Butylene Fumarate Research Articles

Manipulating the Co-crystallization Behavior in Isomorphic Copolymers by Introducing a Third Monomeric Unit

Isomorphism is a distinctive kind of co-crystallization behavior of random copolymers and provides opportunities to regulate the crystalline structure and performance without the loss of crystallinity. Though the intrinsic structural differentiation would induce variation of accommodation capacity in the co-crystal lattice for different co-monomeric units, subtle manipulation of isomorphism has not been realized yet. In this study, butylene adipate (BA) as the crystallizable unit is incorporated into an isomorphism system model of poly(butylene succinate-ran-butylene fumarate) (PBSF) to form the terpolymers of PBSFA, and the crystallization features are investigated. It is confirmed that part of BA (i.e., ≤20 mol %) does not hinder the isomorphism formation in the terpolymers of PBSFA but influences the accommodation capacities of the isomorphic counterparts of butylene succinate (BS) and butylene fumarate (BF). When BA with 10 mol % is copolymerized, the adoption of BS unit in isomorphism becomes less favorable in comparison to the biopolymers of PBSF, showing an increase of the defect Gibbs free energy for the co-crystal and a decrease of the accommodation ratio of BS. However, with a further lifting of the BA content to 20 mol %, the accommodation preference of BS and BF in the isomorphism lattice reverses, and BS turns into a favorable unit instead of BF. Such a transition of accommodation capacity might be due to the deterioration of intersegmental interaction caused by the third co-crystallizable unit of BA. This work directly reveals the differentiation of co-monomeric units in the isomorphic lattice and sheds light on the manipulation of isomorphism.

Promoting Co-Crystallization in Poly(butylene succinate) and Poly(butylene fumarate) Blends via End-Group Functionalization.

Co-crystallization plays a crucial role in the integration and regulation of thermal and mechanical properties in polymer blends, but the poor compatibility of the components in the crystal phase has always been a major obstacle to co-crystallization, which puts forward stricter requests for linkage and interaction between different entities. On the basis of the hydrogen-bonding interaction that can promote chain stacking and thus improve miscibility, we propose that crystalline/crystalline blends of 2-ureido-4[1H]-pyrimidinone (UPy)-functionalized poly(butylene succinate) and poly(butylene fumarate) (PBS-UPy/PBF-UPy) where UPy groups with quadruple hydrogen-bonding interaction are employed to connect different chain ends, could inhibit phase separation and improve co-crystallization. PBS-UPy/PBF-UPy blends exhibit complex component-dependent and cooling-rate-dependent co-crystallization behavior. A high level of co-crystallization occurs in the range of PBS-UPy-rich fractions, and the proportion could approach over 98% under optimized conditions with the aid of UPy quadruple hydrogen bonds interaction. This work enriches the understanding of co-crystallization in crystalline/crystalline polymer blends and provides more possibility for the design of structures and properties of polymer materials.

Asymmetrical formation of isomorphism in the crystalline/crystalline blend of poly(butylene succinate) and poly(butylene fumarate)

Blending is a convenient method to regulate the crystallization behavior and thus the performance of polymer materials, but poor compatibility in crystalline phase for different components remarkably depresses the co-crystallization capability, which poses a great challenge to effective regulation of the properties for crystalline/crystalline blends. In this work, the co-crystallization between two kinds of polyester with similar chain structure, poly(butylene succinate) (PBS) and poly(butylene fumarate) (PBF) is investigated and found to be dependent on the blending ratio and crystallization condition. A new type of co-crystal is only discovered in the PBS-rich blends (i.e., PBS/PBF-6/4 and PBS/PBF-8/2), and, further, it is proved as the isomorphism between PBS and PBF by employing various characterizations of differential scanning calorimeter and Fourier transformation infrared spectrometer and X-ray diffractometer. Both the enhancing cooling rate and the increasing PBS content benefit the growth of isomorphic co-crystal, and, its fraction in the blend of PBS/PBF-8/2 can reach as high as ∼75% during a fast cooling rate of 40 °C/min. In addition, the changes of Gibbs free energy for including butylene fumarate unit into PBS-type crystal and including butylene succinate unit into PBF-type crystal are respectively calculated as −0.96 and 1.94 kJ/mol, revealing the intrinsic thermodynamic driving force for the forming of isomorphism and clarifying why isomorphism only occurs in the PBS-rich blends. Finally, a summary of the crystallization behavior of PBS/PBF blend is reasonably sketched, which will help design the crystalline/crystalline blends with desired structure and performance.

