Xuefei Leng

Facile synthesis and comparative study of poly(L-lactide) with linear-comb and star-comb architecture

In this work, two series of linear-comb and star-comb well defined graft poly(L-lactide) (PLLA) have been synthesized conveniently by one-pot ring-opening polymerization (ROP) of L-lactide using functionalized polybutadiene macroinitiators. The used organocatalyst of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) allows the polymerization of L-lactide to proceed rapidly at room temperature. Kinetic studies of the ROP reaction in this system indicate first-order kinetics in monomer concentration. 1H NMR and GPC techniques are employed to characterize the synthesized polymers, validating the formation of the desired comb structures with controllable chain length. Linear-comb and star-comb graft PLLA were comparatively studied as well as with linear PLLA by DSC and POM. The results reveal that the comb structure gives a remarkable improvement of PLLA crystallization ability in both crystallinity and growth rate of spherulites. Furthermore, the more compacted star-comb structure imposes restriction on chain mobility, which weakens the growth effect to some extent. It is found that the glass transition temperature (Tg) and melting temperature (Tm) significantly depend on the side chain length and backbone structure. Rheological studies of both melt and instinct viscosity of the solution show that star-comb PLLA has the lowest hydrodynamic volume compared with linear-comb PLLA and linear PLLA.

Copolymerization of L-lactide/trimethylene carbonate by organocatalysis: controlled synthesis of comb-like graft copolymers with side chains with different topologies

A series of linear-comb poly(trimethylene carbonate)-block-poly(L-lactide) [lcP(TMC-b-LLA)] with polybutadiene (PB) as backbone and a P(TMC-b-LLA) diblock copolymer as side chain were obtained using controlled synthesis and evaluated as thermoplastic elastomers. The comb-like graft copolymer was achieved using sequential ring-opening polymerization of trimethylene carbonate (TMC) and L-lactide (L-LA) at room temperature (RT) using an organocatalyst, associated with the multi-hydroxyl PB (PB–OH) as a macroinitiator. The thermal and mechanical properties of these graft copolymers were investigated using differential scanning calorimetry, dynamic mechanical analysis and tensile testing. The Youngs modulus (E) and the elongation at break (eb) followed predicted trends as the monomer composition changed. Furthermore, well defined linear-comb PLLA-gradient-PTMC [lcP(LLA-grad-TMC)] and linear-comb PLLA-random-PTMC [lcP(LLA-ran-TMC)] were also synthesized for comparison. Results from 1H and 13C-NMR spectroscopy, and gel permeation chromatography confirmed the formation of the chain microstructures. It was found that the properties of the copolymers depended not only on the comonomer content but also on their topologies. The results showed that the gradient and random structure of the side chain could yield unusual properties: the lcP(LLA-grad-TMC) copolymer possessed a distinctive, broad glass transition temperature in comparison with the other two graft copolymers. The lcP(LLA-ran-TMC) random copolymer performed like a typical rubber with a significant high eb value (eb = 1800%) which was even larger than the pure linear-comb PTMC (eb = 865%). Furthermore, this simple “one-pot” method using an organocatalyst to synthesize comb-like graft copolymers with “block”, “gradient” and “random” side chains is demonstrated systematically in this work.

Rheological properties and crystallization behavior of comb-like graft poly(L-lactide): influences of graft length and graft density

Three series of narrowly dispersed comb-like graft poly(L-lactide) (PLLA) with controlled graft length and graft density have been facilely synthesized and characterized. The structural information was determined by means of 1H NMR, GPC, and viscometry, demonstrating the well-defined grafted structure. The effects of grafting parameters on rheological properties, thermal and crystallization behaviors were investigated systematically to illustrate the structure–property relationships. By the analysis of the rheological behavior, the increase of graft length and graft density can both lead to an elevated value of zero-viscosity (η0), enhanced complex modulus (G*) and increased complex viscosity (η*). Comparatively, graft density contributes more to the improvement of rheological properties than graft length does. For thermal properties, DSC results show that the glass transition temperature (Tg), the melting temperature (Tm) and the crystallization enthalpy (ΔHm) of graft PLLA increase with the chain length and decrease with the graft density. Furthermore, spherulite morphologies and growth rates were studied by polarized microscopy (POM), and the observation revealed a remarkable improvement of radius growth rate of the spherulites (G) when graft density increased. The results indicate that G depends more on the molecular weight of each arm (Mn,arm) than the total Mn.

Synthesis of highly branched poly(δ-valerolactone)s: a comparative study between comb and linear analogues

A large diversity of tailor-made linear-comb and star-comb poly(δ-valerolactone)s (PVL) have been obtained with hydroxylated polybutadiene (HPB) as a macroinitiator and 1,5,7-triazabicyclo-[4.4.0]dec-5-ene (TBD) as a catalyst by a simple “one-step” method. The critical content of this research was to explore systematically the differences in the physicochemistry properties between highly branched PVLs and linear PVLs, including the intrinsic viscosity, rheological properties, and crystallization and melting behavior. Studies of solution behavior and melting behavior elucidated that intrinsic viscosities in solution and complex viscosities in the bulk for comb branched PVLs were much lower compared with their linear and star counterparts. Both WAXD and DSC analysis of PVLs with different topological structures indicated that the comb branched architectures do not alter the structures of the PVL crystallites, but markedly improve the crystallization behavior, e.g. higher crystallinities. Moreover, the influence of the molecular weight of a single arm on the thermal properties and crystallization properties of the obtained linear-comb PVLs was explored. The results demonstrated that the crystallization temperatures (Tcs), melting temperatures (Tms) and crystallinities increased with the increase of molecular weight of a single arm. As such, a structure–property correlation is expected to be constructed which is of great practical importance in the syntheses and applications of highly branched polymers (HBPs).

Relationship between melting behavior and morphological changes of semicrystalline polymers

The present study on the case of poly(hexamethylene succinate) is to provide a basis for a better understanding of the subtle relationship between melting behavior and morphological changes of semicrystalline polymers. The melting behavior and morphological changes of poly(hexamethylene succinate) during both isothermal secondary crystallization and annealing processes were investigated by DSC and SAXS. DSC results showed that, with increasing crystallization time or annealing time, the melting endotherm continuously shifted to higher temperature, which suggested that some minor structural or morphological changes must occur. However, almost no changes at all on the crystal thickness were observed from SAXS measurements. The observed evidence confirmed that the increase in the melting temperature is not attributed to crystal thickening but crystal perfection. More exactly, the rearrangement and smoothing of tie molecules at the folding surface result in the reduction of the fold surface free energy, which dominantly contributes to the increase in the melting peak temperature. The origin of the new endothermic peak observed after annealing at elevated temperature was also discussed. TMDSC results indicated that the annealing peak resulted from the enthalpy relaxation and devitrification transition of rigid amorphous fraction formed by the driving force of thermodynamic nonequilibrium, rather than usually regarded as the melting of thin lamellae or imperfect crystals formed by annealing secondary crystallization.