Thermal Pyrolysis of Polystyrene Aided by a Nitroxide End-Functionality Improved Process and Modeling of the Full Molecular Weight Distribution

A significantly improved thermal pyrolysis process for polystyrene (PS) is reported and mathematically modeled, including the description of the time evolution of the full molecular weight distribution of the polymer during its degradation by direct integration of the balance equations without simplifications. The process improves the styrene yield from 28–39%, reached in our previous report, to 58–75% by optimizing the heating ramp during the initial stage of the pyrolysis process. The process was tested at 390 and 420 °C on samples of conventional PS synthesized via free-radical polymerization (FRP) and PS with a nitroxide end-functionality synthesized via nitroxide mediated polymerization (NMP) with three levels of the nitroxide to initiator (N/I) molar ratio: 0.9, 1.1 and 1.3. The NMP-PS produced with N/I = 1.3 generates the highest styrene yield (75.2 ± 6.7%) with respect to the best FRP-PS yield (64.9 ± 1.2%), confirming the trends observed in our previous study. The mathematical model corrects some problems of a previous model that was based on assumptions that led to significant errors in the predictions; this is achieved by solving the full molecular weight distribution (MWD) without assumptions. The model provides further insight into the initial stages of the pyrolysis process which seem to be crucial to determine the chemical paths of the process and the styrene yield, as well as the influences of the initial heating ramp used and the presence of a nitroxide end-functionality in the polymer.

Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials

Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and tert-butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1′Z)-1,1′-(1,4-phenylene) bis (N-tert-butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt)4 and (PtBA)4 star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (μ-stars) of (PSt)2-μ-(PtBA-b-PSt)2 and (PtBA)2-μ-(PSt-b-PtBA)2) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in μ-stars to afford amphiphilic μ-stars of (PSt)2-μ-(PAA-b-PSt)2 and (PAA)2-μ-(PSt-b-PAA)2. We investigated each polymerization step and characterized the obtained two sets of “sequence-isomeric” μ-stars by FT-IR, 1H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic μ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation (Ŧ) approach (i.e., ESCP-Ŧ-NMP), we demonstrated an interesting and facile strategy for the preparations of μ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials.

Improving Recycled Poly(lactic Acid) Biopolymer Properties by Chain Extension Using Block Copolymers Synthesized by Nitroxide-Mediated Polymerization (NMP)

The aim of this contribution is to assess the use poly(styrene-co-glycidyl methacrylate-b-styrene) copolymers synthesized by nitroxide mediated polymerization (NMP) as chain extenders in the recycling of poly(lactic acid) biopolyester. Concisely, the addition of such block copolymers during the melt processing of recycled poly(lactic acid) (rPLA) leads to important increases in the viscosity average molecular weight of modified polymeric materials. Molar masses increase from 31,000 g/mol for rPLA to 48,000 g mol−1 for the resulting rPLA/copolymer blends (bPLA). Fortuitously, this last value is nearly the same as the one for pristine PLA, which constitutes a first piece of evidence of the molar mass increase of the recycled biopolymer. Thermograms of chain extended rPLA show significant decreases in cold crystallization temperature and higher crystallinity degrees due to the chain extension process using NMP-synthesized copolymers. It was found that increasing epoxide content in the NMP-synthesized copolymers leads to increased degrees of crystallinity and lower cold crystallization temperatures. The rheological appraisal has shown that the addition of NMP synthesized copolymers markedly increases complex viscosity and elastic modulus of rPLA. Our results indicate that P(S-co-GMA)-b-S) copolymers act as efficient chain extenders of rPLA, likely due to the reaction between the epoxy groups present in P(S-co-GMA)-b-PS and the carboxyl acid groups present in rPLA. This reaction positively affects viscometric molar mass of PLA and its performance.

Synthesis of poly (n-butyl acrylate) with tempo by nitroxide mediated polymerization method

It has been observed that acrylate monomers are very difficult to polymerize with the low cost nitroxide catalyst 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO). Therefore, costly acyclic nitroxides such as N-tert-butyl-N-(1-diethylphosphono-2,2-dimethyl)-N-oxyl, (SG1), 2,2,5-Trimethyl-4-phenyl-3-azahexane-3-nitroxide (TIPNO) and TIPNO derivatives have to be used for the polymerization of the acrylic acid derivatives. There are very few reports on the use of TEMPO-derivatives toward the polymerization of n-butyl acrylate. Generally different reducing agents viz. glucose, ascorbic acid, hydroxyacetone etc. have been used to destroy excess TEMPO during the polymerization reaction. The acrylate polymerizations fail in the presence of TEMPO due to the strong C–O bond formed between the acrylate chain end and nitroxide. To the best of our knowledge, no literature report is available on the use of TEMPO without reducing agent or high temperature initiators, toward the polymerization of n-butyl acrylate. The present study has been carried out with a view to re-examine the application of low cost nitroxide TEMPO, so that it can be utilized towards the polymerization of acrylate monomers (e.g. n-butyl acrylate). We have been able to polymerize n-butyl acrylate using the nitroxide TEMPO as initiator (via a macroinitiator). In this synthesis, a polystyrene macroinitiator was synthesized in the first step from TEMPO, after this TEMPO end-capped styrene macroinitiator (PSt-TEMPO) is used to polymerize n-butyl acrylate monomer. The amount of macroinitiator taken was varied from 0.05% to 50% by weight of n-butyl acrylate monomer. The polymerization was carried out at 120°C by bulk polymerization method. The experimental findings showed a gradual increase in molecular weight of the polymer formed and decrease in the polydispersity index (PDI) with increase in amount of PSt-TEMPO macroinitiator taken. In all experiments conversion was more than 80%. These results indicate that the polymerization takes place through controlled polymerization process. Effect of different solvents on polymerization has also been investigated. In the following experiments TEMPO capped styrene has been used as macroinitiator leading to the successful synthesis of poly n-Butyl acrylate. It has been found that styrene macroinitiator is highly efficient for the nitroxide mediated polymerization, even in very small concentration for the synthesis of poly n-butyl acrylate. High concentration of macroinitiator results in the formation of block copolymers of polystyrene and poly ( n-butyl acrylate) viz. polystyrene-block-poly-( n-butyl acrylate). The use of TEMPO toward controlled polymerization is of much importance, because it is the nitroxide commercially available at the lowest cost.