Template synthesis of fibrillar polyaniline complex using a degradable polyelectrolyte

Abstract Functionalized poly(butylene succinate) (PBSS), prepared via sulfonation of poly(butylene fumarate) (PBF), was successfully applied as a novel polymeric dopant for polyaniline (PANI). To obtain a conductive and degradable PANI:PBSS complex, the aniline monomers were polymerized in the presence of a negatively charged polyelectrolyte template (PBSS). The prepared polymers were characterized through proton nuclear magnetic resonance (1HNMR), Fourier transform infrared (FT-IR), ultraviolet–visible spectroscopy (UV–visible spectroscopy), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), X-ray diffraction (XRD) and electrical conductivity measurements. The hydrolytic degradation of PANI:PBSS was also investigated based on FT-IR analysis and weight loss. Based on the results, the semi-crystalline structure of PBF was changed to an amorphous structure in PBSS and PANI:PBSS. The PANI morphology in the presence of the small dopant (HCl) was granular, while it changed into a fibrillar shape in the presence of the macromolecular dopant. The electrical conductivity of PANI:PBSS (28.6 S/m) was slightly smaller than that of the HCl-doped PANI (48.4 S/m). The alkaline solution could hydrolytically degrade PANI:PBSS and after 10 days, a weight loss of 45% was observed.

Effect of graphene oxide on features of functionalizable Poly(Butylene fumarate) and functional Poly(Butylene succinate) doped polyaniline

A novel material that obtained through combining a biodegradable polymer with a conductive polymer, has been successfully developed by graphene oxide (GO). For the first time, unsaturated poly(butylene fumarate) grafted reduced GO (PBF:RGO) was synthesized via in-situ polymerization method and simultaneous in-situ thermal reduction of GO. It was modified through post-polymerization modification to form sulfonated poly(butylene succinate) grafted reduced GO (PBSS:RGO). Then, PBSS:RGO was incorporated as a polymeric dopant in the synthesis of polyaniline (PANI) to prepare the conductive and anticorrosive compound. Functionalizable PBF and PBF:RGO along with functional PBSS and PBSS:RGO were characterized by 1HNMR. Thermal and crystallization properties of PBF and PBF:RGO were studied using thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC) with Avrami and Tobin models. Further investigation of crystallinity and dispersion of graphene sheets in the polymer matrix was carried out by X-ray diffraction (XRD). PBF:RGO exhibits higher thermal stability, higher crystallization rate, and lower crystallinity compared with pristine PBF. Final composites (PANI:PBSS and PANI:RGO:PBSS) were also characterized through Fourier transform infrared (FT-IR), contact angle analysis, electrochemical impedance spectroscopy (EIS) and electrical conductivity measurements. PANI:RGO:PBSS indicates a higher conductivity, higher inhibition efficiency and more hydrophilicity than PANI:PBSS.

Crystallization of isomorphic poly(butylene succinate-co butylene fumarate) biopolyester: Single crystals and ring-banded spherulites

Poly(butylene succinate-co-butylene fumarate) (PBSF) copolymers with butylene fumarate (BF) molar ratio varies from 1% to 40% were synthesized and their single crystals were prepared using a self-seeding method. For PBSFs with low content of BF units, the single crystals are regular hexagonal shape. With the increase of BF molar ratio, the single crystal boundary turns rounded and the aspect ratio decreases. PBSF single crystals with different BF content were prepared at the same temperature, the supercooling degree of the PBSF increases with the increase of BF content, resulting the crystalline density increases and the single crystal size decreases. Selected area electron diffraction (SAED) was used to investigate the crystalline structures of the PBSF single crystals, and the results approve strict isomorphism between butylene succinate (BS) and BF in PBSF, verifying that preparing the single crystal and characterizing the crystalline structure by SAED is a direct method to check for isomorphic polymers. PBSFs can form ring-band spherulites at suitable crystallization temperatures. The band spacing of PBSF increases with the increase of isothermal crystallization temperature. At the same isothermal crystallization temperature, the band spacing PBSF decreases with the increase of BF molar ratios. The crystallization temperature range of forming ring-banded spherulites broadens with the increase of BF molar ratios.

