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The main objective of this work was to design new advanced sorbent phases, alternating copolymers, derived from isosorbide and 2,6-difluorpyridine, to be used for the removal of aromatic organic pollutants present in water at low concentrations. Six different monomers, dianhydrohexitols isomers and bisphenol derivatives, weresynthesized in order to make it possible to study their hydrophilic and hydrophobiceffect on the sorption efficiency of the resulting polymeric phases. Before this study, we have confirmed the chemicals structures, molecular weights, and thermal properties of the obtained polymeric phases. Sorption results show a higher adsorption efficiency of P6 co-poly(ether-pyridine) based on bisphenol substituted with pyridineunits, for all tested pollutants, hydrophobic and hydrophilic ones, due to its less compact structure. Two aromatic organic pollutants, p-hydroxybenzoic acid and toluicacid, were selected as sorbates to study the adsorption characteristic, kinetics and isotherms of the copoly(ether pyridine) P6. Langmuir model led to a better fitting of the sorption isotherms; the sorption of toluic acid is easier than of that p-hydroxybenzoic acid. Comparing 1/n values for benzoic acid was two time lower for P6 compared to that for biochar and for crosslinked methacrylate resin, showing a higher efficiency
εCL was polymerized using the triflates of lanthanum, samarium, magnesium, aluminum, scandium, and bismuth as catalysts. Bismuth triflate proved to be extraordinarily reactive, and catalyzed polymerizations of εCL even at 20 °C. Adding DTBMP reduced the polymerization rate only slightly. Furthermore, no evidence of a cationic mechanism was found by end‐group analyses. Polymerization at 20 °C either in bulk or in solution only yielded polyesters of low or medium molecular weights. Yet addition of alcohols allowed for a proper control of molecular weight and end‐groups. Additionally, low catalyst concentrations and low temperature resulted in narrow molecular weight distributions and polylactones almost free of cyclic compounds.
Copolyesters with an alternating sequence of terephthalic acid and aliphatic dicarboxylic acids were prepared with three different methods. First, dicarboxylic acid dichlorides were reacted with bis(2-hydroxyethyl)terephthalate (BHET) in refluxing 1,2-dichlorobenzene. Second, the same monomers were polycondensed at 0-20 °C in the presence of pyridine. Third, dicarboxylic acid dichlorides and silylated BHET were polycondensed in bulk. Only this third method gave satisfactory molecular weights. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that the copolyesters prepared by the pyridine and silyl methods might have contained considerable fractions of cyclic oligoesters and polyesters despite the absence of transesterification and backbiting processes. The alternating sequences and thermal properties were characterized with 1H NMR spectroscopy and differential scanning calorimetry measurements, respectively. In agreement with the alternating sequence, all copolyesters proved to be crystalline, but the crystallization was extremely slow [slower than that of poly(ethylene terephthalate)]. A second series of alternating copolyesters was prepared by the polycondensation of silylated bis(4-hydroxybut- yl)terephthalate with various aliphatic dicarboxylic acid dichlorides. The resulting copolyesters showed significantly higher rates of crystallization, and the melting temperatures were higher than those of the BHET-based copolyesters. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3371-3382, 2001
2,2-Dibutyl-2-stanna-1,3-dioxepane (DSDOP) was polycondensed with bis(4-chlorothiophenyl) suberat under various reaction conditions, but only moderate molecular weights (Mn 10000) were obtained. The MALDI-TOF mass spectrosmetry revealed the formation of cyclic oligo- and polyesters in addition to linear species having OH, CO2H, and unreacted 4-chlorothiophenyl ester endgroups.
Furthermore, -Caprolactone (-CL) was polymerized with DSDOP as the initiator at monomer/initiator (M/I) ratios of 20 and 50. The resulting tin-containing macrocyclic polylactones were reacted with sebacic acid bis(4-thiocresyl)ester at three different temperatures and with different reaction times. Analogous polycondensations were conducted with suberic acid bis(4-chlorothiophenyl) ester. The presence of thioarylester endgroups in the isolated polyesters was checked by 1H NMR spectroscopy. The highest conversions were found at long reaction times (24 or 72 hours), or after the addition of pyridine and N,N-dimethylaminopyridine as catalysts. Despite high conversions, the number average molecular weights (Mn's) did not exceed values around 20000. Even in the samples having the highest molecular weights, unreacted 4-chlorothiophenylester endgroups were detected by GPC measurements evaluated with a UV-detector. It is concluded that both factors, cyclization and incomplete conversion, contribute to the limitation of the chain growth.
