Stereocomplex Crystallization in Asymmetric Diblock Copolymers Studied by Dynamic Monte Carlo Simulations

Stereocomplex crystallization in asymmetric diblock copolymers was studied using dynamic Monte Carlo simulations,and the key factor dominating the formation of stereocomplex crystallites(SCs)was uncovered.The asymmetric diblock copolymers with higher degree of asymmetry exhibit larger difference between volume fractions of beads of different blocks,and local miscibility between different kinds of beads is lower,leading to lower SC content.To minimize the interference from volume fraction of beads,the SC formation in blends of asymmetric diblock copolymers was also studied.For the cases where the volume fractions of beads of different blocks are the same,similar local miscibility between beads of different blocks and similar SC content was observed.These findings indicate that the volume fraction of beads of different blocks is a key factor controlling the SC formation in the asymmetric diblock copolymers.The SC content can be regulated by adjusting the difference between the contents of beads of different blocks in asymmetric diblock copolymers.

Can Classic Avrami Theory Describe the Isothermal Crystallization Kinetics for Stereocomplex Poly(lactic acid)?

Classic Avrami model and its modifications have found diverse applications in describing the thermal and phase behaviors of inorganic metals and organic polymers. The direct introduction of classic Avrami equation to offer quantitative analyses of crystallization kinetic parameters for enantiomeric poly（lactic acid） （PLA） blends may, however, lead to contradictory conclusions. As revealed by this study, during the characterization of isothermal melt and cold crystallization for stereocomplex PLA containing equal-weight poly（L-lactic acid） and poly（D-lactic acid）, the kinetic parameters yielded by Avrami equation are not in line with the classic crystallization hypotheses or the direct morphological observations. The underlying mechanisms, to some extent, lie in the generation of stereocomplex crystals （SCs） during the cooling/heating which affects the subsequent crystallization dynamics. The huge gap between the melting enthalpies of 100% crystalline SCs （142 J/g） and homo-crystals （HCs, 93 J/g） is most likely responsible for the confusing kinetic parameters acquired from the deduction of Avrami equation, which is based on the integration of enthalpies as a function of crystallization time. This prompts for great care that the classic Avrami equation is not applicable to accurately describe the crystallization kinetics of stereocomplex PLA, given the generation of SCs prior to crystallization and the coexistence of HCs and SCs during crystallization.

Fractionated Crystallization Kinetics and Polymorphic Homocrystalline Structure of Poly(_(L)-lactic acid)/Poly(_(D)-lactic acid)Blends:Effect of Blend Ratio

Stereocomplex(SC)crystallization has been an effective way to improve the physical performances of stereoregular polymers.However,the competition between homo and SC crystallizations can lead to more complicated crystallization kinetics and polymorphic crystalline structure in stereocomplexable polymers,which influences the physical properties of obtained materials.Herein,we select the medium-molecular-weight(MMW)poly(L-lactic acid)/poly(D-lactic acid)(PLLA/PDLA)asymmetric blends with different PDLA fractions(f_(D)=0.01-0.5)as the model system and investigate the effects of f_(D) and crystallization temperature(T_(c))on the crystallization kinetics and polymorphic crystalline structure.We observe the fractionated(i.e.,multistep)crystallization kinetics and the formation of peculiar β-form homocrystals(HCs)in the asymmetric blends under quiescent conditions,which are strongly influenced by both f_(D) and T_(c).Precisely,crystallization of β-form HCs is favorable in the MMW PLLA/PDLA blends with high f_(D)(≥0.2)at a low T_(c)(80-100℃).It is proposed that the formation of metastable β-form HCs is attributed to the conformational matching between β-form HCs and SCs,and the stronger constrain effects of precedingly-formed SCs in the early stage of crystallization.Such effects can also cause the multistep crystallization kinetics of MMW PLLA/PDLA asymmetric blends in the heating process.

Significantly Improved Stereocomplexation Ability in Cyclic Block Copolymers

Stereocomplex crystallization in cyclic polymer blend and cyclic block copolymers was investigated by means of dynamic Monte Carlo simulations.Five polymer systems(linear polymer blend,linear diblock copolymer,cyclic polymer blend,cyclic diblock copolymer and tetrablock copolymer)were established.It was interestingly found that the cyclic polymer blend exhibited the weakest stereocomplexation ability,while the two cyclic block copolymers showed stronger stereocomplexation ability than the linear diblock copolymer.This abnormal improved stereocomplexation ability of the cyclic block copolymers can be attributed to the synergy between the ring chain topology and the block copolymer structure.Compared with the linear block copolymers,the ring chain topology confined segmental motions of cyclic polymer chains to smaller regions,and then the segments belonging to the different blocks in the cyclic block copolymers have more chance to contact with each other.In this way,the cyclic block copolymers had better miscibility between segments belonging to different types of blocks,leading to the stronger stereocomplexation ability.

High Performance Polylactide Toughened by Supertough Polyester Thermoplastic Elastomers:Properties and Mechanism

It is a challenge to develop a biodegradable toughener to toughen polylactic acid(PLA)with both high strength and high toughness,since toughness and strength are mutually exclusive.Here,a series of supertough polyester thermoplastic elastomers(TPEs),poly(L/D-lactide)-b-poly(ε-caprolactone-co-δ-valerolactone)-b-poly(L/D-lactide)s(PLLA-PCVL-PLLA,L-TPEs or PDLA-PCVL-PDLA,D-TPEs),were prepared and blended with a PLLA matrix to toughen PLLA.The mechanical properties of PLLA could be regulated in a wide range by changing blending ratios and TPE structures.For PLLA blends toughened by L-TPEs,the highest elongation at break is up to 425%with the tensile strength of 33.1 MPa and the toughness of 104 MJ/m3.By the stereocomplex crystallization of PLA(sc-PLA),the tensile strength of the PLLA/D-TPE blends further increased to 41.8 MPa with a similar elongation at break(418%)and the toughness up to 128 MJ/m3.The detailed characterizations revealed a toughening mechanism:(I)the added soft segments increased the ductility of the PLLA matrix,(II)the PLLA segments of L-TPEs increased the compatibility between TPEs and PLLA matrix,and(III)the formation of sc-PLA between the PDLA segments in D-TPE and PLLA provided higher tensile strength by enhancing the strength of the crystal skeleton.The toughened PLA using TPEs can maintain original non-toxic and degradable properties,and be applied potentially in surgical sutures,and 3D-printed scaffolds.