Synthesis and characterization of polyester copolymers based on poly(butylene succinate) and poly(ethylene glycol)

A series of polyester copolymers was synthesized from 1,4-succinic acid with 1,4-butanediol and poly(ethylene glycol) through a two-step process of esterification and polycondensation in this article. The composition and physical properties of copolyesters were investigated via GPC, ¹HNMR, DSC and PLM. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), and crystallinity (X_c) of these copolyesters decreased gradually as the content of PEG unit increased. Otherwise, experimental results also showed that the contents of PEG in copolymers had an effect on the molecular weight, distribution, thermal properties, hydrolysis degradation properties, and crystalline morphology of polyester copolymers.     

New biomaterial: triblock copolymers of poly [3(S)-isobutyl-morpholine-2,5-dione]-poly(ethylene oxide)

ABA-type block copolymers with poly[3(S)-isobutyl-morpholine-2,5-dione](PIBMD, A) and poly(ethylene oxide) (M_n = 6000, PEO, B) blocks, PIBMD-b-PEO-b-PIBMD, were synthesised via ring-opening polymerization of 3(S)-isobutyl-morpholine-2,5-dione in the presence of hydroxytelechelic poly(ethylene oxide) with stannous octoate as a catalyst. These block copolymers may find applications in cell encapsulation and in drug delivery. M_n of the resulting copolymers increases with increasing 3(S)-isobutyl-morpholine-2,5-dione content in the feed at constant molar ratio of monomer (M) to catalyst (C) (M/C = 125). No racemization of the leucine residue takes place during both homopolymerization of IBMD and polymerization of IBMD in the presence of PEO and Sn(Oct)₂. The melting temperature of the PIBMD segments in the block copolymers depends on the length of the PIBMD blocks. The melting temperature of the PEO blocks is lower than that of the homopolymer, and the crystallinity of the PEO block decreases with increasing length of the PIBMD blocks. The PIBMD block crystallizes first upon cooling from the melt. This leads to only imperfect crystallization or no crystallization of the PEO blocks.     

Isothermal crystallization kinetics and morphology of biodegradable poly(3-hydroxybutyrate-co-4-hydroxybutyrate)

Isothermal crystallization kinetics and morphology of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] with different 4-hydroxybutyrate (4HB) molar fraction were investigated by differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD), and polarized optical microscopy (POM). The results show that the crystallization mechanism and crystal structure of P(3HB-co-4HB) copolymers are the similar as those of poly(3-hydroxybutyrate) (PHB). While the equilibrium melting point and crystallization rate decrease with the increase of 4HB molar fraction. Banded spherulites are observed in neat PHB and P(3HB-co-4HB) copolymers, and morphology is influenced apparently by the crystallization temperature and 4HB unit.     

Synthesis and characterization of a novel multiblock copolyester containing poly(ethylene succinate) and poly(butylene succinate)

Multiblock copolyester (PBS-b-PES) containing poly(butylene succinate) (PBS) and poly(ethylene succinate) (PES) was successfully synthesized by chain-extension of dihydroxyl terminated PBS (HO-PBS-OH) and PES (HO-PES-OH) using 1,6-hexmethylene diisocyanate (HDI) as a chain extender. The chemical structures, molecular weights, crystallization behaviors, thermal and mechanical properties of the copolyesters were characterized by proton nuclear magnetic resonance spectroscopy (¹H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA), wide-angle X-ray diffraction (WAXD), tensile testing and hydrolytic degradation. High-molecular-weight copolyesters with M_w more than 2.0 × 10⁵ g mol⁻¹ were easily obtained through chain-extension. The copolyesters showed a single glass transition temperature (T_g) which increased with PES content. The melting point temperature (T_m) and relative degree of crystallinity (X_c) of the copolyesters decreased first and then increased with PES content. The copolyesters manifested excellent mechanical properties, for example, PBS₅-b-PES₅ had fracture stress of 61.8 MPa and fracture strain of 1173%. The chain-extension reaction provided a very effective way to produce high molecular weight multiblock copolyesters.     

Synthesis, characterization and hydrolytic degradation of degradable poly(butylene terephthalate)/poly(ethylene glycol) (PBT/PEG) copolymers

Hydrolytic degradable PBT/PEG copolymer was synthesized by macromolecular transesterification method from PBT and PEG macromonomers. The resultant copolymers were characterized by ¹H-NMR and GPC. The non-isothermal crystallization behavior of these copolymers was studied by differential scanning calorimetry (DSC). The water absorption and hydrolytic degradation behavior of PBT/PEG copolymers were also studied in detail. This work was partly presented in 6^th ASBM, July 19–22, 2004, Emei City, Chingdu, China. Fan LY is the co-first author for this work.     

