Filtern
Dokumenttyp
- Zeitschriftenartikel (11)
Sprache
- Englisch (11)
Referierte Publikation
- ja (11)
Schlagworte
- Polyesters (11) (entfernen)
Organisationseinheit der BAM
Investigation of the Thermal Stability of Proteinase K for the Melt Processing of Poly(L‑lactide)
(2022)
The enzymatic degradation of aliphatic polyesters offers unique opportunities for various use cases in materials science. Although evidently desirable, the implementation of enzymes in technical applications of polyesters is generally challenging due to the thermal lability of enzymes. To prospectively overcome this intrinsic limitation, we here explored the thermal stability of proteinase K at conditions applicable for polymer melt processing, given that this hydrolytic enzyme is well established for its ability to degrade poly(L-lactide) (PLLA). Using assorted spectroscopic methods and enzymatic assays, we investigated the effects of high temperatures on the structure and specific activity of proteinase K. Whereas in solution, irreversible unfolding occurred at temperatures above 75−80 °C, in the dry, bulk state, proteinase K withstood prolonged incubation at elevated temperatures. Unexpectedly little activity loss occurred during incubation at up to 130 °C, and intermediate levels of catalytic activity were preserved at up to 150 °C. The resistance of bulk proteinase K to thermal treatment was slightly enhanced by absorption into polyacrylamide (PAM) particles. Under these conditions, after 5 min at a temperature of 200 °C, which is required for the melt processing of PLLA, proteinase K was not completely denatured but retained around 2% enzymatic activity. Our findings reveal that the thermal processing of proteinase K in the dry state is principally feasible, but equally, they also identify needs and prospects for improvement. The experimental pipeline we establish for proteinase K analysis stands to benefit efforts directed to this end. More broadly, our work sheds light on enzymatically degradable polymers and the thermal processing of enzymes, which are of increasing economical and societal relevance.
Poly(alkylene isophthalate)s were prepared by different methods, either in solution or in bulk. The SEC measurements were evaluated in such a way that all oligomers were included. In solution (monomer conc. 0.10.7 mol/L) large fractions of rings were formed and high dispersities (up to 12) were obtained, which disagree with theoretical predictions. Polycondensations in bulk did neither generate cyclics by 'back-biting' nor by end-to-end cyclization, when the maximum temperature was limited to 210 °C. The dispersities of these perfectly linear polyesters were again higher than the theoretical values. Regardless of the synthetic method monomeric cycles were never observed. Furthermore, SEC measurements performed in tetrahydrofuran and in chloroform and SEC measurements performed in three different institutes were compared. Finally, SEC measurements of five samples were performed with universal calibration and a correction factor of 0.71 ± 0.02 was found for normal calibration with polystyrene.
Poly(ester urethane)s derived from lactide, isosorbide, terephthalic acidm abd various diisocyanates
(2014)
Isosorbide-initiated oligomerizations of ʟ-lactide were preformed in bulk using SnCl2 as catalyst. The resulting telechelic OH-terminated oligoesters were in situ subjected to simultaneous polycondensation and polyaddition with mixtures of terephthaloyl chloride and diisocyanates. Most polymerizations were conducted with 4,4'-diisocyanatodiphenyl methane and 2,4-diisocyanato toluene. The consequences of excess diisocyanate and four different catalysts were studied. The isosorbide/lactide ratio and the terephthalic acid/diisocyanate ratio were varied. Number average molecular weights up to 15 kDa with polydispersities around 3–5 were obtained. Depending on the chemical structure of the copolyester and on the feed ratio, incorporation of urethane groups may reduce or enhance the glass-transition temperature, but the thermal stability decreases dramatically regardless of composition.
Isosorbide, succinyl chloride and isophthaloyl chloride are polycondensed under various reaction conditions. The heating in bulk with or without catalysts as well in an aromatic solvent without catalyst, and polycondensation with the addition of pyridine only yield low molar mass copolyesters. However, heating in chlorobenzene with addition of SnCl2 or ZnCl2 produces satisfactory molar masses. The number average molecular weights (Mn) of most copolyesters fall into the range of 7000–15,000 Da with polydispersities (PD) in the range of 3–9. The MALDI-TOF mass spectra almost exclusively displayed peaks of cyclics indicating that the chain growth was mainly limited by cyclization and not by side reactions, stoichiometric imbalance or incomplete conversion. The glass-transition temperatures increased with the content of isophthalic acid from 75 to 180 °C and the thermo-stabilities also followed this trend.
