Jingru Sun

Chiral Salan Aluminium Ethyl Complexes and Their Application in Lactide Polymerization

Synthetic routes to aluminium ethyl complexes supported by chiral tetradentate phenoxyamine (salan-type) ligands [Al(OC(6)H(2)(R-6-R-4)CH(2))(2){CH(3)N(C(6)H(10))NCH(3)}-C(2)H(5)] (4, 7: R=H; 5, 8: R=Cl; 6, 9: R=CH(3)) are reported. Enantiomerically pure salan ligands 1-3 with (R,R) configurations at their cyclohexane rings afforded the complexes 4, 5, and 6 as mixtures of two diastereoisomers (a and b). Each diastereoisomer a was, as determined by X-ray analysis, monomeric with a five-coordinated aluminium central core in the solid state, adopting a cis-(O,O) and cis-(Me,Me) ligand geometry. From the results of variable-temperature (VT) (1)H NMR in the temperature range of 220-335 K, (1)H-(1)H NOESY at 220 K, and diffusion-ordered spectroscopy (DOSY), it is concluded that each diastereoisomer b is also monomeric with a five-coordinated aluminium central core. The geometry is intermediate between square pyramidal with a cis-(O,O), trans-(Me,Me) ligand disposition and trigonal bipyramidal with a trans-(O,O) and trans-(Me,Me) disposition. A slow exchange between these two geometries at 220 K was indicated by (1)H-(1)H NOESY NMR. In the presence of propan-2-ol as an initiator, enantiomerically pure (R,R) complexes 4-6 and their racemic mixtures 7-9 were efficient catalysts in the ring-opening polymerization of lactide (LA). Polylactide materials ranging from isotactically biased (P(m) up to 0.66) to medium heterotactic (P(r) up to 0.73) were obtained from rac-lactide, and syndiotactically biased polylactide (P(r) up to 0.70) from meso-lactide. Kinetic studies revealed that the polymerization of (S,S)-LA in the presence of 4/propan-2-ol had a much higher polymerization rate than (R,R)-LA polymerization (k(SS)/k(RR)=10.1).

Investigation of poly(lactide) stereocomplexes: 3-armed poly(L-lactide) blended with linear and 3-armed enantiomers.

Stereocomplex poly(lactide)s (sc-PLAs) were obtained from solution blending of 3-armed poly(L-lactide) (3PLLA) and linear poly(D-lactide) (PDLA) and between enantiomeric 3PLAs. Differential scanning calorimetry and wide-angle X-ray diffraction results indicated that racemic crystallites were preferentially produced in all the binary blends. The melting temperature and fusion enthalpy of racemic crystallites were remarkably different through varying the structure, constituent, and molecular weight of PLA. Through this investigation, higher melting temperatures were obtained in the middle molecular weight binary blends, and the highest melt temperature of racemic crystallites reached to 246 °C, it was the highest reported value until now. In similar molecular weight blends (or the linear PLA was similar to each branch of 3PLA enantiomers), with the composition of 3PLA increasing, the phase separation molecular weight decreased gradually (M(linear/linear blends) > M(linear/3-armed blends) > M(3-armed/3-armed blends)). The structure distinction between 3PLA and linear PLA induced different thermal properties and phase behaviors of the 3PLLA/PDLA and 3PLLA/3PDLA blends. The thermal properties of these mixtures and its variations provided basic data for their industrial applications.

Crystallization Behavior of Asymmetric PLLA/PDLA Blends

The effects of the addition of poly(D-lactide) (PDLA) on the crystallization behavior of poly(L-lactide)(PLLA) were investigated by means of differential scanning calorimetry (DSC) and temperature-dependent X-ray diffraction(XRD). When the blends were cooled from different temperatures (250, 240, and 190 °C) at the rate of cooling of 5 °C/min, stereocomplex (sc) crystallites could stay at diverse states. Accordingly, the stereocomplexes acted as a nucleation agent exerting distinct effects on PLLA crystallization. The speculated mechanisms of the stereocomplex formation and the effectiveness as a nucleating agent are schematically described. Moreover, temperature-dependent XRD was carried out to further investigate the melt-crystallization behavior of PLLA/PDLA blends in real time. Temperature-dependent XRD results indicated that even at 240 °C the stereocomplex crystallites in all blend samples existed clearly, which could not be detected by DSC. These XRD results further suggest that the onset T(c) values for the PLLA α-form crystals formation were 160, 120, 140, and 160 °C, respectively, for neat PLLA, PLLA/PDLA 95/5, 90/10, and 80/20 as well as 70/30 samples.

An Optical Microscopy Study on the Phase Structure of Poly(l-lactide acid)/Poly(propylene carbonate) Blends

The dependence of phase structure of PLLA/PPC blends on the blend ratio, the heat-treatment temperature and time was investigated by optical microscopy. It is found that, at lower PPC content, e.g., less than 30%, the PLLA crystalline spherulites fill the whole space with the PPC dispersed in the amorphous region of PLLA. No evident phase separation has been observed under optical microscope. When the content of PPC reaches 40%, phase separation takes place. The phase separation of the PLLA/PPC blend happens prior to the crystallization of PLLA. Therefore, the heat-treatment temperature and time are the two most important factors that control the phase structure of the blend. At low heat-treatment temperatures, e.g., lower than 190 °C, the PPC and the amorphous PLLA part compose a continuous phase with the crystalline PLLA domains dispersed in it. When the sample was heat-treated at 200 °C for 5 min, a bicontinuous phase structure was observed. With further increase of the heat-treatment temperature, the crystalline PLLA composes the continuous phase with PPC domains randomly dispersed in it. Similar phase reversal phenomenon has also been observed by heat-treating the samples at 200 °C for different times. It is further confirmed that the crystallization of PLLA in the blends is influenced by the different phase structures. For example, the crystallinity of PLLA in the blend increases with increasing heat-treatment temperature.

