Crystallization Of Copolymers Research Articles

How the Aliphatic Glycol Chain Length Determines the Pseudoeutectic Composition in Biodegradable Isodimorphic poly(alkylene succinate-ran-caprolactone) Random Copolyesters.

We synthesize four series of novel biodegradable poly(alkylene succinate-ran-caprolactone) random copolyesters using a two-step ring-opening/transesterification and polycondensation process with ε-caprolactone (PCL) as a common comonomer. The second comonomers are succinic acid derivatives, with variations in the number of methylene groups (nCH2) in the glycol segment, nCH2 = 2, 4, 8, and 12. The obtained copolyesters were poly(ethylene succinate-ran-PCL) (ESxCLy), poly(butylene succinate-ran-PCL) (BSxCLy), poly(octamethylene succinate-ran-PCL) (OSxCLy), and poly(dodecylene succinate-ran-PCL) (DSxCLy). We discovered a new mixed isodimorphic/comonomer exclusion crystallization in ESxCLy copolymers. The BSxCLy, OSxCLy, and DSxCLy copolymers display isodimorphic behavior. Our findings revealed a significant variation in the pseudoeutectic point position, from mixed isodimorphism/comonomer exclusion crystallization to isodimorphism with pseudoeutectic point variation from 54% to up to 90%. Moreover, we established a link between the melting temperature depression slope variation and the comonomer inclusion/exclusion balance, providing valuable insights into the complex topic of isodimorphic random copolymers.

Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide)

The Crystallization Morphology and Conformational Changes of Polypropylene Random Copolymer Induced by a Novel β-Nucleating Agent.

The crystal morphology and conformational changes during crystallization of a polypropylene random copolymer (PPR) are the basis for understanding its crystallization process. In this work, novel rare-earth β-nucleating agent WBN-28 was directly added into PPR to induce β-crystallization. The results of differential scanning calorimetry (DSC) showed that it has an excellent β-crystal-induced effect. The β-crystal content could surpass 85%, calculated from wide-angle X-ray diffraction (WAXD) data. The morphology of the β-crystal and α-crystal was intuitively observed via a polarizing optical microscope (POM). The β-crystallites were interconnected to naturally develop plate-like crystalline regions possessing a certain size, and the α-crystallites with sufficient thicknesses possessed a cross-hatched phenomenon. The bundle-like supramolecular structure of the β-crystal induced by WBN-28 was further observed via a scanning electron microscope (SEM). The conformational changes in the crystallization process of PPR were resolved via high-resolution infrared spectroscopy to understand its β-crystallization in depth. The conformational changes during the crystallization of PPR were found to be different from those of the isotactic polypropylene homopolymer (PPH); they had their own characteristics. This will provide guidance for understanding the β-crystallization of PPR in depth.

Crystal Polymorphism and Phase Transition of Isodimorphic Copolyamides Based on Even–Even and Odd–Even Comonomer Units: Synergistic Effects of Copolymer Composition and Crystallization Temperature

Crystal Polymorphism and Phase Transition of Isodimorphic Copolyamides Based on Even–Even and Odd–Even Comonomer Units: Synergistic Effects of Copolymer Composition and Crystallization Temperature

Linearly-Changed Thermal Behavior and Depressed Brill Transition in Long-Chain Polyamides Substituted by Methyl Side Groups.

Side substitution is an effective way of functionalizing and modifying the properties of polyamides. Meanwhile, side substitution would significantly influence the crystallization kinetics and polymorphic phase transition of polyamides, which, however, has not been well elucidated. Herein, we synthesized the side-substituted long-chain polyamides with various content of methyl pendent groups and investigated their crystallization and phase transition behaviors. We find that the thermal parameters of side-substituted polyamides vary linearly with the side group content, analogous to the isomorphic crystallization of random copolymers. All the solution-crystallized polyamides experience the α-γ Brill transition during heating, with the Brill transition temperature linearly decreasing as the side group content increases. Intriguingly, the γ-α transition of polyamides during cooling is suppressed with the presence of side methyl groups due to the difficulty in H-bond reorganization and gauche-trans conformational changes. This work has demonstrated the critical role of side substitution in the polymorphic crystallization and phase transition of long-chain polyamides.

