Polyphosphazene/nano-hydroxyapatite composite microsphere scaffolds for bone tissue engineering

The nontoxic, neutral degradation products of amino acid ester polyphosphazenes make them ideal candidates for in vivo orthopedic applications. The quest for new osteocompatible materials for load bearing tissue engineering applications has led us to investigate mechanically competent amino acid ester substituted polyphosphazenes. In this study, we have synthesized three biodegradable polyphosphazenes substituted with side groups, namely, leucine, valine, and phenylalanine ethyl esters. Of these polymers, the phenylalanine ethyl ester substituted polyphosphazene showed the highest glass transition temperature (41.6 degrees C) and, hence, was chosen as a candidate material for forming composite microspheres with 100 nm sized hydroxyapatite (nHAp). The fabricated composite microspheres were sintered into a three-dimensional (3-D) porous scaffold by adopting a dynamic solvent sintering approach. The composite microsphere scaffolds showed compressive moduli of 46-81 MPa with mean pore diameters in the range of 86-145 microm. The 3-D polyphosphazene-nHAp composite microsphere scaffolds showed good osteoblast cell adhesion, proliferation, and alkaline phosphatase expression and are potential suitors for bone tissue engineering applications.     

Biomedical applications of degradable polyphosphazenes

This article describes the synthesis of biodegradable polyphosphazenes. The rate of degradation can be varied in a controllable manner by the introduction of hydrolysis-sensitive amino acid ester side groups or by blending of polymers. Biodegradable polyphosphazenes can be used for the preparation of drug-containing implants and this is illustrated for devices containing the cytostatic agent mitomycin C. This article reviews data about the degradation characteristics of poly[(amino acid ester)phosphazene] derivatives that have been discussed previously. Some new data about MMC-containing poly[(organo)phosphazene] devices are discussed as well. (c) 1996 John Wiley & Sons, Inc.     

Miscibility of bioerodible polyphosphazene/poly(lactide-co-glycolide) blends

We have previously demonstrated the feasibility of blending bioerodible polyphosphazenes with poly(lactide-co-glycolide) (PLGA) to form versatile polymeric materials with altered bioerosion properties. These studies demonstrated the effective neutralization of the acidic degradation products of PLGA by the polyphosphazene hydrolysis products. In the present study, five new polymers of dipeptide polyphosphazenes poly[(ethyl glycinato)x(glycyl-ethyl glycinato)yphosphazene] and novel blends of these polyphosphazenes with poly(lactide-co-glycolide) (PLGA) were synthesized and fabricated. The miscibility was analyzed using differential scanning calorimetry and scanning electron microscopy. Hydrogen bonding within the blends was assessed by attenuated total reflectance infrared spectroscopy. The phosphazene component of the blend contained varying ratios of the glycyl-glycine ethyl ester to the glycine ethyl ester. Poly[(ethyl glycinato)0.5(glycine ethyl glycinato)1.5phosphazene formed completely miscible blends with PLGA (50:50) and PLGA (85:15). This is ascribed to the multiple hydrogen-bonding sites within the side groups of the polyphosphazene. The components of the blend act as plasticizers for each other because a glass transition temperature for each blend was detected at a lower temperature than for each individual polymer. A hydrolysis study showed that unblended solid poly[(ethyl glycinato)0.5(glycyl ethyl glycinato)1.5phosphazene] hydrolyzed in less than 1 week. However, the blends degraded at a slower rate than both parent polymers. This is attributed to the buffering capacity of the polyphosphazene hydrolysis products, which increases the pH of the degradation media from 2.5 to 4, thereby slowing the degradation rate of PLGA.     

