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Alcohol-initiated ROPs of L-lactide were performed in bulk at 160 °C for 72 h with variation of the catalyst or with variation of the initiator (aliphatic alcohols). Spontaneous crystallization was only observed when cyclic Sn(II) compounds were used as a catalyst. Regardless of initiator, high melting crystallites with melting temperatures (Tm) of 189–193 °C were obtained in almost all experiments with Sn(II) 2,2′-dioxybiphenyl (SnBiph) as catalyst, even when the time was shortened to 24 h. These HTm poly(lactide)s represent the thermodynamically most stable form of poly(L-lactide). Regardless of the reaction conditions, such high melting crystallites were never obtained when Sn(II) 2-ethylhexanoate (SnOct2) was used as catalyst. SAXS measurements evidenced that formation of HTm poly(L-lactide) involves growth of the crystallite thickness, but chemical modification of the crystallite surface (smoothing) seems to be of greater importance. A hypothesis, why the “surface smoothing” is more effective for crystallites of linear chains than for crystallites composed of cycles is discussed.
SnOct2 (Sn(II) 2-ethylhexanoate) catalyzed ROPs of L-lactide were performed in bulk with eight different alcohols as initiators. The time was varied between 1 h and 24 h for all initiators. For two initiators the temperature was also lowered to 115 ◦C. Even-numbered chains were predominantly formed in all polymerizations at short times, but the rate of transesterification (e.g. even/odd equilibration) and the molecular weight distribution were found to depend significantly on the nature of the initiator. Observed transesterification reactions also continued in solid poly (L-lactide), and with the most active initiator, almost total equilibration was achieved even at 130 ◦C. This means that all chains including those of the crystallites were involved in transesterification reactions proceeding across the flat surfaces of the crystallites. The more or less equilibrated crystalline polylactides were characterized by DSC and SAXS measurements with regard to their melting temperature (Tm), crystallinity and crystal thickness.
A set of strained aromatic macrocycles based on [n]cyclo2,7-(4,5,9,10-tetrahydro)pyrenylenes is presented with size dependent photophysical properties. The K-region of pyrene was functionalized with ethylene glycol groups to decorate the outer rim and thereby confine the space inside the macrocycle. This confined space is especially pronounced for n = 5, which leads to an internal binding of up to 8.0×104 M–1 between the ether-decorated [5]cyclo-2,7-pyrenylene and shape complementary crown ether–cation complexes.
Both, the ether-decorated [n]cyclo-pyrenylenes as well as one of their host–guest complexes have been structurally characterized by single crystal X-ray analysis. In combination with computational methods the structural and thermodynamic reasons for the exceptionally strong binding have been elucidated. The presented rim confinement strategy makes cycloparaphenylenes an attractive supramolecular host family with a favorable, size-independent read-out signature and binding capabilities extending beyond fullerene guests.
The definition of the term “conversion” is discussed for a variety of polymer syntheses. It is demonstrated that in contrast to organic and inorganic chemistry several different definitions are needed in polymer science. The influence of increasing conversion on structure and topology of homo- and Copolymers is illustrated. Chain-growth polymerizations, such as radical polymerization or living anionic polymerizations of vinyl monomers, condensative chain polymerization, two and three-dimensional step-growth polymerizations, ring–ring or chain–chain equilibration and chemical modification of polymers are considered.
Ring-opening polymerizations (ROPs) of L-lactide are performed in bulk at 130°C with tin(II) 2-ethylhexanoate as catalyst and various phenols of differentacidity as initiators. Crystalline polylactides having phenyl ester end groups are isolated, which are almost free of cyclics. The dispersities and molecular weights are higher than those obtained from alcohol-initiated ROPs under identical conditions. Polymerizations at 160°C yield higher molecular weights than expected from the monomer/initiator ratio and a considerable fraction of cycles. The fraction of cycles increases with higher reactivity of the ester end group indicating that the cycles are formed by end-to-end cyclization.
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
In contrast to other cyclic tin bisphenoxides, polymerizations of glycolide and l-lactide with the spirocyclic tin(IV) bis-1,1′-bisnapthoxide yield linear chains having a 1,1′-bisnapthol end group and no cycles. In the case of l-lactide, LA/Cat ratio and temperature are varied and at 160 °C or below, all polylactides mainly consist of even-numbered chains. A total predominance of even-numbered chains is also found for homopolymerization of glycolide, or the copolymerization of glycolide and l-lactide, when conducted <120 °C.