Very long-time crystallization kinetics for ethylene-methacrylic acid ionomers neutralized with zinc, sodium, lithium and magnesium

Papers by our group [1] (Grady et al., 2013) and another group [2] (Paul et al. 2012) examined crystallization of random copolymers of ethylene and methacrylic acid after room temperature annealing. Similar conclusions were reached concerning the crystallization process; primary crystals were either unchanged or changed very little after annealing while secondary crystallization occurred over long time scales after annealing. The current work confirms these general conclusions for four different cations (Zn2+, Na+, Li+ and Mg2+), with the latter two not studied in either of the previous studies. Even after 6 years of annealing at room temperature, the crystallization rate is constant with logarithmic time, i.e. the material continues to crystallize. The acid copolymer does not crystallize with room temperature annealing, although secondary crystals of the acid copolymer thicken with annealing.

An efficient β-nucleating agent with high lattice matching rate for plate-like crystallization of polypropylene random copolymer.

It is challenging to naturally produce large amounts of β-crystals by directly adding a commercial β-nucleating agent (β-NA) into polypropylene random copolymer (PPR) at present. In this work, a novel rare earth β-NA WBN-28 was directly introduced into PPR to prepare β-PPR with high β-crystal conversion. The results of differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) indicated that it is an efficient β-NA for PPR. The β-conversion rate (β-CR) could surpass 85% when the nucleating agent content was mere 0.05%. With the further increment of nucleating agent, the β-CR increased gradually, which could reach 89.5% and 86.9% respectively calculated by DSC and WAXD when the addition amount was 0.4%. The incredible high β-CR delayed the βα-recrystallization in isothermal crystallization. The fusion peak of α-crystal was unobserved below the isothermal crystallization temperature of 122 °C when the addition amount was more than 0.2%. Furthermore, there was a highly ordered structure in WBN-28 with the periodicity of 12.89 Å, which was approximately twice of the unit cell parameter in the c direction of β-PP, indicating a high lattice matching rate between them. Intuitively observed by polarizing optical microscope (POM), the crystal grains of the blends with β-NA were more refined and finally crystallized in a plate-like shape. The forming process of the plate-like β crystalline regions were proposed by scanning electron microscope (SEM) and POM.

The nature of crystallographic defects in noncrystalline tubular network block copolymers

Defects are symmetry breaking features within a crystal. They can be created during growth as well as by applied mechanical forces. We address point, line and surface defects in block copolymer crystals, concentrating on the structure of defects in the tubular network double gyroid and double diamond phases. Experimental results using 3D slice and view scanning electron microscopic tomographic imaging for many types of defects are presented and the nature of the structural details and symmetries are described. Often defects are considered detrimental to the properties and performance of the material, but if the mesoscale defects in 3D periodic block copolymers can be controlled, they can be utilized to achieve various advantageous such as new optical functionalities.

Biodegradable Polyhydroxyalkanoates with a Different Set of Valerate Monomers: Chemical Structure and Physicochemical Properties.

The properties, features of thermal behavior and crystallization of copolymers containing various types of valerate monomers were studied depending on the set and ratio of monomers. We synthesized and studied the properties of three-component copolymers containing unusual monomers 4-hydroxyvalerate (4HV) and 3-hydroxy-4-methylvalerate (3H4MV), in addition to the usual 3-hydroxybutyrate (3HB) and 3-hydroxyvalerate (3HV) monomers. The results showed that P(3HB-co-3HV-co-4HV) and P(3HB-co-3HV-co-3H4MV) terpolymers tended to increase thermal stability, especially for methylated samples, including an increase in the gap between melting point (Tmelt) and thermal degradation temperature (Tdegr), an increase in the melting point and glass transition temperature, as well as a lower degree of crystallinity (40-46%) compared with P(3HB-co-3HV) (58-66%). The copolymer crystallization kinetics depended on the set and ratio of monomers. For terpolymers during exothermic crystallization, higher rates of spherulite formation (Gmax) were registered, reaching, depending on the ratio of monomers, 1.6-2.0 µm/min, which was several times higher than the Gmax index (0.52 µm/min) for the P(3HB-co-3HV) copolymer. The revealed differences in the thermal properties and crystallization kinetics of terpolymers indicate that they are promising polymers for processing into high quality products from melts.

