Distinctive Polymorphism-like Isodimorphism in Poly(propylene succinate-ran-propylene fumarate)

Co-crystallization of different monomeric units fundamentally contributes to the versatile and tunable performance of random copolymers.At present,the crystallization manners of random binary copolymers have been divided into three categories:isomorphism,isodimorphism and comonomer exclusion.Each category,however,has its own advantages and disadvantages.Therefore,it is challenging to design and prepare random copolymer sharing the advantages of isomorphism and isodimorphism through a new co-crystallization manner beyond the ones already exist.On the basis of previous study on poly(alkylene succinate-ran-alkylene fumarate)whose co-crystallization can be extensively and finely regulated by simply varying the chemical structure of alkylene,random copolymers of poly(propylene succinate-ranpropylene fumarate)(PPSF)are synthesized using 1,3-propanediol as the diol source.The thermal properties and crystal structure of PPSF are investigated,and,intriguingly,it is proved that PPSF is an isodimorphism system while displays similar composition-dependent thermal properties and crystallinity as isomorphism.That is,PPSF exhibits a novel co-crystallization behavior that has rarely been discovered,which would combine the advantages of both isomorphism and isodimorphism.Consequently,PPSF could be termed as a new-type,special compositiondependent polymorphism.Besides,the altering of PPS-like to PPF-like crystal structure of PPSF when changing chain composition has been proved to originate from the shift of dominant inter-segment interaction from van der Waals forces to strong hydrogen-bonding interaction.This work enriches the co-crystallization manner of random copolymers,leading to more diverse performance design of polymer materials.

Multiple Endothermic Peaks Resulted from Different Crystal Structures in an Isomorphous Copolymer Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The multiple endothermic peaks of poly（3-hydroxybutyrate-co-3-hydroxyvalerate） （P（HB-co-HV）） in differential scanning calorimetry （DSC） results, as one representative phenomenon of polymer with unique cocrystallization behavior, were generally considered as the results of melting/recrystallization. In this study, wide angle X-ray diffraction （WAXD） and small angle X-ray scattering （SAXS） experiments were conducted to analyze the phenomena of multiple endothermic peaks in DSC results. The results of these analyses indicated that the multiple endotherms were mainly caused by different lamellae structures. For P（HB-co-HV） with lower HV content, it was comprised of two structures of HV total exclusion and HV partial inclusion in the crystal lamellae. For P（HB-co-HV） with higher HV content, it was also comprised of two structures of HV total inclusion and HV partial inclusion in the crystal lamellae. However, only structure with HV partial inclusion in the crystal lamellae remained existing after first melting peak for all samples.