Linear chains having a bisnaphthol end group are again the main reaction products of ring-expansion polymerizations (REP) of 𝝐-caprolactone, but above 150 °C cycles are also formed.
One series of BiSub-catalyzed ring-opening polymerizations (ROPs) is per-formed at 160 °C for 3 days with addition of difunctional cocatalysts to find out, if poly(l-lactide) crystallizes directly from the reaction mixture. An analogous series is performed with monofunctional cocatalysts. High Tm crystal-lites (Tm > 190 °C) are obtained from all bifunctional cocatalysts, but not from all monofunctional ones. It is shown by means of SAXS measurements that the high Tm values are mainly a consequence of a transesterification–homogenization process across the lamellar surfaces resulting in thickness and smoothing of the surfaces. An unusual enthalpy-driven modification of the molecular weight distribution is found for samples that have crystallized during the polymerization. A third series of ROPs is performed at 170 °C for 2 h followed by annealing at 120 °C (2 h) to induce crystallization. Complete transformation of the resulting low Tm crystallites (Tm < 180 °C) into the high Tm crystallites by annealing at 170 °C for 1 d is not achieved, despite variation of the cocatalyst.
Cyclic polylactides were prepared in bulk at 170 °C, crystallized at 120 °C and then annealed at temperatures between 130 and 170 C with variation of catalyst, catalyst concentration and annealing time. The transformation of the initially formed low melting (LTm) crystallites, having melting temperatures (Tm) <180 °C into high melting (HTm) crystallites having Tm values > 189 °C was monitored by means of DSC measurements and characterized in selected cases by SAXS measurements. It was confirmed that the formation of HTm crystallites involves a significant growth of the thickness of the lamellar crystallites along with smoothing of their surface. Annealing at 170 °C for 1 d or longer causes thermal degradation with lowering of the molecular weights, a gradual transition of cyclic into linear chains and a moderate decrease of lamellar thickness. An unexpected result revealed by MALDI TOF mass spectrometry is a partial reorganization of the molecular weight distribution driven by a gain of crystallization enthalpy.
The catalytic potential of tin(II)acetate, tin(IV)acetate, dibutyltin-bis-acetate and dioctyl tin-bis-acetate was compared based on polymerizations of L-lactide conducted in bulk at 160 or 130C. With SnAc2 low-Lac/Cat ratios (15/1–50/1) were studied and linear chains having one acetate and one carboxyl end group almost free of cyclics were obtained. Higher monomer/catalyst ratios and lower temperatures favored formation of cycles that reached weight average molecular weights (Mw's) between 100,000 and 2,500,000. SnAc4 yielded mixtures of cycles and linear species under all reaction conditions. Dibutyltin- and dioctyl tin bis-acetate yielded cyclic polylactides under most reaction conditions with Mw's in the range of 20,000–80,000. Ring-opening polymerizations performed with ε-caprolactone showed similar trends, but the formation of COOH-terminated linear chains was significantly more favored compared to analogous experiments with lactide. The reactivity of the acetate catalysts decreased in the following order: SnAc2> SnAc4>Bu2SnAc2 Oct2SnAc2.
Polymerizations of L-lactide catalyzed either by neat SnCl2 or by SnCl2 + difunctional cocatalysts were conducted in bulk at 180, 160 and 140 °C with variation of the Lac/Cat ratio and time. With neat SnCl2 poly(L-lactide) having weight average molecular weights (uncorrected Mw’s) up to 190 000 g mol−1 were obtained mainly consisting of linear chains. Addition of salicylic acid or 1,1-bisphenol yielded a higher fraction of cyclic polylactides but lower molecular weights. Furthermore, SnCl2 was compared with Bu2SnCl2 and various other metal chlorides and the best results were obtained with SnCl2. With ethyl L-lactate as initiator SnCl2-catalyzed ROPs were performed at 120 °C and the lac/initiator ratio was varied. All these experiments were conducted under conditions allowing for comparison with ROPs catalyzed with neat Sn(II)-2-ethyhexanoate. Such a comparison was also performed with ε-caprolactone as monomer.
1:1 Copolymerizations of glycolide (GL) and L-lactide (LA) is performed in bulk at 100°C and at 160°C with four cyclic tin catalysts. The resulting copolyesters are characterized by SEC measurements, 1H and 13C NMR spectroscopy and by MALDI TOF mass spectrometry. At 160°C and longer reaction time (22 h) nearly complete conversion of both monomers is achieved, and cyclic copolymers with nearly random sequences are formed. At shorter times (0.5-3.0 h, depending on catalyst) the conversion of LA is incomplete, and only cyclics having even numbers of lactyl units are obtained. At 100°C at 22 h again cycles mainly consisting of even numbered lactyl units are formed, but with even and odd numbers of glycolyl units. Copolymerization of lactide at 160°C with small amounts of GL show that formation of high Tm crystallites (Tm > 190°C) is hindered even when only > 2% of GL is added. For polyglycolide containing a smaller amount of lactide complete solubility in hexafluoroisopropanol is only observed around and above 20 mol% of lactide.