偶联法制备聚羟基丁酸酯/聚乙二醇共聚物及其性能

利用二异氰酸酯为偶联剂,采用不同分子量的聚乙二醇(PEG)与聚羟基丁酸酯(PHB)进行偶联反应,制备一系列聚羟基丁酸酯/聚乙二醇共聚物。利用红外光谱(FT-IR)、差示扫描量热(DSC)、广角X射线衍射(WAXD)、表面水相接触角及力学性能实验对共聚物进行了分析研究。结果表明,偶联聚乙二醇后,PHB链的规整度降低,PHB的结晶度下降,非结晶区增大,同时表面亲水性变好,当采用高分子量的PEG后,共聚物的拉抻应力-应变曲线中出现了明显的屈服点,断裂伸长率也有了较大的提高,达到了11%,韧性得到改善,力学性能有一定程度的提高。     

Nucleation,growth and morphology of poly(hydroxybutyrate) and its copolymers

Measurements of the melting temperatures, growth rates and nucleation rates of meltcrystallized polyhydroxybutyrate (PHB) and two poly(hydroxybutyrate-co-hydroxyvalerate) (PHB/HV) copolymers are reported for crystallization over a wide range of temperature. Examples are shown of the spherulitic morphologies obtained. From the variation in melting point with crystallization temperature values for the equilibrium melting points of PHB and PHB/HV are obtained. Growth and nucleation rate measurements are analysed using secondary nucleation theory to obtain approximations to surface energies within the crystals. PHB and PHB/7% HV are described well by secondary nucleation theory. PHB/23% HV exhibits more complex crystallization and melting behaviour, which suggests temperature-dependent exclusion of HV units from the crystals.     

Thermal behaviour of poly(ε-caprolactone)-poly(ethylene glycol)-poly(ε-caprolactone) tri-block copolymers

Thermal behavior of poly(-caprolactone)-poly(ethylene glycol)-poly(-caprolactone) tri-block copolymers with different block lengths is examined. Thermal behavior of specimens crystallized under the isothermal and dynamic condition are characterized by DSC. Also WAXD and SAXS are employed to investigate the structure. Depending on the relative length of each block, tri-block copolymers can be classified into three groups: PCL dominant crystallization; PEG dominant crystallization; and the competing case. When the crystallization of PEG and PCL are competing, the crystallization of each block shows strong dependency on the thermal hystory of crystallization, leading to multiple melting and crystallization peaks. Also, the typical micro-phase separation of block copolymers seems to play an important role, competing with crystallization, especially under the dynamic crystallization condition.     

Synthesis and characterization of novel biodegradable pentablock copolymers from L‐lactide,p‐dioxanone and poly (ethylene glycol)

ABCBA type pentablock copolymers, in which the A, B and C blocks are poly (p‐Dioxanone) (PPDO), poly (L‐Lactide) (PLLA), and polyethylene glycol (PEG), respectively, were synthesized via a two‐step ring‐opening polymerization in bulk using stannous octoate as the catalyst. PLA‐b‐PEG‐b‐PLA Triblock copolymer was synthesized at first and then p‐Dioxanone monomers as the other blocks were added to it. In the first step, poly ethylene glycol and, in the second step, triblock copolymer acts as the macro initiator. The obtained copolymers were identified by ?1&/sup;H&/I;, ?13&/sup;CNMR&/I; and IR&/I; spectroscopy. The intrinsic viscosity of copolymers was measured in chloroform/phenol (3/1 v/w) solution. The thermal properties, such as melting point, melting enthalpy and crystallinity, were studied. From the results of differential scanning calorimetry and thermal gravimetric analysis, it was observed that the PPDO blocks show similar crystallization behavior like homopolymer and also melting temperature of two PPDO end blocks raise with an increase in DON content in copolymer.     

Block copolymers of L-lactide and poly(ethylene glycol) for biomedical applications

Poly (L-lactide)-poly (oxyethylene)-poly (L-lactide) block copolymers obtained in bulk, by a ring opening mechanism, from poly (ethylene glycol)s (PEG)s and L-lactide (LA), at 120–140°C, in the absence of added catalysts are described. By using PEGs with different molecular masses, 3000 and 35000, respectively, and varying the initial molar ratio LA to PEG, two series of copolymers with different molecular masses, relative length of blocks and hydrophilicity were obtained. Physico-chemical characterization of the copolymers had been previously performed. The morphological characteristics of the copolymers were investigated by means of X-ray diffractometry, optical and scanning electron microscopy. The biological properties of the materials were determined by evaluating their cytotoxicity, cytocompatibility, hemocompatibility and degradability using different standard tests. The results obtained indicate that the block copolymers synthesized may be useful for biomedical applications, in particular as resorbable drug vehicles. The materials are brittle and their mechanical properties are not appropriate for implant devices.     