Tyrosine-bearing polyphosphazenes

Tyrosine-functionalized polyphosphazenes were synthesized, and their hydrolytic stability, pH-sensitive behavior, and hydrogel-forming capabilities were investigated. The physical and chemical properties of the polymers varied with the type of linkage between the tyrosine unit and phosphazene backbone. Poly[(ethyl glycinat-N-yl)(ethyl tyrosinat-N-yl)phophazenes] (linkage via the amino group of tyrosine) were found to be hydrolytically erodible. The rate of hydrolysis was dependent on the ratio of the two side groups, the slowest rate being associated with the highest concentration of tyrosine. The hydrolysis products were identified as phosphates, tyrosine, glycine, ammonia, and ethanol derived from the ester group. The hydrolytically stable phenolic-linked tyrosine derivatives were prepared from N-t-BOC-L-tyrosine methyl ester and alkoxy-based cosubstituents. Polyphosphazenes with both propoxy and phenolic-linked tyrosine side groups showed a pH-sensitive solubility behavior, which was dependent on the ratio and nature of the two side groups. The polymer was soluble in aqueous media below pH 3 and above pH 4. From pH 3-4, the polymer was insoluble. Replacement of propoxy by trifluoroethoxy units yielded a polymer that was insoluble in aqueous media at all pH values. Replacement of propoxy by methoxyethoxyethoxy groups gave a polymer that was soluble at all pH values. Exposure of both the propoxy and methoxyethoxyethoxy polymers to calcium ions in aqueous media caused gel formation due to ionic cross-linking through the carboxylate groups.     

Mechanical properties of peptidoglycan as determined from bacterial thread

Experiments are described in which the tensile strength, the extensibility and the initial Young's modulus of bacterial cell wall have been determined as functions of relative humidity in the range 11-98%. Data on stress relaxation and recovery are also given. Standard fibre-measuring technique has been used on 'bacterial thread', made from a cell-separation-suppressed mutant of Bacillus subtilis. The data show that peptidoglycan, the load bearing polymer in the cell wall, behaves very much like other viscoelastic polymers. Its mechanical behaviour when dry is that of a glassy polymer with tensile strength about 300 MPa and modulus about 20 GPa. When wet, it is weaker and much less stiff with tensile strength about 3 M Pa and modulus 10 M Pa. The relaxation data indicate a wide spectrum of relaxation times. The results are discussed in terms of the structure of peptidoglycan and its orientation in the bacterial cell wall. The way in which mechanical behaviour depends strongly on humidity is compared with that of other biopolymers in terms of possible hydrogen-bond density and the ordering of water molecules. The possibility of a well-defined glass transition is briefly examined.     

Preparation and characterization of biodegradable poly-3-hydroxybutyrate-starch blend films

Bacterial polyesters have attracted much attention as biodegradable biocompatible polymers. Poly-3-hydroxybutyrate, a microbially produced thermoplastic, has similar material properties to polypropylene. Its potential application as biodegradable and biocompatible plastics is well documented. However, due to high cost it is used mainly in biomaterials for medical applications. Materials with useful properties may result from blending bacterial polyhydroxybutyrate (PHB) with other polymers. In this paper, the compatibility of PHB with starch for improved properties and cost reduction is discussed. The thermal and mechanical properties of the blended films were studied by means of thermogravimetry, differential scanning calorimetry and an automated material testing system. The results revealed that blend films had a single glass transition temperature for all the proportions of PHB:starch tested. The nature of all combinations was found to be crystalline. The tensile strength was optimum for the PHB:starch ratio of 0.7:0.3 (wt/wt). The variation in tensile strength, Young's modulus, extension needed to break, thermal stability, glass transition temperature, melting temperature, for the different proportions of PHB:starch are discussed.     

