Phase behavior of biodegradable amphiphilic poly(l,l-lactide)-b-poly(ethylene glycol)-b-poly(l,l-lactide)

This study describes the miscibility phase behavior in two series of biodegradable triblock copolymers, poly(l-lactide)-block-poly(ethylene glycol)-block-poly(l-lactide) (PLLA-PEG-PLLA), prepared from two di-hydroxy-terminated PEG prepolymers (M_n = 4000 or 600 g mol⁻¹) with different lengths of poly(l-lactide) segments (polymerization degree, DP = 1.2-145.6). The prepared block copolymers presented wide range of molecular weights (800-25,000 g mol⁻¹) and compositions (16-80 wt.% of PEG). The copolymer multiphases coexistance and interaction were evaluated by DSC and TGA. The copolymers presented a dual stage thermal degradation and decreased thermal stability compared to PEG homopolymers. In addition, DSC analyses allowed the observation of multiphase separation; the melting temperature, T_m, of PLLA and PEG phases depended on the relative segment lengths and the only observed glass transition temperature (T_g) in copolymers indicated miscibility in the amorphous phase.     

Synthesis and characterization of poly(phenylene oxide) graft copolymers by atom transfer radical polymerizations

A series of comb-like poly(phenylene oxide)s (PPO) graft copolymers with controlled grafting density and length of grafts were synthesized by atom transfer radical polymerization (ATRP). The α-bromo-poly(2,6-dimethyl-1,4-phenylene oxide)s (BPPO) were used as macroinitiators to polymerize vinyl monomers and the graft copolymers carrying polystyrene (PS), poly(p-acetoxystyrene) (PAS), and poly(methyl methacrylate) (PMMA) as side chains were synthesized and characterized by NMR, FTIR, GPC, DSC and TGA. The composition-dependent glass-transition temperatures (T_g) of PPO-g-PS exhibited good correlation with theoretical curve in Couchman equations except for the cases of low PS content (<40 mol%) copolymers in which a positive deviation was observed due to enhanced molecular interactions. The increase in monomer/initiator ratio led to the increase of degree of polymerization and the decrease of polydispersity. Despite the immiscibility nature between PPO and PMMA, the PPO-g-PMMA exhibited enhanced compatibilization as apparent single T_g in a wide temperature window throughout various compositions revealing an efficient segmental mixing on a molecular scale due to grafting structure.     

Novel synthesis of biodegradable amphiphilic linear and star block copolymers based on poly(ε‐caprolactone) and poly(ethylene glycol)

Biodegradable, amphiphilic, diblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol) (PCL‐b‐PEG), triblock poly(ε‐caprolactone)‐block‐poly(ethylene glycol)‐block‐poly(ε‐caprolactone) (PCL‐b‐PEG‐b‐PCL), and star shaped copolymers were synthesized by ring opening polymerization of ε‐caprolactone in the presence of poly(ethylene glycol) methyl ether or poly(ethylene glycol) or star poly(ethylene glycol) and potassium hexamethyldisilazide as a catalyst. Polymerizations were carried out in toluene at room temperature to yield monomodal polymers of controlled molecular weight. The chemical structure of the copolymers was investigated by ¹H and ¹³C NMR. The formation of block copolymers was confirmed by ¹³C NMR and DSC investigations. The effects of copolymer composition and molecular structure on the physical properties were investigated by GPC and DSC. For the same PCL chain length, the materials obtained in the case of linear copolymers are viscous whereas in the case of star copolymer solid materials are obtained with low T_g and T_m temperatures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3975–3985, 2007     

Mechanical, thermal and degradation properties of poly(d,l-lactide)/poly(hydroxybutyrate-co-hydroxyvalerate)/poly(ethylene glycol) blend

The mechanical, thermal and biodegradable properties of poly(d,l-lactide) (PDLLA), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and poly(ethylene glycol) (PEG) blends were studied. The influence of PEG on the tensile and impact strengths of the blends was investigated. The results showed that the toughness and elongation at break of the PDLLA/PHBV (70/30) blends were greatly improved by the addition of PEG, and the notched Izod impact strength increased about 400% and the elongation at break increased from 2.1% to 237.0%. The thermal and degradation properties of the blends were investigated by differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA), it was found that the thermal stability of PHBV in the presence of PDLLA was improved. The degradation test showed that the addition of PEG could notably accelerate the biodegradation of the blends in the soil at room temperature, and the mass loss is about 20% after 30 days of the storage.     