How 4-(7-Octen-1-yl)-N,N-diphenylaniline co-units induce strong melt memory effects in isotactic polypropylene random copolymers

The random incorporation of comonomer units in isotactic polypropylene usually disrupts the chemical regularity of the macromolecular chain, thereby remarkably affecting the crystallization and melting processes. We study the influence of a novel comonomer 4-(7-Octen-1-yl)-N,N-diphenylaniline (ODPA), in the concentration range of 1.1–6.8 mol%, on the crystallization and self-nucleation behavior of isotactic polypropylene copolymers. Non-isothermal and isothermal differential scanning calorimetry experiments demonstrated that crystallization kinetics are significantly retarded upon comonomer incorporation as the ODPA co-units are excluded to the amorphous regions. Furthermore, ODPA comonomer incorporation leads to a sharp increase in nucleation density; thus, spherulitic superstructures become significantly smaller. Remarkably, the ODPA co-units induce a strong melt memory effect that can persist even above the equilibrium melting temperature for copolymers with 4.4–6.8 mol% ODPA. The width of Domain IIa (exclusive melt-memory domain), an indicator of the self-nucleation strength, starts to increase sharply once the content of ODPA exceeds 1.8 mol%. In contrast, the width of Domain IIb (self-seeding domain) remains constant. We attribute the self-nucleation effect in these ODPA copolymers to the aggregation of co-units in the interlamellar amorphous regions that hinder, upon melting, the motion of the chain sequences that were initially packed within the crystal lattice. In this way, to reach the isotropic melt state, the sample must be heated to much higher temperatures than its apparent or even equilibrium melting point, depending on the comonomer content. Consequently, nucleation upon cooling from the self-nucleated melt becomes easier and faster.

Biobased Copolymers via Cationic Ring-Opening Copolymerization of Levoglucosan Derivatives and ε-Caprolactone.

Simultaneous ring-opening copolymerization is a powerful strategy for the synthesis of highly functional copolymers from different types of cyclic monomers. Although copolymers are essential to the plastics industry, environmental concerns associated with current fossil-fuel-based synthetic polymers have led to an increasing interest in the use of renewable feedstock for polymer synthesis. Herein, we report a scalable synthetic platform to afford unique polysaccharides with different pendant functional groups from biomass-derived levoglucosan and ε-caprolactone via cationic ring-opening copolymerization (cROCOP). Biocompatible and recyclable bismuth triflate was identified as the optimal catalyst for cROCOP of levoglucosan. Copolymers from tribenzyl levoglucosan and ε-caprolactone, as well as from tribenzyl and triallyl levoglucosan, were successfully synthesized. The tribenzyl levoglucosan monomer composition ranged from 16% to 64% in the copolymers with ε-caprolactone and 22% to 79% in the copolymers with triallyl levoglucosan. The allylic levoglucosan copolymer can be utilized as a renewably derived scaffold to modify copolymer properties and create other polymer architectures via postpolymerization modification. Monomer reactivity ratios were determined to investigate the copolymer microstructure, indicating that levoglucosan-based copolymers have a gradient architecture. Additionally, we demonstrated that the copolymer glass transition temperature (Tg, ranging from -44.3 to 33.8 °C), thermal stability, and crystallization behavior could be tuned based on the copolymer composition. Overall, this work underscores the utility of levoglucosan as a bioderived feedstock for the development of functional sugar-based copolymers with applications ranging from sustainable materials to biomaterials.