Study of biodegradable polylactide/poly(butylene adipate-co-terephthalate) blends

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using most conventional polymer processing methods. PLA is high in strength and modulus (63 MPa and 3.4 GPa, respectively) but brittle (strain at break 3.8%) while PBAT is flexible and tough (strain at break approximately 710%). In view of their complementary properties, blending PLA with PBAT becomes a natural choice to improve PLA properties without compromising its biodegradability. In this study, PLA and PBAT were melt blended using a twin screw extruder. Melt elasticity and viscosity of the blends increased with the concentration of PBAT. Crystallization of the PLA component, phase morphology of the blend, mechanical properties, and toughening mechanism were investigated. The blend comprised an immiscible, two-phase system with the PBAT evenly dispersed in the form of approximately 300 nm domains within the PLA matrix. The PBAT component accelerated the crystallization rate of PLA but had little effect on its final degree of crystallinity. With the increase in PBAT content (5-20 wt %), the blend showed decreased tensile strength and modulus; however, elongation and toughness were dramatically increased. With the addition of PBAT, the failure mode changed from brittle fracture of the neat PLA to ductile fracture of the blend as demonstrated by tensile test and scanning electron microcopy (SEM) micrographs. Debonding between the PLA and PBAT domains induced large plastic deformation in PLA matrix ligaments.     

Fabrication and Characterization of Native and Oxidized Potato Starch Biodegradable Films

The need to replace conventional polymers due to environmental pollution caused by them has led to increased production of biodegradable polymers such as starch. Thus, the application possibilities of starch have increased. In this study, we produced and characterized biodegradable films derived from native and oxidized potato starch. The film-forming solution was prepared with different concentrations of extracted starch (native or oxidized) and a plasticizer (glycerol or sorbitol). Then, the mechanical, barrier, morphological, and structural properties of the films were characterized. The moisture content of the films varied from 15.35?±?1.31 to 21.78?±?0.49%. The elastic modulus of the films ranged from 219?±?14.97 to 2299?±?62.91 MPa. The film of oxidized starch plasticized with sorbitol in the lowest content was the most resistant and flexible; moreover, this film also presented lower water vapor permeability and low solubility in water. Fourier-transform infrared spectroscopic analysis of the biodegradable films indicated the presence of same functional groups as those of starch with bands in the same regions. The film thickness was lower for the films plasticized with glycerol whereas the color variation (Δ?) was lower for the ones plasticized with sorbitol. In case of both plasticizers, the increase in their content decreased the Δ? value. All the biodegradable films presented stability against water absorption owing to their low solubility in water. Morphological evaluation revealed the presence of partially gelatinized starch granules in the films. The roughness parameter (Rq) of the films varied from 3.39 to 10.9 nm, indicating that their surfaces are smooth. X-ray diffraction studies showed a B-type pattern for the starches, which is representative of tubers. Further, the films present higher relative crystallinity (RC) compared to the starches. The biodegradable starch films are uniform, transparent and with low solubility in water. The oxidation of starch and use of sorbitol as a plasticizer resulted in improved properties of the starch films, which is suitable for application.     

Viscoelastic properties of linseed oil-based medium chain length poly(hydroxyalkanoate) films: effects of epoxidation and curing

Medium-chain-length poly(hydroxyalkanoate) (mcl-PHA) polymers derived from linseed oil (PHA-L) have a relatively small molar mass and contain a high concentration of unsaturated side-chains. As such, these polymers are amorphous and take on the consistency of a viscous liquid at room temperature. In order to increase the application potential of this material, the side-chain olefinic groups of PHA-L were converted to epoxy derivatives (PHA-LE) using m-chloroperoxybenzoic acid (m-CPBA). Epoxidation resulted in a 37% conversion of olefinic to epoxy groups. The epoxy groups enhanced the PHA-LE film susceptibility to crosslinking upon exposure to air. PHA-LE films began to crosslink and stiffen in less than 25 days, whereas PHA-L films began to crosslink between days 50 and 75. The PHA-LE films showed an increase in tensile strength (TS, from 4.8 to 20.7 MPa) and Young's modulus (YM, from 12.9 to 510.6 MPa) between 25 and 100 days. In contrast, PHA-L had a TS of 25.0 MPa and YM of 767.8 MPa after 100 days. Epoxidation helped induce crosslink formation; however, aging for 100 days ultimately resulted in crosslinked films from both PHA-L and PHA-LE with higher strength and durability than the original materials.     