Matrix‐assisted ionization (MAI) mass spectrometry does not require voltages, a laser beam, or added heat to initiate ionization, but it is strongly dependent on the choice of matrix and the vacuum conditions. High charge state distributions of nonvolatile analyte ions produced by MAI suggest that the ionization mechanism may be similar to that of electrospray ionization (ESI), but different from matrix‐assisted laser desorption/ionization (MALDI). While significant information is available for MAI using mass spectrometers operating at atmospheric and intermediate pressure, little is known about the mechanism at high vacuum.
Eleven MAI matrices were studied on a high‐vacuum time‐of‐flight (TOF) mass spectrometer using a 266 nm pulsed laser beam under otherwise typical MALDI conditions. Detailed comparisons with the commonly used MALDI matrices and theoretical prediction were made for 3‐nitrobenzonitrile (3‐NBN), which is the only MAI matrix that works well in high vacuum when irradiated with a laser.
Screening of MAI matrices with good absorption at 266 nm but with various degrees of volatility and laser energies suggests that volatility and absorption at the laser wavelength may be necessary, but not sufficient, criteria to explain the formation of multiply charged analyte ions. 3‐NBN produces intact, highly charged ions of nonvolatile analytes in high‐vacuum TOF with the use of a laser, demonstrating that ESI‐like ions can be produced in high vacuum. Theoretical calculations and mass spectra suggest that thermally induced proton transfer, which is the major ionization mechanism in MALDI, is not important with the 3‐NBN matrix at 266 nm laser wavelength. 3‐NBN:analyte crystal morphology is, however, important in ion generation in high vacuum.
The 3‐NBN MAI matrix produces intact, highly charged ions of nonvolatile compounds in high‐vacuum TOF mass spectrometers with the aid of ablation and/or heating by laser irradiation, and shows a different ionization mechanism from that of typical MALDI matrices.
L-lactide was polymerized in bulk at 120, 140, 160 and 180°C with neat tin(II) 2-ethylhexanoate (SnOct2) as catalyst. At 180°C the Lac/Cat ratio was varied from 25/1 up to 8 000/1 and at 160°C from 25/1 up to 6 000/1. The vast majority of the resulting polylactides consist of cycles in combination with a small fraction of linear chains having one octanoate and one COOH end group. The linear chains almost vanished at high Lac/Cat ratios, as evidenced by MALDI-TOF mass spectrometry and measurements of intrinsic viscosities and dn/dc values. At Lac/Cat ratios <1000/1 the number average molar masses (Mn) are far higher than expected for stoichiometic initiation, and above 400/1 the molar masses vary relatively little with the Lac/Cat ratio. At 180° slight discoloration even at short times and degradation of the molar masses were observed, but at 160°C or below colorless products with weight average molar masses (Mw) up to 310 000 g mol-1 were obtained. The formation of high molar mass cyclic polylactides is explained by a ROPPOC (Ring-Opening Polymerizatiom with simultaneous Polycondensation) mechanism with intermediate formation of linear chains having one Sn-O-CH end group and one mixed anhydride end group. Additional experiments with tin(II)acetate as catalyst confirm this interpretation. These findings together with the detection of several transesterification mechanisms confirm previous critique of the Jacobson-Stockmayer theory.
A new concept called “Ring-Opening Polymerization (ROP) combined with simultaneous POlyCondensation” (ROPPOC) is presented and discussed. This synthetic strategy is based on the intermediate formation of chains having two end groups that can react with each other. The ROPPOC syntheses are subdivided into three groups according to the nature of the chain ends: two ionic end groups, one ionic and one covalent chain end and a combination of two reactive covalent end groups may be involved, depending on the catalyst. The usefulness for the preparation of cyclic polymers is discussed with a review of numerous previously published examples. These examples concern to following classes of cyclic polymers: polypeptides, polyamides, polyesters, including polycarbonates, and cyclic polysiloxanes. It is demonstrated, that the results of certain ROPPOC syntheses are in contradiction to the Jacobson-Stockmayer theory. Finally, the usefulness of ROPPOCs for the detection of polydisperse catenanes is discussed.