Thermal and Crystallization Properties of a Polyhydroxyalkanoate Binary Copolymer Containing 3-Hydroxybutyrate and 3-Hydroxy-2-Methylvalerate Units

Polyhydroxyalkanoates (PHAs) are aliphatic polyesters synthesized intracellularly by microorganisms as a carbon-storage substance. Among the various PHAs, 3-hydroxybutyrate (3HB)-based copolymers are crystalline polymers widely used as biodegradable plastics. Recently, PHAs containing α-carbon-methylated monomers, such as 3-hydroxy-2-methylbutyrate (3H2MB) and 3-hydroxy-2-methylvalerate (3H2MV), have been synthesized and characterized. However, a binary copolymer of 3HB and 3H2MV, P(3HB-co-3H2MV), had not yet been synthesized, and its material properties had not been investigated. In this study, P(3HB-co-11 mol% 3H2MV) (PHBMV11) was synthesized with recombinant Escherichia coli LSBJ, using trans-2-methyl-2-pentenoic acid as the 3H2MV precursor. The thermal properties of PHBMV11 were characterized using differential scanning calorimetry (DSC), and the results were compared with those of P(3HB-co-12 mol% 3-hydroxyvalerate) (PHBV12) to explore the effect of α-carbon methylation in the comonomer unit. PHBMV11 exhibited a higher enthalpy of fusion during the DSC heating process and higher crystallization temperature during the DSC cooling process than those of PHBV12. The half-crystallization time of PHBMV11 was slightly longer than that of the P(3HB) homopolymer and much shorter than that of PHBV12 previously reported. The α-carbon methylation of the 3H2MV unit also has a positive effect on the crystallization of 3HB-based copolymers, as the 3H2MB unit demonstrated previously.

Comonomer Inclusion in Single Crystals of Isodimorphic Random Copolymers of Butylene Succinate and ε-Caprolactone

Random copolymers exhibit diverse crystallization behavior depending on whether comonomers are excluded or included in the crystalline phase. To understand the crystallization behavior of crystallizable isodimorphic random copolymer, in this work, we selected poly[(butylene succinate)-ran-(ε-caprolactone)], BSxCLy, copolyesters and studied their single crystal structure and morphology. The single crystals of PBS homopolymer and BS-rich copolymers were prepared by the self-seeding method in o-dichlorobenzene. The prepared single crystals were characterized by atomic force microscopy (AFM) and transmission electron microscopy. The suitable seeding temperature and the dissolution temperature of the copolymers decreased with the comonomer content. The morphological features, including size, shape, layer number, and thickness, of the single crystals depend on the seeding temperature, crystallization temperature, and, most interestingly, the composition. The size of the single crystals increased with the seeding temperature, while the aspect ratio increased with the crystallization temperature. Higher CL content in the copolymers contributed to multilayered crystals and curved edges. These characteristics were explained by the difference in growth rate and the number of dislocations, both of which are expected to be influenced by the comonomers. As revealed by AFM, the thickness of the single crystals increased with CL contents, which is the opposite of what has been reported for copolymers with high degree of comonomer exclusion. Electron diffraction of the single crystals showed smaller lattice expansion as compared to melt crystallized samples, indicating a lower degree of comonomer inclusion of CL units.

Molecular modeling and its applications in crystallizable copolymers

共聚是调控高分子材料结晶性能的有效手段，因而共聚物链单元的序列结构对其结晶行为的影响机制是高分子结构与性能关系研究中的重要科学问题。本文从可结晶共聚物链单元序列化学结构的分子建模出发，围绕无规共聚物和嵌段共聚物序列结构对其结晶行为的调控机制，总结了近年来采用动态蒙特卡罗（Monte Carlo）分子模拟方法所开展的相关研究进展。以静态条件下温度调控结晶和动态条件下应变诱导结晶这两个方面为脉络，本文结合线型低密度聚乙烯结晶、两嵌段共聚物自组装受限结晶和热塑性弹性体取向诱导结晶等典型应用案例，旨在表明有效的分子建模有助于我们深入理解共聚物结晶的微观调控机制，以便更好地从事高分子材料的基础研究和应用开发.