Poly(organo phosphazene) nanoparticles surface modified with poly(ethylene oxide)

The use of biodegradable derivatives of poly(organo phosphazenes) for the preparation of nanoparticles and their surface modification with the novel poly(ethylene oxide) derivative of poly(organo phosphazene) has been assessed using a range of in vitro characterization methods. The nanoparticles were produced by the precipitation solvent evaporation method from the derivative co-substituted with phenylalanine and glycine ethyl ester side groups. A reduction in particle size to less than 200 nm was achieved by an increase in pH of the preparation medium. The formation (and colloidal stability) of these nanoparticles seems to be controlled by two opposite effects: attractive hydrophobic interactions between phenylalanine ester groups and electrostatic repulsions arising from the carboxyl groups formed due to (partial) hydrolysis of the ester bond(s) at the high pH of the preparation medium. The poly[(glycine ethyl ester)phosphazene] derivative containing 5000-Da poly(ethylene oxide) as 5% of the side groups was used for the surface modification of nanoparticles. Adsorbed onto the particles, the polymer produced a thick coating layer of approximately 35 nm. The coated nanoparticles exhibited reduced surface negative potential and improved colloidal stability toward electrolyte-induced flocculation, relative to the uncoated system. However, the steric stabilization provided was less effective than that of a Poloxamine 908 coating. This difference in effectiveness of the steric stabilization might indicate that, although both the stabilizing polymers possess a 5000-Da poly(ethylene oxide) moiety, there is a difference in the arrangements of these poly(ethylene oxide) chains at the particle surface. (c) 1996 John Wiley & Sons, Inc.     

Synthesis of biodegradable and electroactive multiblock polylactide and aniline pentamer copolymer for tissue engineering applications

To obtain one biodegradable and electroactive polymer as the scaffold for tissue engineering, the multiblock copolymer PLAAP was designed and synthesized with the condensation polymerization of hydroxyl-capped poly( l-lactide) (PLA) and carboxyl-capped aniline pentamer (AP). The PLAAP copolymer exhibited excellent electroactivity, solubility, and biodegradability. At the same time, as one scaffold material, PLAAP copolymer possesses certain mechanical properties with the tensile strength of 3 MPa, tensile Young 's modulus of 32 MPa, and breaking elongation rate of 95%. We systematically studied the compatibility of PLAAP copolymer in vitro and proved that the electroactive PLAAP copolymer was innocuous, biocompatible, and helpful for the adhesion and proliferation of rat C6 cells. Moreover, the PLAAP copolymer stimulated by electrical signals was demonstrated as accelerating the differentiation of rat neuronal pheochromocytoma PC-12 cells. This biodegradable and electroactive PLAAP copolymer thus possessed the properties in favor of the long-time application in vivo as nerve repair scaffold materials in tissue engineering.     

Synthesis and mechanical properties of quaternary salts of chitosan-based films for food application

A novel method is described to synthesize quaternary salts of chitosan with dimethylsulfate and subsequently cast films. In an attempt to improve both mechanical and hydrophobic characteristics, the chitosan was previously modified by N-alkylation, introducing 4, 8 and 12 carbons moieties into the polymeric chain. Analysis by FTIR and solid-state CP-MAS (13)C NMR spectroscopy confirmed the success of both alkylation and quaternization processes. The average degree of quaternization of these N-methylated derivatives was calculated to be 35%. DMA measurements indicated that chitosan and its derivative films are typically brittle materials, exhibiting similar non-linear viscoelastic behaviors. The films of unmodified chitosan have a very small strain (approximately 2.8%), though they were the most resistant films (Young's modulus=2283 MPa; tensile strength >44.0 MPa). In general, the alkyl-chitosan derivatives appear to be more plastic than chitosan films but less resistant, e.g., for butyl chitosan: maximum strain=13.1%; tensile strength=13.4 MPa and Young's modulus=171 MPa. Conversely the quaternization reaction increased the hardness of the parent sample, viz. for quaternary salt of dodecyl chitosan: maximum strain=2.6%; tensile strength=38.3 MPa and Young's modulus=1792 MPa.     