Synthesis and characterization of biodegradable triblock copolymers based on bacterial poly[(R)‐3‐hydroxybutyrate] by atom transfer radical polymerization

Biodegradable poly(tert‐butyl acrylate)–poly[(R)‐3‐hydroxybutyrate]–poly (tert‐butyl acrylate) triblock copolymers based on bacterial poly[(R)‐3‐hydroxybutyrate] (PHB) were synthesized by atom transfer radical polymerization. The chain architectures of the triblock copolymers were confirmed by ¹H NMR and ¹³C NMR spectra. Gel permeation chromatography analysis was used to estimate the molecular weight characteristics and lengths of the PHB and poly(tert‐butyl acrylate) blocks of the copolymers. The thermal properties of the copolymers were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). TGA showed that the triblock copolymers underwent stepwise thermal degradation and had better thermal stability than their respective homopolymers, whereas DSC analyses showed that a microphase‐separation structure was formed only in the triblock copolymers with the longer PHB block. As a similar result, from wide‐angle X‐ray diffraction experimentation, the crystalline phase of PHB could not be seen evidently in the triblock copolymers with the shorter PHB block. The enzymatic hydrolysis of the copolymer films was carried at 37 °C and pH 7.4 in a potassium phosphate buffer with an extracellular PHB depolymerase from Penicillum sp. The biodegradability of the triblock copolymers increased with an increase in the PHB block content. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4857–4869, 2005     

Thermal properties and applications of low molecular weight polyhydroxybutyrate

The properties of the low molecular weight polyhydroxybutyrate (LMWPHB) and LMWPHB plasticized polyhydroxybutyrate (PHB) are studied using differential scanning calorimetry (DSC), thermogravimetric analysis, wide-angle X-ray diffraction (WAXD), polarized optical microscope (POM), mechanical, and biodegradation tests. The results of DSC, WAXD, and POM indicate that LMWPHB has a lower glass transition temperature (T _g), crystallinity, crystallization rate, melting temperature (T _m), and crystal size than PHB due to its much smaller molecular weight. The tensile strength, T _g, T _m, crystallinity, crystallization rate, and thermal stability of LMWPHB plasticized PHB decrease, while the flexibility and biodegradation rate increase with the increasing content of the added LMWPHB. It is confirmed that LMWPHB can be used to improve the brittleness and control the biodegradation rate of PHB.     

Preparation and characterization of poly(m-xylylene oxamide) and its copolymer

New polyoxamides, poly(m-xylylene oxamide) (PMXD2) and its copolymer with 2-methyl-1,5- pentanediamine (P(MXD2/M52)) with relative viscosity up to 4.6 were synthesized via spray/solid state polymerization. The obtained polyoxamides were characterized by FTIR, NMR, WAXD, DSC and TGA. The T_m of the copolymers decreased with increasing percentage of poly(2-methyl-1,5- pentaneoxamide) (PM52) in the copolymer from 346°C for 100% poly(meta-xylyleneoxamide) (PMXD2) to 277°C for copolymers of PMXD/PM52 (60/40). TGA analysis revealed that the thermal stability of the copolymers compared well with commercial PA6 and XRD studies suggested the copolymers possessed high crystallinity. DMA profile of the PMXD/PM52 (70/30) copolymer showed better mechanical performance with a storage modulus of about 7.2 GPa as compared to 1.8 GPa of PA6 at 25°C.     