The kinetics of isothermal cold crystallization and tensile properties of poly(ethylene terephthalate)

The exothermic peak that is frequently observed during the heating scan of a differential scanning calorimetry (DSC) experiment of poly(ethylene terephthalate) (PET) is due to a cold crystallization process, originating from the rearrangement of amorphous regions into a crystalline phase. In this work the isothermal cold crystallization kinetics of PET was investigated by using DSC, X-ray diffraction and tensile experiments. The isothermal crystallization rate was determined as a function of temperature, and the Avrami analysis was conducted. The results showed that at low temperatures the cold crystallization is a two-regime process, whereas at high temperatures just one stage is observed. The rate constant for isothermal crystallization K increased and the half time of crystallization (t_½) decreased with increasing crystallization temperature. The Avrami exponent n was close to 2, and this corresponds to a disc-like morphology formed by heterogeneous nucleation. Cold crystallization increased the crystallinity and therefore the tensile properties of the samples were enhanced.     

聚乙二醇／聚乙烯醇共混物的相变特性与结晶

通过溶液共混法制备了系列PEG4000／PVA共混物，并采用DSC、WAXD、FT-IR等手段对共混体系的相变特性及结晶进行了探讨。结果表明：共混体系具有可逆的固-固相转变特性。共混物的熔点（Tm）基本保持不变，而结晶峰值温度（Tc）与PEG／PVA质量百分含量有关。其相变焓是随着PEG含量的增加而逐渐增加。聚乙烯醇的存在对共混体系中PEG的结晶和熔融过程均有所影响，但共混体系与纯PEG4000具有相同的衍射线、衍射角和面间距，且并未发现新的衍射峰出现。共混体系中x射线衍射峰的半峰宽度大于纯PEG的半峰宽度，说明共混过程使PEG结晶粒子变小。     

PPSK／PPS共聚物的合成及其初步研究

用４，４＾’－二氟苯酮、１，４－二氯苯和硫化钠为原料，常压下采用分开预聚和共预聚两种不同的预聚方式，合成了聚苯硫醚酮－聚苯硫醚共聚物。用红外光谱、Ｘ射线衍射、差示热扫描和热失重分析等手段，对共聚物进行了初步表征。结果表明，不同配比的共聚物均为结晶性高聚物，并且具有良好较好的耐热性能，对于可溶性的共聚物还测定了其对数比浓粘度。     

Synthesis and thermal properties of polystyrene-graft-PEG copolymers as new kinds of solid–solid phase change materials for thermal energy storage

A series of polystyrene-graft-PEG₆₀₀₀ copolymers were synthesized as new kinds of polymeric solid–solid phase change materials (SSPCMs). The synthesized SSPCMs storage latent heat as the soft segments PEG₆₀₀₀ of the copolymers transform from crystalline phase to amorphous phase and therefore they can keep its solid state during the phase transition processing. The graft copolymerization reaction between polystyrene and PEG was verified by Fourier transform infrared (FT-IR) and ¹H NMR spectroscopy techniques. The morphology of the synthesized SSPCMs was characterized by polarization optical microscopy (POM). Thermal energy storage properties, thermal reliability and thermal stability of the synthesized SSPCMs were investigated by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis methods. The DSC results showed that the synthesized SSPCMs had typical solid–solid phase transition temperatures in the range of 55–58 °C and high latent heat enthalpy in the range of 116–174 J g⁻¹. The TG analysis findings showed that the synthesized SSPCMs had high thermal durability above their working temperatures. Also, thermal conductivity measurements indicated that the synthesized PCMs had higher thermal conductivity compared to that of polystyrene. The synthesized polystyrene-graft-PEG₆₀₀₀ copolymers as new kinds of SSPCMs could be used for thermal energy storage.     

Thermal Properties of PHB/PEG Blends

Thermal properties of PHB and PHB/PEG blends were investigated by differential scanning calorimetry (DSC) and melt index (Ml) test. DSC thermograms indicate that two components of blend are miscible. From the DSC thermogram, we can also conclude that the melting point of PHB descends with the increased content of PEG, this can improve PHB processing properties.From Ml data, we may draw the same conclusion.     

Effect of surface modification of nanosilica on crystallization,thermal and mechanical properties of poly(vinylidene fluoride)

Composites were prepared by solution blending ploy(vinylidene fluoride) (PVDF) and nanosilica which modified by different organic modifiers. Infrared analysis showed that the crystalline structure of PVDF was changed by the addition of RNS-A (silica with amino terminated group), while similar crystalline structure as pure PVDF was observed for composites with DNS-0 and DNS-2, unmodified silica and alkyl terminated group silica, respectively. With differential scanning calorimeter (DSC) and dynamic mechanic thermal analysis (DMTA) techniques, crystalline structure, thermal, and mechanical properties of the composite films were examined. As the DSC results showed, addition of SiO₂ would lead to the increased cooling crystallization temperature (T _c), implying that SiO₂ nanoparticles could act as nucleating agents, however the degree of crystallinity of PVDF was not elevated significantly. In the complementary modulated DSC curves, multi-melting peaks associated with non-reversing portion were observed and were explained from the viewpoint of melting-recrystallization in the DSC heating scan. In addition, dynamic mechanical properties as well as the thermal stability of the composites are also influenced by SiO₂. As manifested by the corresponding DMTA and thermogravimetric analysis (TGA) results, a strong interaction should exist between PVDF and SiO₂ nanoparticles.     