Flame retarded poly(butylene terephthalate) (PBT) is required for electronic applications and is mostly achieved by low molar mass additives so far. Three phosphorus-containing polyesters are suggested as halogen-free and polymeric flame retardants for PBT. Flame retardancy was achieved according to cone calorimeter experiments showing that the peak heat release rate and total heat evolved were reduced because of flame inhibition and condensed-phase activity. The presented polymers containing derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide form immiscible blend systems with PBT. Shear-rheology shows an increase in storage moduli at low frequencies. This is proposed as quantitative measure for the degree of phase interaction. The phase structure of the blends depends on the chemical structure of the phosphorus polyester and was quite different, depending also on the viscosity ratio between matrix and second phase. A lower viscosity ratio leads to two types of phases with spherical and additionally continuous droplets. Addition of the flame retardants showed no influence on the dielectric properties but on the mechanical behavior. The polymeric flame retardants significantly diminish the impact strength because of several reasons: (1) high brittleness of the phosphorus polyesters themselves, (2) thermodynamic immiscibility, and (3) weak phase adhesion. By adding a copolymer consisting of the two base polymers to the blend, an improvement of impact strength was obtained. The copolymer particularly acts as compatibilizer between the phases and therefore leads to a smaller phase size and to a stronger phase adhesion due to the formation of fibrils.
Pyrolysis, fire behaviour and mechanical properties of a blend of poly(butylene terephthalate) (PBT) with a phosphorus polyester (PET-P-DOPO) are investigated and compared with PBT/aluminium diethylphosphinate (AlPi-Et) composites. The PBT/PET-P-DOPO is immiscible and exhibits gas-phase and condensed-phase activity, whereas AlPi-Et in PBT results mainly in flame inhibition. Only higher loadings of AlPi-Et yield significant condensed-phase activity. Using the same phosphorus content, PBT/PET-P-DOPO and PBT/AlPi-Et exhibit similar reductions in fire load (22%) and flame spread (17% assessed by fire growth rate, FIGRA), compared with PBT. In contrast to AlPi-Et, the addition of PET-P-DOPO does not decrease the tensile strength of PBT. Thus, PET-P-DOPO is an interesting alternative to low-molecular-weight flame retardants.
Using three different catalysts, water-initiated polymerizations of ε-caprolactone were conducted in bulk with variation of the monomer/water ratio. The resulting CH2OH and CO2H- terminated polylactones were subjected in situ to azeotropic polycondensations. With Bi-triflate and temperatures, the polycondensations were not much successful and involved side reactions. With ZnCl2, and especially SnCl2, considerably higher molar masses were achieved. The substitution of toluene for chlorobenzene for refluxing gave better results. The polycondensations broadened the molar mass distribution of the ROP-based prepolymers, and polydispersities between 1.4–1.8 were obtained. The MALDITOF mass spectra revealed that the polycondensations significantly enhanced the fraction of rings due to efficient 'end-biting' reactions. By comparison with copolymerization experiments and Sn methoxide-initiated polymerizations, it was demonstrated that equilibration reactions, such as the formation of rings by 'back-biting,' did not occur.
Flame retardancy for thermoplastics is a challenging task where chemists and engineers work together to find solutions to improve the burning behavior without strongly influencing other key properties of the material. In this work, the halogen-free additives aluminum diethylphosphinate (AlPi-Et) and a mixture of aluminum phosphinate (AlPi) and resorcinol-bis(di-2,6-xylyl phosphate) (AlPi-H + RXP) are employed in neat and reinforced poly(butylene terephthalate) (PBT), and the morphology, mechanical performance, rheological behavior, and flammability of these materials are compared. Both additives show submicron dimensions but differ in terms of particle and agglomerate sizes und shapes. The overall mechanical performance of the PBT flame-retarded with AlPi-Et is lower than that with AlPi-H-RXP, due to the presence of larger agglomerates. Moreover, the flow behavior of the AlPi-Et/PBT materials is dramatically changed as the larger rod-like primary particles build a percolation threshold. In terms of flammability, both additives perform similar in the UL 94 test and under forced-flaming combustion. Nevertheless, AlPi-Et performs better than AlPi-H + RXP in the LOI test. The concentration required to achieve acceptable flame retardancy ranges above 15 wt %.
Dielectric spectroscopy (10-2 Hz to 106 Hz) was employed to investigate the molecular dynamics of hyperbranched polyesters where the number of the generation is systematically varied from 2 to 5. As a first result, the dielectric properties depends strongly on the generation of the hyperbranched polymers. For higher generations (3 to 5) at temperatures below Tg two relaxation processes are observed, a γ-process at lower temperatures and a β-process at higher ones. The apparent activation energies are around 100 kJ/mol which seems to be too high for truly localized processes. For the Generation 2, only the γ-process is observed. For all investigated polymers the dielectric α-relaxation could not be observed because of strong conductivity effects. Therefore, the conductivity is systematically analyzed which obeys the peculiarities found to be characteristic for semiconducting disordered materials. Especially, the Barton/Nakajima/Namikawa relationship is found to be valid.
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.