Gamma irradiation effects on poly(hydroxybutyrate)

Brazilian poly(hydroxybutyrate), PHB, as well as its copolymer, poly(hydroxybutyrate-co-valerate), P(HB-co-HV), containing 6.3 mol% of valerate, were irradiated with γ radiation (⁶⁰Co) at ambient temperature and in the presence of oxygen. The viscosity-average molar mass (M_v) was analyzed by the viscosity technique using an Ostwald-type capillary viscometer. The polymers showed a decrease in molar mass with the increase in dose, reflecting the scissions that occurred at random in the main chain. The value G (scissions/100 eV of energy transferred to the system) and the parameter α (scissions per original molecule) were also obtained by the viscosity technique. The melting temperature (T_m) was determined by differential scanning calorimetry (DSC) and showed a decrease with increasing irradiation dose. Analyses of DSC also revealed double endothermic peaks, associated with the polymorphic transitions, which became a single peak with increased dose. Thermogravimetry analysis (TGA) revealed small differences between the decomposition temperatures of the irradiated and non-irradiated samples. The degree of crystallinity of PHB samples, on the other hand, which were obtained by the DSC and X-ray diffraction techniques, increased with the irradiation dose. Changes in the lattice parameter of the irradiated samples and in the size of the crystallites were also observed by X-ray diffraction. The samples used in this work did not pass through any purification process and were analyzed in powder form, exactly as they arrived from the factory.     

Single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes

The single-step synthesis of proton conducting poly(vinylidene fluoride) (PVDF) graft copolymer electrolytes is demonstrated. The graft copolymers of PVDF backbone with poly(sulfopropyl methacrylate) (PVDF-g-PSPMA) and poly(styrene sulfonic acid) (PVDF-g-PSSA) were synthesized using PVDF as a macroinitiator for atom transfer radical polymerization (ATRP). ¹H NMR and FT-IR spectroscopy show that the “grafting from” method using ATRP was successful and the maximum grafting degrees were 35 and 25 wt% for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. The IEC values were 0.63 and 0.45 meq/g, the water uptakes were 46.8 and 33.4 wt% and the proton conductivities were 0.015 and 0.007 S/cm at room temperature, for PVDF-g-PSPMA and PVDF-g-PSSA, respectively. Both membranes exhibited excellent thermal stability up to around 350 °C, verified by thermal gravimetric analysis (TGA).     

Characterization and degradation of the poly(methylphenylsiloxane)–poly(methyl methacrylate) graft copolymer

Poly(methylphenylsiloxane)–poly(methyl methacrylate) graft copolymers (PSXE-g-PMMA) were prepared by condensation reaction of poly(methylphenylsiloxane)-containing epoxy resin (PSXE) with carboxyl-terminated poly(methyl methacrylate) (PMMA), and they were characterized by gel permeation chromatography (GPC), infrared (IR), and ²⁹Si and ¹³C nuclear magnetic resonance (NMR). The microstructure of the PSXE-g-PMMA graft copolymer was investigated by proton spin–spin relaxation T₂ measurements. The thermal stability and apparent activation energy for thermal degradation of these copolymers were studied by thermogravimetry and compared with unmodified PMMA. The incorporation of poly(methylphenylsiloxane) segments in graft copolymers improved thermal stability of PMMA and enhanced the activation energy for thermal degradation of PMMA. © 1998 John Wiley & Sons, Inc. J. Polym. Sci. A Polym. Chem. 36: 2521–2530, 1998     

Compatibilizing effect of a graft copolymer on bacterial poly(3‐hydroxybutyrate)/poly(methyl methacrylate) blends