Biodegradability and mechanical properties of starch films from Andean crops

Different Andean crops were used to obtain starches not previously reported in literature as raw material for the production of biodegradable polymers. The twelve starches obtained were used to prepare biodegradable films by casting. Water and glycerol were used as plasticizers. The mechanical properties of the starch based films were assessed by means of tensile tests. Compost tests and FTIR tests were carried out to assess biodegradability of films. The results show that the mechanical properties (UTS, Young's modulus and elongation at break) of starch based films strongly depend on the starch source used for their production. We found that all the starch films prepared biodegrade following a three stage process and that the weight loss rate of all the starch based films tested was higher than the weight loss rate of the cellulose film used as control.     

Vapor Barrier Properties and Mechanical Behaviors of Composite Hydroxypropyl Methylcelluose/Zein Nanoparticle Films

Composite films of hydroxypropyl methylcellulose and zein nanoparticles (ZNP) were prepared to create a biopolymer-based film with reduced vapor permeability and potential for active-packaging applications. Microscopy verified the dispersion of ZNP with diameter of ~100 nm throughout the width and depth of the films, with ZNP forming sub-micrometer clusters of nanoparticles at loaded volume fractions >0.15. Incorporation of non-hygroscopic ZNP increased film-water contact angles to >70 degrees and decreased water vapor permeability of films by ~10–30%. Extensional measurements of films described an increase in tensile strength from 27 kPa to 49 kPA, a decreased capacity to elongate, and an initial increase followed by gradual decrease in Young’s moduli with increasing ZNP fractions. Decreased elasticity was observed within microscale regions of the films at higher ZNP volume fractions using dynamic force spectroscopy, and the trends were strongly correlated with bulk Young’s moduli of the composite films. A mathematical model rationalized the initially increased and subsequently decreased Young’s modulus by the change in ZNP dispersion/clustering combined with a collapse of the interfacial zone surrounding ZNP.     

Synthesis, characterization, and in vitro degradation of a biodegradable photo-cross-linked film from liquid poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylate

There has been little study on the effect of composition or molecular weight on the biodegradation rate of photo-cross-linked biodegradable aliphatic polyesters though such information is important for tissue engineering scaffolds. We have synthesized a new series of photopolymerizable linear poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylates with different molecular weights (Mn = 1800, 4800, and 9300 Da) and compositions (20%, 40%, and 60% epsilon-CL) and studied their biodegradation rates. The resultant oligomers were amorphous and appeared as viscous liquids at room temperature. Liquid-to-solid polymerization was carried out by UV irradiation in the presence of a photoinitiator. The photocuring yield was high (greater than 95%), and the photo-cross-linked polymers were amorphous and rubbery. Mechanical measurements showed that the polymers can be stretchable or rigid; the high molecular weight/low epsilon-CL network has a strain of 176% and a modulus of 1.66 MPa while the low molecular weight/high epsilon-CL network has a strain of 21% and a modulus of 12.3 MPa. In a 10 week in vitro biodegradation study, the polymers exhibited a two-stage degradation behavior. In the first stage, the polymer weight and strain remained almost constant, but a linear decrease in the Young's modulus (E) and ultimate stress (sigma) were observed. Lower oligomer molecular weight or epsilon-CL content correlated with a faster decrease in Young's modulus. In the second stage, which began when the Young's modulus dropped below 1 MPa, there was rapid weight loss and strain increase. The lower the epsilon-CL content, the earlier the second stage happened. Low molecular weight and high epsilon-CL content correlated with a longer modulus half-life (time for the modulus to degrade to 50% of its initial value). The degradation results suggest principles that may be helpful in predicting the biodegradation behavior of similar polymeric cross-linked networks. Films formed from these new polymers have excellent biocompatibility with smooth muscle cells.     

