Poly(butylene succinate) (PBS) and its copolymers are a family of biodegradable polymers with excellent biodegradability, thermoplastic processability and balanced mechanical properties. In this article, production of the monomers succinic acid and butanediol, synthesis, processing and properties of PBS and its copolymers are reviewed. The physical properties and biodegradation rate of PBS materials can be varied in a wide range through copolymerization with different types and various contents of monomers. PBS has a wide temperature window for thermoplastic processing, which makes the resin suitable for extrusion, injection molding, thermoforming and film blowing. Finally, we summarized industrialization and applications of PBS.
Strict isomorphism between butylene succinate and butylene fumarate in poly(butylene succinate-co-butylene fumarate) (PBSF) was revealed by DSC and wide-angle X-ray diffraction results. They adopt the same crystal modification, with only a little difference in crystal lattice parameters. The melting point of the copolymer increases linearly with increasing molar ratio of butylene fumarate and the melting enthalpy hardly changes, which meet the requirement of strict isomorphism. The introduction of unsaturated comonomer, fumaric acid, into PBS can enhance the total crystallization rate and the radial growth rate of spherulites. Consequently, PBF and PBSF are highly efficient polymeric nucleating agents for PBS and its copolymers. In this work, strict isomorphism provides us a new method to find polymeric nucleating agent.
Real-time atomic force microscopy observation was carried out during crystallization in
thin films of chiral poly(R-3-hydroxybutyrate-co-R-3-hydroxyhexanoate) copolymer, and the development
details of single lamellae in the banded spherulites are revealed for the first time. The lamellae exhibit
complicated growth behaviors: twisting, bending, backward growth, and branching. The lamellae
continuously twist to show alternating edge-on and flat-on views along the radii of the spherulites. Giant
screw dislocations bring forth to the birth of new lamellae. Interaction between the leading and trailing
lamellae contributes to cooperative stacking of the twisting crystals. The lamellae twist before screw
dislocations appear, demonstrating that screw dislocations are not causal of twisting. All the observed
twisting occurs in the right-handed sense, likely resulting from the chirality of the crystal structure.
Increased crystallization temperature results in decreased magnitude of lamellar twisting and bending.
Models for morphological development are discussed in the context of these observations.
Conditions
of rapid processing often drive polymers to adopt nonequilibrium
molecular conformations, which, in turn, can give rise to structural,
dynamical, and mechanical properties that are significantly different
from those in thermodynamic equilibrium. However, despite the possibility
to control the desired nonequilibrium properties of polymers, a rigorous
microscopic understanding of the processing–property relations
is currently lacking. In an attempt to stimulate progress along this
topical direction, we focus here on three prototypical and apparently
different cases: spin-coated polymer films, rapidly drawn polymer
fibers, and sheared polymer melts. Inspired by the presence of common
observations in the chosen cases, we search for order parameters as,
for example, topological correlations and heterogeneities, which may
allow characterizing the processing-induced behavior of polymers.
We highlight that such approaches, necessitating concerted efforts
from theory, simulations, and experiments, can provide a profound
understanding leading to predictable and tunable properties of polymers.
Abstract:It is the aim of this article to review the major theories of polymer crystallization since up to now we still have not completely comprehended the underlying mechanism in a unified framework. A lack of paradigm is an indicator of immaturity of the field itself; thus, the fundamental issue of polymer crystallization remains unsolved. This paper provides an understanding of the basic hypothesis, as well as relevant physical implications and consequences of each theory without too much bias. We try to present the essential aspects of the major theories, and intuitive physical arguments over rigorously mathematical calculations are highlighted. In addition, a detailed comparison of various theories will be made in a logical and self-contained fashion. Our personal view of the existing theories is presented as well, aiming to inspire further open discussions. We expect that new theories based on the framework of kinetics with direct consideration of long-range multi-body correlation will help solve the remaining problems in the field of polymer crystallization.
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