Dynamic Monte Carlo Simulations of Strain-Induced Crystallization in Multiblock Copolymers: Effects of Asymmetric Block Rigidity.

Thermoplastic elastomers such as polyether-b-polyamides (or -polyesters), polyurethanes (or with -urea) and olefin block copolymers are commonly processed through a stretching process for achieving high elasticity and high toughness in their products, while the size diversity of semicrystalline microdomains of hard blocks appears as the key factor. By means of dynamic Monte Carlo simulations of strain-induced crystallization of locally concentrated and diluted crystallizable blocks alternatingly connected with noncrystallizable blocks in diblock and tetrablock copolymers, we have studied the size diversity of semicrystalline microdomains presumably raised by local concentration fluctuations of crystallizable blocks and found the dilution effects to persist from diblock to tetrablock copolymers. In the present work, we continued to study the effects of asymmetric block rigidity between crystallizable and noncrystallizable blocks on strain-induced crystallization of concentrated and diluted crystallizable blocks in diblock copolymers. The results showed that when crystallizable blocks hold higher thermodynamic rigidity than noncrystallizable blocks, the large semicrystalline domains become larger and the small semicrystalline domains become more, enhancing their size diversity. However, asymmetric kinetic rigidity has little effect. Our observations imply that industrial stretching processing could enhance the toughness of semicrystalline thermoplastic elastomers when their crystallizable blocks hold a higher thermodynamic rigidity relative to noncrystallizable blocks. Our integrated approach paved the way for a better understanding of the structure-property relationship in thermoplastic elastomers.

Dynamic Monte Carlo simulations of strain-induced crystallization in multiblock copolymers: Effects of microphase separation

Semicrystalline multiblock copolymers holding alternatingly crystallizable and noncrystallizable blocks are good thermoplastic elastomers that are commonly processed through strain-induced crystallization. The crystalline microdomains play the role of physical crosslinks in the network of noncrystallizable blocks for high elasticity, and meanwhile their size diversity determines high toughness. We scheduled three integrated steps to study three physical effects of the coexisting noncrystallizable components, i.e. dilution, microphase separation and asymmetric block rigidity, on the size diversity of crystalline microdomains yielded by strain-induced crystallization in multiblock copolymers. We firstly considered the dilution effects in the extremely concentrated and diluted cases presumably generated by concentration fluctuations of crystallizable blocks, as responsible for the large-end and small-end crystalline microdomains, respectively. Our dynamic Monte Carlo simulations of strain-induced crystallization of the extremely concentrated and diluted crystallizable blocks in diblock and tetrablock copolymers demonstrated the dilution effects that the concentrated cases exhibit crystallization similar with bulk homopolymers, but the diluted cases make smaller crystalline microdomains than the cases without stretching, thus strain-induced crystallization in these two cases enhances the size diversity of crystalline microdomains (DOI: 10.1039/D2SM00193D). Hereby in the second step, we further compared the concentrated and diluted cases of strain-induced crystallization with and without microphase separation, and observed that microphase separation influences little to the concentrated cases, but makes more rather than smaller crystalline microdomains in the diluted cases, thus enhances their size diversity in a way different from the dilution effects. Higher extents of microphase separation will however weaken this enhancement. Our observations paved the way towards a better understanding of strain-induced crystallization in thermoplastic elastomers.

Steroid-Based Liquid Crystalline Polymers: Responsive and Biocompatible Materials of the Future

Steroid-based liquid crystal polymers and co-polymers have come a long way, with new and significant advances being made every year. This paper reviews some of the recent key developments in steroid-based liquid crystal polymers and co-polymers. It covers the structure–property relationship between cholesterol and sterol-based compounds and their corresponding polymers, and the influence of chemical structure and synthesis conditions on the liquid crystalline behaviour. An overview of the nature of self-assembly of these materials in solvents and through polymerisation is given. The role of liquid crystalline properties in the applications of these materials, in the creation of nano-objects, drug delivery and biomedicine and photonic and electronic devices, is discussed.