Interaction between proteins and polyphosphazene derivatives having a galactose moiety

For tissue engineering applications, it is necessary to balance the need for specific biological interactions with the need to prevent unfavorable nonspecific interactions. For this purpose, novel poly[(organo)phosphazenes] were synthesized having galactose and/or poly(ethylene glycol) (PEG) side chains. The synthesis was described previously. Here, we investigate the human serum albumin (HSA) adhesion to these polymers using surface plasmon resonance (SPR). We could conclude that the incorporation of PEG reduced the protein adsorption. The influence of the galactose moieties was investigated using SPR and a sugar-lectin binding assay. The interaction between a lectin (Peanut agglutinin, PNA or Ricinus communis-agglutinin, RCA) and the polyphosphazene derivatives was evaluated. Type IIA polymers, having aminohexyl-galactose, phenylalanine ethyl ester, and glycine ethyl ester side chains, were capable of binding with the lectin. As the amount of galactose was increased, the extent of the galactose specific lectin binding was also increased (higher RU or absorbance). PEG containing polymers failed to bind specifically with the lectin. The presence of PEG, either as a spacer or as additional chains, interfered with the establishment of contact between the galactose and the binding site on the lectin. The adsorption of PNA or RCA to these types of polymers was attributed to nonspecific interactions. SPR was also used to determine rate and equilibrium constants. In addition the effect of the addition of water soluble polyphosphazenes on the enzymatic cleavage of o-nitrophenyl-beta-D-galactopyranoside was investigated. The galactose moieties were not available as inhibitors because of the presence of PEG.     

Novel conjugated linseed oil-styrene-divinylbenzene copolymers prepared by thermal polymerization. 1. Effect of monomer concentration on the structure and properties

A variety of novel opaque, white polymers ranging from rubbery materials to tough and rigid plastics have been prepared by the thermal polymerization at 85-160 degrees C of varying amounts of 87% conjugated linseed oil, styrene, and divinylbenzene. Gelation of the reactants typically occurs at temperatures higher than 120 degrees C, and fully cured thermosets are obtained after postcuring at 160 degrees C. The fully cured thermosets have been determined by Soxhlet extraction to contain approximately 35-85% cross-linked materials. The microcomposition of these polymers, as determined by 1H NMR spectroscopy, indicates that the cross-linked materials are composed of both soft oily and hard aromatic phases. After solvent extraction, the insoluble materials exhibit nanopores well distributed throughout the polymer matrixes. Dynamic mechanical analysis of these polymers indicates that they are phase separated with a soft rubbery phase having a sharp glass transition temperature of -50 degrees C and a hard brittle plastic phase with a broadened glass transition temperature of 70-120 degrees C. These polymers possess cross-link densities of 0.15-2.41 x 10(4) mol/m3, compressive Young's moduli of 12-438 MPa, and compressive strengths of 2-27 MPa. These materials are thermally stable below 350 degrees C and exhibit a major thermal degradation of 72-90% at 493-500 degrees C.     