We prepared 2,2-dibutyl-2-stanna-1,3-dithiacycloalkanes from dibutyltin oxide and ,-dimercaptoalkanes. Heterocycles with five-, six-, seven-, or nine-ring members were used as bifunctional monomers for polycondensations with aliphatic dicarboxylic acid chlorides. These polycondensations conducted in bulk were highly exothermic and yielded poly(thio ester)s with number average molecular weights (Mn's) in the range of 5000-30,000 Da. These poly(thio ester)s proved to be rapidly crystallizing materials with melting temperatures in the range of 90-150 °C. In addition to the success of the new synthetic approach, two interesting and unpredictable results were obtained. All volatile species detectable by matrix assisted laser desorption induced-time of flight (MALDI-TOF) mass spectrometry were cyclic oligo- and poly(thio ester)s. Second, several polyesters showed a reversible first-order change of the crystal modification as identified by differential scanning calorimetry measurements and X-ray scattering with variation of the temperature. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3656-3664, 2000
Numerous polycondensations of isosorbide and suberoyl chloride or other aliphatic dicarboxylic acid dichlorides were performed with pyridine as a catalyst and HCl acceptor. The reaction conditions were varied to optimize both the molecular weight and the fraction of cyclic oligo- and polyesters. Furthermore, we attempted to obtain the cyclic monomer by catalyzed back-biting degradation of the molten cyclic polyesters above 220 °C in vacuo. The polyesters were characterized by viscosity and size exclusion chromatographic measurements as well as matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In selected cases, mixtures of linear and cyclic polyesters were treated with a hot solution of partially methylated ß-cyclodextrin in methanol. This treatment allowed for a selective extraction of the linear chains up to approximately 5000 Da.
L-lactide (LA) was polymerized in toluene by means of neat tin(II) 2-ethylhexanoate (SnOct2). Concentration, time and temperature were varied. The isothermally crystallized polyLAs (PLA) were characterized in the virgin state with regard to topology, molar mass, melting temperature (Tm), crystal modification, high or low Tm morphology, crystallinity and crystal thickness. Even a small amount of solvent favored cyclization relative to polymerization in bulk, so that cyclic polylactides were obtained at 115 ◦C and even at 95 ◦C. At all temperatures the α-modification of PLA was obtained along with crystallinities up to 90%. With 6 M solution the high Tm morphology with Tm’s > 190 ◦C was obtained at 115 ◦C. The crystal thickness of crystallites grown from solution at 115 ◦C was on the average 10–20% higher than that of PLA polymerized in bulk. At a polymerization temperature of 75 ◦C cyclization was incomplete and fewer perfect crystallites were formed. A new hypothesis for the crystal growth of cyclic polyLAs is proposed.
L-Lactide was polymerized in bulk at 140 °C with three different cyclic tin catalysts and the time was varied from 1 d up to 14 d. The MALDI TOF spectra confirmed the formation of cyclic polylactides (PLAs) and displayed a characteristic change of peak intensity distribution with formation of a “saw tooth pattern”. This pattern confirms a previous hypothesis that cyclic PLAs tend to form crystallites with extended ring conformation and relatively smooth surface. This type of crystallites is formed under thermodynamic control by transesterification on the surface of the crystallites. In this way PLAs with extraordinarily high melting temperatures (Tm's up to 200.6 °C) and extraordinarily high melting enthalpy were obtained (ΔHm's up to 105 J g−1). These ΔHm values require a revision of the maximum ΔHm value calculated in the literature for ideal PLA crystals.
Ring-expansion polymerizations (REPs) catalyzed by two cyclic tin catalysts(2-stanna-1.3-dioxa-4,5,6,7-dibenzazepine [SnBiph] and
2,2-dibutyl-2-stanna-1,3-dithiolane [DSTL) are performed at 140 °C in bulk.
Small amounts (4 vol%) of chlorobenzene or other solvents are added to facilitate transesterification reactions (ring–ring equilibration) in the solid poly(l-lactide)s. In the mass range up to m/z 13 000 crystalline PLAs displaying a so-called saw-tooth pattern in the MALDI-TOF mass spectra are obtained indicating the formation of extended-ring crystals. The characteristics of extended-ring crystallites and folded-ring crystallites are discussed. Furthermore, extremely high melting temperatures (Tm’s up to 201.2 °C) and melting enthalpies (𝚫Hm’s up to 106 J g−1)) are found confirming that 𝚫Hmmax, the 𝚫Hm of a perfect crystal, is around or above 115 J g−1 in contrast to literature data.
This article reviews the usefulness of tin(II) and tin(IV) salts and compounds as catalysts for the polymerization of lactides. The text is subdivided into nine parts mainly reflecting different polymerization strategies, such as ring-opening polymerization (ROP), ring-expansion polymerization (REP), ROP combined with simultaneous polycondensation (ROPPOC), various catalysts with unknown polymerization mechanisms, and polycondensation of lactic acid. Since the toxicity of tin salts and compounds is a matter of concern and frequently mentioned in numerous publications, the first section deals with facts instead of myths about the toxicity of tin salts and compounds.