversion. Polyamide grades of different thermal and analytical properties were received, underlining that the quality of the salt is a corner stone for subsequent DSSP. These findings can be further exploited also to the DSSP of other semi-aromatic polyamides. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 42987.

The direct solid state polycondensation (DSSP) reaction of tetramethylenediammonium and hexamethylenediammonium terephthalate (4 T and 6 T salts) in a laboratory scale autoclave reactor was investigated. The autoclave reactor is 3 orders of magnitude larger than the TGA micro-reactor we used previously. The larger scale reactor allows more extensive analyses such as analysis of the formed condensate by titration and allows investigation of operating conditions that are important on industrial scale, such as batch (closed system) versus semibatch (open system) operation and flow of nitrogen used. Comparing the two scales has given important insight into the parameters that are important in scaling-up direct solid-state polycondensation. Furthermore, the effect of scaling up on the quality of the final semiaromatic polyamide products was determined, by comparing the obtained thermal properties, the solution viscosity and the end-group concentrations obtained by 1H-NMR spectroscopy. When operating the open reactor with a gentle nitrogen stream, the results show that products of similar properties were obtained from the micro and the laboratory scale reactors if critical parameters like temperature and pressure time profile were kept the same. The solid character of the reacting mass was retained only when maintaining the reactor at atmospheric pressure, allowing the condensation water to be removed. When keeping the autoclave reactor closed, both polyamide (PA) products (i.e., PA4T and PA6T) were agglomerated as a result of a solid melt transition (SMT) during the direct solid state polycondensation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 45080.