The stereocomplex formation and phase separation of PLLA/PDLA blends with different optical purities and molecular weights

In this study, the poly(L-lactide)/poly(D-lactide) (PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and phase separation behaviors of these blends are investigated. Results reveal that optical purity and molecular weight do not vary the crystal structure of PLA stereocomplex (sc) and homochiral crystallites (hc). As the optical purity increasing in the blends, the melting temperature of sc (Tsc) and the content of sc (ΔHsc) increased, while the melting temperature of hc (Thm) hardly changes, although the content of hc (ΔHhm) decreased gradually. The Tsc and ΔHsc are also enhanced as the molecular weight of PDLA reduces, and the ΔHhm reduces rapidly even though the Thm does not vary apparently. With lower optical purities of PLLA and higher molecular weights of PDLA, three types of crystals form in the blends, i.e., PLA sc, PLLA hc and PDLA hc. As molecular weight decreases and optical purity enhances, the crystal phase decreases to two (sc and PDLA hc), and one (sc) finally. This investigation indicates that the phase separation behavior between PLLA and PDLA in the PLLA/PDLA blends not only depends on molecular weights, but also relies on the optical purities of polymers.

Synergistic effect of PLA–PBAT–PLA tri-block copolymers with two molecular weights as compatibilizers on the mechanical and rheological properties of PLA/PBAT blends

Two types of polylactide–poly(butylene adipate-co-terephthalate)–polylactide (PLA–PBAT–PLA) tri-block copolymers with different molecular weights (CP1 and CP2) were synthesized as compatibilizers for PLA/PBAT blends. Synergistic effects of CP1 and CP2 on the mechanical and rheological properties of the blends have been studied in detail. The addition of small amounts of CP1 and CP2 remarkably increased the elongation at the break point. 0.5 and 0.5 wt% of CP1 and CP2 led to an increase of elongation by over eightfold. Thermal, morphological and rheological analyses showed that addition of CP1 and CP2 increased the miscibility and interfacial bonding strength between PLA and PBAT, in addition to decreasing the melt viscosity. It was thought that the low-molecular-weight compatibilizer CP1 with high mobility would have a positive effect during the transportation of the high-molecular-weight CP2 from the matrix to the interface. In addition, CP2 played a key role in improving the interaction at the interface.

The formation and transition behaviors of the mesophase in poly(D-lactide)/poly(L-lactide) blends with low molecular weights

The poly(D-lactide)/poly(L-lactide) (PDLA/PLLA) blends with low molecular weights were cast from solution. After heating to above the melting temperature, followed by cooling at various rates, DSC, WAXD and FTIR studies revealed that a mesomorphic phase developed in the PDLA/PLLA 90/10 and 80/20 (or 10/90 and 20/80) specimens when the temperature window spanned from 80 °C to 110 °C. The mesophase melted and reorganized into crystallites after the temperature increased to ∼130 °C. Although the formation and transition of the mesophase was observed at lower temperatures in partially crystallized specimens, the mesophase could exist steadily when the temperature did not exceed 100 °C. The content of the mesophase was proven to be strongly dependent on the cooling rate, the D/L weight ratio and the molecular weights in the blends. The formation of the mesophase could be explained by the fact that the crystallization of the PLA matrix was disturbed by the addition of small amount of enantiomeric PLA.

The morphology and spherulite growth of PLA stereocomplex in linear and branched PLLA/PDLA blends: effects of molecular weight and structure

Linear and three-armed poly(L-lactide)/poly(D-lactide) (PLLA/PDLA, 3PLLA/3PDLA and 3PLLA/PDLA) specimens were prepared through a solution mixing method, and the morphology and the spherulite growth of poly(lactide) stereocomplex crystallites (PLA sc) from the melt with various structures and molecular weights were investigated. Polarized optical microscopy images revealed that regular spherulites and a visible boundary developed in all of the PLLA/PDLA blends with relatively lower molecular weights (Mn 3PLLA/PDLA > 3PLLA/3PDLA).

Facile preparation of corn starch nanoparticles by alkali-freezing treatment

In this article a facile way of producing starch-based nanoparticles (SNPs) with high yields and predictable size by an alkali-freezing treatment is presented. A new mix solvent, sodium hydroxide–urea aqueous solution, has been developed to disperse corn starch. After refreezing, thawing, stirring at room temperature and dialysis, resultant aqueous suspensions of SNPs are obtained and characterized using a scanning electron microscope (SEM) and dynamic light scattering (DLS) to learn the particle morphology, mean size and size distribution. By adjusting parameters such as the sodium hydroxide : urea ratio and temperature, the size of particles can be controlled from micro- to nanometer. Furthermore, this process that leads to the nanoparticles causes no changes in the structures of the starch granules as characterized by IR or 1H-NMR. Freeze-dried SNPs were found to be amorphous as revealed by wide-angle X-ray diffraction (WAXD).