From blue fluorescence to red fluorescence: Solid-state oxidative coupling polymerization of fluorene and anthracene or naphthalene

Through the solid-state oxidative coupling polymerization, a series of fluorene-co-anthracene copolymer (PFA) and fluorene-co-naphthalene copolymers (PFN) were synthesized using FeCl3 as the oxidant. The structures of the copolymers were characterized by FT-IR and 1H NMR spectra, showing the random structures composed of fluorene units and 9,10-anthracene units or 1,4-linked naphthalene units. The increasing fluorene units in the backbones resulted in the increasing crystallization of copolymers by XRD patterns. All the copolymers exhibited good thermal stability. The optical properties could be adjusted by using different fluorene and anthracene or naphthalene ratios. Moreover, the polymer concentrations that affected the photoluminescence emission ranged from blue light to red light. The concentration-induced discoloration property also could be observed from the copolymers on the filter paper of TLC plates. This is attributed to the change in the effective conjugation length of a single polymer and the formation of polymer aggregates and excimers. These unique properties endow the PFA and PFN with potential applications in optoelectronics. Especially, these polymers exhibit enhanced emissions and on/off fluorescent switching which senses THF vapor efficiently.

Controlled Crystallization of Diblock Copolymers on Carbon materials: Effect of Block Length

The fabrication of sophisticated hybrid mesostructures involving carbon nanomaterials and organic building blocks has attracted great attention due to their tunable properties and potential applications. Herein, we report the precisely controlled structure and morphology of diblock copolymers-carbon materials hybrid mesostructures, in which nano/micron- disc shape and honeycomb structure were fabricated on the surfaces of carbon nanotube (CNT), carbon nanofiber (CNF), and graphite, respectively. Synthesized ethylene/functional cyclic olefin block copolymers (PE-b-HPNBMA) showed a narrow dispersity, allowing the formation of nanohybrid shish-kebab structures (NHSK) with a highly uniform disc-shape crystalline size and period. The tunability of HPNBMA block length and functional substituent enables not only control of the nanocrystal size but also flexible design of the surface chemical structure, which can endow diblock copolymers-carbon materials hybrid mesostructures with specific properties. As proof of the ability, superhydrophobic (contact angle > 150°) NHSK films with tunable adhesion were successfully produced.

Dynamic Monte Carlo simulations of strain-induced crystallization in multiblock copolymers: effects of dilution.

Multiblock copolymers containing alternating semicrystalline and molten blocks are good thermoplastic elastomers. Their crystallization in the stretching process is however complicated by the dilution effects, prior microphase separation and contrast chain rigidity of the molten blocks. We designed our systematic investigation with three integrated steps, and herein, as the first step, we considered only the dilution effects without prior microphase separation and contrast chain rigidity. We compared two extreme situations of local dilution separately corresponding to parallel-posited and antiparallel-posited block copolymers upon strain-induced crystallization. Our dynamic Monte Carlo simulations of diblock and tetrablock copolymers demonstrated that the stretching introduces a constraint on the diffusion of locally posited crystallizable blocks along the stretching direction for crystallization and thus enhances the dilution effects to result in a higher diversity in crystal stabilities. We observed that the strain-induced crystallization of parallel-posited copolymers behaved like the melt crystallization of homopolymers; in contrast, the strain-induced crystallization of antiparallel-posited copolymers yielded crystallites near the block junction, which are relatively small and less stable due to their local dilution suppressing their melting points. Similar to the case of spider dragline silks, two contrasting stabilities of crystallites in semicrystalline multiblock copolymers explain their good toughness. Our modeling approach paves the way toward a better understanding of the structure-property relationship in the semicrystalline thermoplastic elastomers.