Cyclic poly(L-lactide)s were prepared by ring-opening polymerization combined with simultaneous polycondensation (ROPPOC) in bulk at 160 ° with dibutyltin bis(4-cyanophenoxide) as catalyst. It is demonstrated by MALDI TOF mass spectrometry and 1H NMR end group analyses that cycles are formed by endto-end cyclization in addition to “back-biting” transesterification. Formation of high molar mass cyclic poly L-lactide)s by means of several more reactive ROPPOC catalysts presented previously and in new experiments is discussed. These experimental results, together with theoretical arguments, prove that part of the Jacobson–Stockmayer theory is wrong. The critical monomer concentration, above which end-toend cyclization is seemingly impossible, does not exist and reversible like irreversible polycondensations can theoretically proceed up to 100% conversion, so that finally all reaction products will necessarily adopt a cyclic architecture.
Ring–Ring Equilibration in Solid, Even-Numbered Cyclic Poly(l-lactide)s and their Stereocomplexes
(2020)
Even-numbered cyclic poly(d-lactide) and poly(l-lactide) are prepared by ringexpansion polymerization. The cyclic pol(l-lactide) is annealed either at 120 or at 160 °C for several days. The progress of transesterification in the solid state is monitored by the formation of odd-numbered cycles via matrix-assisted laser desorption/ionization-time of flight mass spectrometry. The changes of the crystallinity are monitored by differential scanning calorimetry, wideand small-angle x-ray scattering (WAXS and SAXS) measurements. Despite total even-odd equilibration at 160 °C, the crystallinity of poly(l-lactide) is not reduced. Furthermore, the crystallinity of the stereocomplexes of both cyclic polylactides do not decrease or vanish, as expected, when a blocky or random stereosequence is formed by transesterification. This conclusion is confirmed by 13C NMR spectroscopy. These measurements demonstrate that transesterification is a ring–ring equilibration involving the loops on the surfaces of the lamellar crystallites thereby improving crystallinity and 3D packing of crystallites without significant broadening of the molecular weight distribution.
A new kind of high melting (HTm) pol(L-lactide) was discovered when cyclic poly(L-lactide)s were prepared by ring-expansion polymerization with cyclic tin catalysts at 130–160 °C in bulk. By DSC measurements with 10 K min−1 melting temperatures (Tm) in the range of 190–196 °C were found. The WAXS and SAXS measurements evidenced that not a new crystal lattice but a well-ordered morphology and a higher perfection of the crystallites are responsible for the high Tm values and high crystallinities. Under identical reaction conditions SnOct2-catalyzed and alcohol-initiated ROPs do not yield these crystallites.
Furthermore, it was found that the standard crystallites are kinetically favored upon rapid crystallization, whereas the high melting form of poly(L-lactide) is thermodynamically more stable.
Two sets of polystyrene nanoparticles (PSNPs) with comparable core sizes but different carboxyl group densities were made and separated using asymmetric flow field flow fractionation (AF4), capillary electrophoresis (CE), and the off-line hyphenation of both methods. Our results revealed the significant potential of two-dimensional off-line AF4-CE hyphenation to improve the separation and demonstrated for the first time, the applicability of CE to determine the functional group density of nanoparticles (NPs). Compared to the result acquired with conductometric titration, the result obtained with synthesized 100 nm sized PSNPs revealed only a slight deviation of 1.7%. Commercial 100 nm sized PSNPs yielded a deviation of 4.6 %. For 60 nm sized PSNPs, a larger deviation of 10.6 % between both methods was observed, which is attributed to the lower separation resolution.
The structure and composition of polycarbonate polydimethylsiloxane copolymer (PC-co-PDMS) was investigated by applying various analytical approaches including chromatographic separation methods, spectrometric, and spectroscopic detection techniques. In particular, size exclusion chromatography (SEC) and liquid adsorption chromatography operating at different conditions (e.g. using gradient solvent systems) were used to achieve separations according to molar mass and functionality distribution. The coupling of both techniques resulted in fingerprint two-dimensional plots, which could be used to easily compare different copolymer batches. Matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry was applied for structural investigations. The different ionization behavior of both comonomers, however, strongly limited the applicability of this technique. In contrast to that, Fourier-transform Infrared (FTIR) spectroscopy could be used to quantify the amount of PDMS in the copolymer at different points in the chromatogram. The resulting methodology was capable of distinguishing PC-co-PDMS copolymer from PC homopolymer chains present in the material.