Novel reverse thermoresponsive injectable poly(ether carbonate)s

The water solutions of polymers displaying reverse thermal gelation (RTG), such as poly(ethylene oxide)/poly(propylene oxide)/poly(ethylene oxide) triblocks, exhibit a pronounced viscosity increase as temperature rises, within a very narrow temperature interval. Unfortunately, the viscosity increase attained by these solutions is not large enough, resulting in systems displaying limited stability and short residence times. This paper introduces a new family of reverse thermoresponsive alternating [A-B] _n block copolymers, comprising poly(ethylene oxide) (PEO), and poly(propylene oxide) (PPO) chains, using phosgene as the molecule connecting both components. The effect of various compositional and structural parameters on both the C _i (minimal gelation concentration) and T _i (minimal gelation temperature) of these systems was investigated. The copolymers were characterized by GPC, ¹H-NMR, FT-IR, and DSC and the rheological behavior of the water solutions was studied using a Brookfield viscometer. The water systems were also studied by dynamic light scattering (DLS) and fluorescence spectroscopy. The copolymers developed exhibited clearly superior rheological properties, when compared to existing RTG-displaying PEO–PPO–PEO triblocks. For example, while the viscosity of a 15% water solution of the commercially available Pluronic F-127 achieved 5000 Pa.s, at 37 °C, poly(ether carbonate) water solutions (15%) attained viscosities between 25 000 and 150 000 Pa.s.     

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer

Effect of glycerol cross-linking and hard segment content on the shape memory property of polyurethane block copolymer is comprehensively investigated. Phase separation of hard and soft segment is dependent on glycerol cross-linking and hard segment content as judged from FT-IR and DSC data. Hydrogen bonding and dipole–dipole interaction between hard segments provides strong interaction between copolymer chains in addition to chemical cross-linking by glycerol. As the hard segment content increases, the copolymer shows better tensile mechanical properties and higher melting temperature of soft segment (T _m). Effect of glycerol cross-linking on mechanical properties and T _m of soft segment is low compared to hard segment effect. Although XRD peak at 2θ = 19.5° is observed, clear difference between the copolymers with various hard segment and cross-linking content is not observed. Significant increase in shape recovery rate in the case of 30 wt% hard segment copolymer is observed after glycerol cross-linking. The drastic change of the properties of polyurethane block copolymer is discussed in the point of copolymer chain interaction.     

Miscibility and melting properties of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting properties of binary crystalline blends of poly(ethylene 2,6-naphthalate)/poly(trimethylene terephthalate) (PEN/PTT) have been investigated with differential scanning calorimetry (DSC). The glass transition and cold crystallization behaviors indicated that in PEN/PTT blends, there are two different amorphous phases and the PEN/PTT blends are immiscible in the amorphous state. The polymer–polymer interaction parameter, , calculated from equilibrium melting temperature depression of the PEN component was −1.791 × 10⁻⁵ (300 °C), revealing miscibility of PEN/PTT blends in the melt state.     

Structure formation and miscibility of sheets from PBT and LCP blends

Sheets from blends containing poly(butylene terephthalate) (PBT) and liquid crystalline polymer (LCP) were prepared using a twin-screw extruder. The LCP used is a copolymer composed of 20 mol % ethylene terephalate (PET) and 80 mol % p-hydroxybenzoic acid (PHB). Thermal behavior, viscoelastic properties, and structure of the sheets of various compositions were investigated by using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), microwave orientation analysis (MOA), and wide angle x-ray diffraction (WAXD). X-ray diffractograms of extruded sheets from PBT, LCP, and their blends show a high degree of orientation along extrusion direction. The orientation is mainly due to the high crystallization rate of PBT, although crystallization and orientation of PBT in the PBT and LCP blends could also be induced by adding LCP. In the PBT and LCP blends, the thermal properties of the constituents are slightly changed indicating that PBT and LCP are partially miscible. DSC measurements show that as the amount of LCP added to the blend increased, the melting point T _m of PBT in the blends decreased. The single glass transition temperature T _g for the PBT and LCP was observed by DMA. Furthermore, no evidence of transesterification in PBT and LCP blends was observed by WAXD.