Effects of isomorphic poly(butylene succinate-co-butylene fumarate) on the nucleation of poly(butylene succinate) and the formation of poly(butylene succinate) ring-banded spherulites

The composition of isomorphic PBSF can dramatically affect the nucleation efficiency, the formation temperature of ring-banded spherulite and the band spacing of the PBS.

Crystallization and photo‐curing kinetics of biodegradable poly(butylene succinate‐co‐butylene fumarate) short‐segmented block copolyester

AbstractShort‐segmented block copolymers of poly(butylene succinate‐co‐butylene fumarate) were synthesized and their crystallinity and crosslinking behavior were investigated. 1H NMR was used to characterize the microstructure and composition of the copolyesters. Molecular weight determination was performed using gel permeation chromatography. Based on the DSC results all copolyesters were crystalline and the degree of crystallinity of the copolymers did not change with butylene fumarate mole fraction due to co‐crystallization of the butylene succinate and butylene fumarate groups. Crosslinked copolyesters showed a lower crystallization rate and degree of crystallinity while the crystallization temperature shifted to higher temperatures compared with uncrosslinked copolyesters due to the formation of nucleating agents by crosslinkages. Photo‐DSC was used to investigate the crosslinking kinetics for UV‐initiated photo‐curing. Three kinetics parameters including the rate constant (k) and the orders of the initiation and propagation reactions (m and n, respectively) were determined for the quenched and unquenched copolymers. © 2016 Society of Chemical Industry

Regulating the polymorphism behaviour and crystal transformation of poly(butylene adipate) by incorporating butylene fumarate units into the crystal lattice

Copolymerized butylene fumarate units benefit the formation of β-form poly(butylene adipate) at high temperature by cocrystallizing into the crystal lattice.

Efficient synthesis of ionic triblock copolyesters and facile access to charge‐reversal hybrid micelles

ABSTRACTNovel carboxyl‐ and amino‐functionalized copolyesters, based on poly(ε‐caprolactone)‐block‐poly(butylene fumarate)‐block‐poly(ε‐caprolactone), were efficiently synthesized via Michael‐type thiol‐ene click chemistry. The resulting amphiphilic copolyesters with controllable molecular weights and abundant positively or negatively charged groups could spontaneously form pH‐sensitive micelles in aqueous solutions, as confirmed by transmission electron microscopy, dynamic light scattering, fluorescence probing technique, and zeta potential analyses. Importantly, charge‐reversal hybrid micelles can be obtained by co‐assembly of carboxyl‐ and amino‐functionalized copolyesters. The surface charges of hybrid micelles reversed rapidly from negative to positive at isoelectric point via protonation of surface carboxyl and amino groups. Interestingly, the hybrid micelles showed apparent pH‐triggered Nile red‐release behavior in acidic condition resembling tumor intracellular environment, which is fairly desirable for drug delivery. Our work indicates that co‐assembly is a facile but efficient way to prepare charge‐reversal micelles, which have great potential to be used as intelligent drug delivery systems for cancer therapy. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 1259–1267

Functional polyester with widely tunable mechanical properties: The role of reversible cross-linking and crystallization

A novel strategy for preparation of unsaturated polyester-based functional materials with widely tunable mechanical properties has been reported in present work. The biodegradable and crystallizable poly(butylene fumarate) oligomer (PBF) bearing reactive carbon–carbon double bonds on the backbone was functionalized by Michael addition with furfurylamine (FA), followed by incorporating bismaleimide (BMI) as cross-linker to form a reversibly cross-linked polyester (PBF-FA-BMI). The obtained material was systematically characterized by a combination of differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), rheometry measurement, wide-angle X-ray scattering (WAXS) as well as mechanical property testing. The in-situ FTIR and rheology measurements demonstrated the competition process of DA reaction and crystallization for dynamic conditions and isothermal conditions. The characteristic of dynamically chemical structure variation and crystallization behavior provides a possibility to tune the mechanical property of PBF-FA-BMI. By thermal treatment, the structure programming of the material can be facilely achieved, which undergoes from a typically elastomer to plastic. A schematic illustration of thermo-responsive conversion and recyclability is proposed for the cross-linked polyester.

