RESUMEN

Unsaturated polydienes are frequently hydrogenated to yield polyolefins that are more chemically stable. Here, the effects of partial hydrogenation on the phase behavior and nanostructure of polyisoprene-containing block copolymers are investigated. To ensure access to the order-disorder transition temperature (TODT) over a wide temperature range, we examine copolymers with at least one random block. Dynamic rheological and scattering measurements indicate that TODT increases linearly with increasing hydrogenation. Small-angle scattering reveals that the temperature-dependence of the Flory-Huggins parameter changes and the microdomain period increases, while the interfacial thickness decreases. The influence of hydrogenation becomes less pronounced in more constrained multiblock copolymers.

RESUMEN

Block copolymers have been extensively studied due to their ability to spontaneously self-organize into a wide variety of morphologies that are valuable in energy-, medical-, and conservation-related (nano)technologies. While the phase behavior of bicomponent diblock and triblock copolymers is conventionally governed by temperature and individual block masses, it is demonstrated here that their phase behavior can alternatively be controlled through the use of blocks with random monomer sequencing. Block random copolymers (BRCs), i.e., diblock copolymers wherein one or both blocks are a random copolymer comprised of A and B repeat units, have been synthesized, and their phase behavior, expressed in terms of the order-disorder transition (ODT), has been investigated. The results establish that, depending on the block composition contrast and molecular weight, BRCs can microphase-separate. We also report that large variation in incompatibility can be generated at relatively constant molecular weight and temperature with these new soft materials. This sequence-controlled synthetic strategy is extended to thermoplastic elastomeric triblock copolymers differing in chemistry and possessing a random-copolymer midblock.

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RESUMEN

The crystallization behavior of microbially synthesized poly(3-hydroxybutyrate) (PHB) and its copolymers [P(HB-co-HHx)] containing 2.5, 3.4, and 12 mol % 3-hydroxyhexanoate (HHx) comonomer and the melting of the resultant crystals were studied in detail using time-resolved small-angle X-ray scattering and differential scanning calorimetry. The polyesters were found to undergo primary crystallization as well as secondary crystallization. In the primary crystallization, the thicknesses of the lamellar crystals were sensitive to the crystallization temperature, but no thickening was observed throughout the entire crystallization at a given temperature. The thickness of the lamellar crystals in the PHB homopolymer was always larger than that of the amorphous layers. In the copolymers, by contrast, the randomly distributed HHx comonomer units were found to be excluded from the lamellar crystals into the amorphous regions during the isothermal crystallization process. This interrupted the crystallization of the copolymer chains, resulting in the formation of lamellar crystals with thicknesses smaller than those of the amorphous layers. The lamellar crystals in the copolymers had lower electron densities compared to those formed in the PHB homopolymer. On the other hand, secondary crystallization favorably occurred during the later stage of isothermal crystallization in competition with the continuous primary crystallization, forming secondary crystals in amorphous regions, in particular in the amorphous layers between the primarily formed lamellar crystal stacks. Compared to the primarily formed lamellar crystals, the secondary crystals had short-range-ordered structures of smaller size, a broader size distribution, and a lower electron density.

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Polyhydroxyalkanoates (PHAs) are biodegradable aliphatic polyesters, known to be produced by many common microorganisms. Nodax is a recently introduced family of PHA copolymers comprising 3-hydroxybutyrate units and a relatively small amount of other medium chain length 3-hydroxyalkanoate (mcl-3HA) comonomers with side groups of at least three carbon units or more. There are several different grades of copolymers available, depending on the average molecular weight, average mcl-3HA content within the copolymer, and side group chain length of the chosen mcl-3HA unit. PHA copolymers with different mcl-3HA types and contents can be made either by bacterial fermentation or by chemical synthesis. The incorporation of mcl-3HA units into PHAs effectively lowers the crystallinity and T(m) in a manner similar to the effect of alpha-olefins in linear low-density polyethylene. The T(m) can be lowered well below the thermal decomposition temperature of PHAs to make this material much easier to process. The reduced crystallinity provides the ductility and toughness required for many practical applications. The mcl-3HA content regulates the T(m) and crystallinity of copolymer almost independently of the branch size, as long as more than three carbons are present in the side group. On the other hand, the side group chain length of the mcl-3HA has a profound effect on the flexibility of copolymer.

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Properties of polymer alloys comprising poly(lactic acid) and Nodax copolymers are investigated. Nodax is a family of bacterially produced polyhydroxyalkanoate (PHA) copolymers comprising 3-hydroxybutyrate (3HB) and other 3-hydroxyalkanoate (3HA) units with side groups greater than or equal to three carbon units. The incorporation of 3HA units with medium-chain-length (mcl) side groups effectively lowers the crystallinity and the melt temperature, Tm, of this class of PHA copolymers, in a manner similar to that of alpha olefins controlling the properties of linear low density polyethylene. The lower Tm makes the material easier to process, as the thermal decomposition temperature of PHAs is then relatively low. The reduced crystallinity provides the ductility and toughness required for many plastics applications. When a small amount of ductile PHA is blended with poly(lactic acid) (PLA), a new type of polymer alloy with much improved properties is created. The toughness of PLA is substantially increased without a reduction in the optical clarity of the blend. The synergy between the two materials, both produced from renewable resources, is attributed to the retardation of crystallization of PHA copolymers finely dispersed in a PLA matrix as discrete domains.

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We report an electrospray ionisation multistage mass spectrometry (ESI-MSn) method that utilises molecular mass information for determination of sequence distribution and chemical structure of mass-selected macromolecules of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) biopolyester, PHBH. On the basis of ESI-MSn studies of PHBH oligomers obtained by partial alkaline depolymerisation of natural PHBH containing 13-14 mol% of hydroxyhexanoate (HH) units, the microstructure of this bacterial copolyester was assessed up to the level of 28 repeat units. The subtle structural details of the PHBH were evaluated based on sequencing of individual macromolecular ions thus showing the utility of this technique for the analysis of biological copolyester macromolecules. It was confirmed that both HH and hydroxybutyrate (HB) units of the PHBH copolymer are randomly distributed.

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