Mechanical properties of a biodegradable bone regeneration scaffold

Poly (Propylene Fumarate) (PPF), a novel, bulk erosion, biodegradable polymer, has been shown to have osteoconductive effects in vivo when used as a bone regeneration scaffold (Peter, S. J., Suggs, L. J., Yaszemski, M. J., Engel, P. S., and Mikos, A. J., 1999, J. Biomater. Sci. Polym. Ed., 10, pp. 363-373). The material properties of the polymer allow it to be injected into irregularly shaped voids in vivo and provide mechanical stability as well as function as a bone regeneration scaffold. We fabricated a series of biomaterial composites, comprised of varying quantities of PPF, NaCl and beta-tricalcium phosphate (beta-TCP), into the shape of right circular cylinders and tested the mechanical properties in four-point bending and compression. The mean modulus of elasticity in compression (Ec) was 1204.2 MPa (SD 32.2) and the mean modulus of elasticity in bending (Eb) was 1274.7 MPa (SD 125.7). All of the moduli were on the order of magnitude of trabecular bone. Changing the level of NaCl from 20 to 40 percent, by mass, did not decrease Ec and Eb significantly, but did decrease bending and compressive strength significantly. Increasing the beta-TCP from 0.25 g/g PPF to 0.5 g/g PPF increased all of the measured mechanical properties of PPF/NVP composites. These results indicate that this biodegradable polymer composite is an attractive candidate for use as a replacement scaffold for trabecular bone.     

Investigating the structure-property relationship of bacterial PHA block copolymers

Mechanical testing of solvent cast films consisting of short-chain-length (SCL) polyhydroxyalkanoate (PHA) films suggested that films consisting of block copolymers retained more elasticity over time with respect to films of similar random copolymers of comparable composition. Two experimental techniques, wide angle X-ray scattering (WAXS) and uniaxial extension, were used to quantitatively investigate the structure-property relationship of bacterially synthesized PHA block copolymers of poly(3-hydroxybutyrate) (PHB) homopolymer and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) random copolymer (PHBV) segments. Uniaxial testing experiments yielded the Young's modulus, ultimate tensile strength, and the elongation until fracture of the films. Percent crystallinity was determined by deconvolution of amorphous and crystalline scattering peaks obtained from WAXS. Two PHBV films containing either 8% 3-hydroxyvalerate monomer (3HV) or 29% 3HV exhibited a quick transition to brittle behavior, decreasing to less than 20% percent elongation at fracture within a few days after annealing. Conversely, the block copolymer samples remained higher than 100% elongation at fracture a full 3 months after annealing. Because block copolymers covalently link polymers that would otherwise form thermodynamically separate phases, the rates and degrees of crystallization of the block copolymers are less than the random copolymer samples. These differences translate into materials that extend the property space of biologically synthesized SCL PHA.     

High Molecular Weight Poly(butylene succinate-co-butylene furandicarboxylate) Copolyesters: From Catalyzed Polycondensation Reaction to Thermomechanical Properties

Novel potentially biobased aliphatic-aromatic copolyesters poly(butylene succinate-co-butylene furandicarboxylate) (PBSFs) in full composition range were successfully synthesized from 2,5-furandicarboxylic acid (FA), succinic acid (SA), and 1,4-butanediol (BDO) via an esterification and polycondensation process using tetrabutyl titanate (TBT) or TBT/La(acac)(3) as catalyst. The copolyesters were characterized by size exclusion chromatography (SEC), Fourier transform infrared (FTIR), (1)H NMR, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and their tensile properties were also evaluated. The weight average molecular weight (M(w)) ranges from 39?000 to 89?000 g/mol. The copolyesters are random copolymers whose composition is well controlled by the feed ratio of the diacid monomers. PBSFs have excellent thermal stability. The glass transition temperature (T(g)) increases continuously with ?(BF) and agrees well with the Fox equation. The crystallizability and T(m) decrease with increasing butylene furandicarboxylate (BF) unit content (?(BF)) from 0 to 40 mol %, but rise again at ?(BF) of 50-100 mol %. Consequently, the tensile modulus and strength decrease, and the elongation at break increases with ?(BF) in the range of 0-40 mol %. At higher ?(BF), the modulus and strength increase and the ultimate elongation decreases. Thus, depending on ?(BF), the structure and properties of PBSFs can be tuned ranging from crystalline polymers possessing good tensile modulus (360-1800 MPa) and strength (20-35 MPa) to nearly amorphous polymer of low T(g) and high elongation (～600%), and therefore they may find applications in thermoplastics as well as elastomers or impact modifiers.