Enhanced crystallization rate of biodegradable poly(butylene succinate-co-ethylene succinate) by poly(butylene fumarate) as an efficient polymeric nucleating agent

PBF may significantly enhance the nonisothermal melt crystallization behavior of biodegradable PBES by acting as an efficient polymeric nucleating agent.

Role of Poly(butylene fumarate) on Crystallization Behavior of Poly(butylene succinate)

The details of poly(butylene fumarate) (PBF) as highly effective nucleating agent for poly(butylene succinate) (PBS) were systematically studied via X-ray diffraction, differential scanning calorimeter, polarized optical microscopy, and atom force microscopy. All results show that PBF can significantly improve the melt-crystallization temperature and the degree of crystallinity of PBS during the nonisothermal crystallization process. Both crystallization time span and spherulitic size of PBS decrease drastically with the addition of a small amount of PBF, which shows that PBF not only enhances the primary nucleation of PBS by epitaxial mechanism, but also greatly accelerates the secondary nucleation during spherulite growth. The secondary nucleation parameters of PBS, Kg and G0, are notably improved just with a small amount of PBF. Furthermore, the appearance of wrinkles on PBF-nucleated PBS ultrathin film visually suggests that PBF indeed affects the subsequent growth behavior, besides the primary nuclea...

Novel Poly(butylene fumarate) and Poly(butylene succinate) Multiblock Copolymers Bearing Reactive Carbon–Carbon Double Bonds: Synthesis, Characterization, Cocrystallization, and Properties

Widespread application of biodegradable polyesters is restrained by inferior mechanical properties, higher cost, and lack of reactive functional sites for further modification. A new class of multiblock copolymers bearing reactive sites on the main chains, composed of poly(butylene fumarate) (PBF) and poly(butylene succinate) (PBS), has been designed and synthesized to enhance the biodegradability of PBF and expand its application, while retaining the mechanical properties. The chemical structures of the copolymers were confirmed by 1H NMR spectra and GPC. The two segments are compatible in both the amorphous and crystalline region, and form cocrystals because of their similar nature. The multiblock copolymers possess satisfactory thermal and mechanical properties. The degradation rate of copolymers is substantially accelerated by the copolymerization with PBS. The novel polymer may be directly used as biodegradable materials or be postfunctionalized to modify the physicochemical properties or to endow the polymers with special properties.

Synthesis, characterization and properties of novel linear poly(butylene fumarate) bearing reactive double bonds

Poly(butylene fumarate) (PBF) bearing reactive double bonds on the polymer main chains has been designed and synthesized by coupling with hexamethylene diisocyanate (HDI) under very mild condition. The chemical structure, conformational structure, crystal structure and molecular weight of PBF were systematically characterized by ATR-FTIR, 1H NMR, 13C NMR, GPC and WARD. The thermal properties, mechanical properties and biodegradability of PBF were carefully studied by DSC, mechanical testing and enzymatic degradation. The results of 1H NMR and 13C NMR spectra indicate that no isomerization or Ordelt saturation reaction of trans CC took place during the bulk polymerization and the reaction just proceeded in the way we designed. Linear PBF with high-molecular-weight has been successfully synthesized. This new type of uncrosslinked polyester is shown to have many merits such as relatively high melting point (Tm), satisfactory processability and good mechanical properties. The impact strength of PBF is higher than 200 J/m; tensile and flexural strength can reach to 41.0 and 26.7 MPa, respectively.

Novel Unsaturated Aliphatic Polyesters: Synthesis, Characterization, and Properties of Multiblock Copolymers Composing of Poly(Butylene Fumarate) and Poly(1,2-Propylene Succinate)

Widespread application of biodegradable polyesters is restrained by various disadvantages such as inadequate thermomechanical properties, high cost, and lack of reactive sites for further modification. Poly(butylene fumarate) (PBF), as a novel and low-cost aliphatic polyester, possesses good physical properties and reactive double bonds along with the polymer backbones which can be potentially modified to endow the polyester with specific properties. However, the biodegradation rate of PBF is too slow to meet the requirement of practical application. In this contribution, amorphous poly(1,2-propylene succinate) (PPS) was copolymerized with PBF to decrease the crystallinity (Xc) and accelerate the biodegradability of PBF via chain-extension with diisocyanate. The chemical structures of the copolymers were confirmed by 1H NMR spectra and gel permeation chromatography (GPC). The crystal structure and physicochemical properties were investigated by wide-angle X-ray diffraction (WAXD), differential scanning ca...

Isomorphism in Poly(butylene succinate-co-butylene fumarate) and Its Application as Polymeric Nucleating Agent for Poly(butylene succinate)

Strict isomorphism between butylene succinate and butylene fumarate in poly(butylene succinate-co-butylene fumarate) (PBSF) was revealed by DSC and wide-angle X-ray diffraction results. They adopt the same crystal modification, with only a little difference in crystal lattice parameters. The melting point of the copolymer increases linearly with increasing molar ratio of butylene fumarate and the melting enthalpy hardly changes, which meet the requirement of strict isomorphism. The introduction of unsaturated comonomer, fumaric acid, into PBS can enhance the total crystallization rate and the radial growth rate of spherulites. Consequently, PBF and PBSF are highly efficient polymeric nucleating agents for PBS and its copolymers. In this work, strict isomorphism provides us a new method to find polymeric nucleating agent.

Conductive Electrospun and Micro-StereoLithographically Produced Porous Scaffolds as Potential Neural Interface Materials

ABSTRACTOur overall intent is to develop improved electrically active prosthetic devices to allow interactions between regenerated nerve fibers (axons) and external electronics. To allow for infiltration of axons, these devices must be highly porous. Additionally, they must exhibit selective and structured conductivity to allow the connection of electrode sites with external circuitry with tunable electrical properties that enable the transmission of neural signals through physical connections to external circuitry (e.g. through attached wires.) The chosen material must be biocompatible with minimal irresolvable inflammatory response to allow intimate contact with regenerated nerve tissue and mechanically compatible with the surrounding nervous tissue.We have utilized electrospinning and projection lithography as tools to create conductive, porous networks of non-woven biocompatible fibers in order to meet the materials requirements for the neural interface. The biocompatible fibers were based on the known biocompatible material poly(dimethyl siloxane) (PDMS) as well as a newer biomaterial material developed in our laboratories, poly(butylene fumarate) (PBF). Both of the polymers cannot be electrospun using conventional electrospinning techniques due to their low glass transition temperatures, so in situ crosslinking methodologies were developed to facilitate micro- and nano-fiber formation during electrospinning. The conductivity of the electrospun fiber mats was controlled by varying the loading with multi-walled carbon nanotubes (MWNTs).

Synthesis and rheological study of some maleic and fumaric acid stereoregular polyesters, 2. Polyesters derived from 1,4‐dibromobutane or 1,8‐dibromooctane

AbstractConfigurationally pure, high‐molecular‐weight poly(butylene maleate)s, poly(butylene fumarate)s, poly(octamethylene maleate)s, and poly(octamethylene fumarate)s were synthesized by reaction of the corresponding potassium dicarboxylates and dibromoalkanes in 1‐methyl‐2‐pyrrolidone at 95 to 114°C. The polyfumarates show about ten times higher dynamic viscosities at 150°C than the polymaleates of the same limiting viscosity numbers, which might be attributed to the more extended conformations of the former.

Synthèse et étude des propriétés rhéologiques de polyesters stéréoréguliers à base d'acide maléique et d'acide fumarique

AbstractPure poly(butylene maleate) and poly(butylene fumarate) of high molecular weights were synthesized by reaction of the corresponding caesium and potassium dicarboxylates with 1,4‐dibromobutane in 1‐methyl‐2‐pyrrolidone at 110°C. During the reaction a substantial amount of oligomeric products, consisting mainly of cyclic compounds, is formed. From the study of the rheological properties at high temperatures (175 to 240°C) it was concluded that some crosslinking occurs rather than isomerization.