Blends of isotactic (natural) poly(3‐hydroxybutyrate) (PHB) and poly(methyl methacrylate) (PMMA) are partially miscible, and PHB in excess of 20 wt % segregates as a partially crystalline pure phase. Copolymers containing atactic PHB chains grafted onto a PMMA backbone are used to compatibilize phase‐separated PHB/PMMA blends. Two poly(methyl methacrylate‐g‐hydroxybutyrate) [P(MMA‐g‐HB)] copolymers with different grafting densities and the same length of the grafted chain have been investigated. The copolymer with higher grafting density, containing 67 mol % hydroxybutyrate units, has a beneficial effect on the mechanical properties of PHB/PMMA blends with 30–50% PHB content, which show a remarkable increase in ductility. The main effect of copolymer addition is the inhibition of PHB crystallization. No compatibilizing effect on PHB/PMMA blends with PHB contents higher than 50% is observed with various amounts of P(MMA‐g‐HB) copolymer. In these blends, the graft copolymer is not able to prevent PHB crystallization, and the ternary PHB/PMMA/P(MMA‐g‐HB) blends remain crystalline and brittle. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1390–1399, 2002     

聚β-羟基丁酸酯辐照接枝顺丁烯二酸酐及产物表征

探索了一种提高聚β羟基丁酸酯(PHB)热稳定性的方法,即用60Coγ射线辐照对PHB进行顺丁烯二酸酐(MAH)的接枝,采用1HNMR、13CNMR、TGA、DSC、XRD等方法对辐照接枝产物进行了表征.1HNMR、13CNMR谱图结果表明MAH单体接枝到了PHB上.TGA测试表明,辐照接枝产物的热稳定性显著提高,如接枝率为0.52%的样品热分解温度提高了36K.DSC研究表明辐照接枝产物的熔融温度和结晶温度均降低.此外,由于引入极性单体顺丁烯二酸酐,接枝产物的结晶度降低,同时亲水性提高.     

聚β-羟基丁酸酯顺丁烯二酸酐接枝共聚物的研究

采用DSC、TGA、POM和WAXD等方法对聚 β 羟基丁酸酯 (PHB)及其接枝顺丁烯二酸酐共聚物 (PHB g MA)的结晶行为、热稳定性和生物降解特性进行了研究 .结果表明接枝产物的热稳定性明显优于PHB ,热分解温度提高了 2 0余度 ;结晶行为发生很大的变化 .结晶速率减小 ,结晶温度降低 ,冷结晶温度升高 ,球晶的织态结构也随着MA接枝量的变化发生明显变化 ,并且接枝MA促进了PHB的生物降解     

Multiple melting behaviour of poly(3-hydroxybutyrate-co-hydroxyvalerate) using step-scan DSC

Melting behaviour and crystal morphology of poly(3-hydroxybutyrate) (PHB) and its copolymer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with various hydroxyvalerate (HV) contents [5 wt.% (PHB5V), 8 wt.% (PHB8V) and 12 wt.% (PHB12V)] have been investigated by conventional DSC, step-scan differential scanning calorimetry (SDSC), wide angle X-ray diffraction (WAXRD) and hot stage polarised optical microscopy (HSPOM). Crystallisation behaviour of PHB and its copolymers were investigated by isothermal crystallisation kinetics. Thermal properties were investigated after isothermal crystallisation treatment. Multiple melting peak behaviour was observed for all polymers. SDSC data revealed that PHB and its copolymers undergo melting-recrystallisation-remelting during heating, as evidenced by exothermic peaks in the IsoK baseline (C_p,IsoK, non-reversing signal). An increase in degree of crystallinity due to significant melt-recrystallisation was observed for isothermally crystallised polymers. SDSC proved a convenient and precise method for measurement of the apparent thermodynamic specific heat (C_p,ATD, reversing signal). PHB and PHBV showed different crystal morphologies for similar crystallisation condition. HSPOM results showed that the crystallisation rates reduced and sizes of spherulites were significantly increased as HV content increased.     

Silver sulfide/poly(3-hydroxybutyrate) nanocomposites: Thermal stability and kinetic analysis of thermal degradation

The non-isothermal degradation of poly(3-hydroxybutyrate) (PHB) and silver sulfide/poly(3-hydroxybutyrate) (Ag₂S/PHB) nanocomposites was investigated using thermogravimetric (TG) analysis. In the composite materials, Ag₂S caused the degradation of PHB at a lower temperature as opposed to that of neat PHB. Moreover, an increase Ag₂S loading in the PHB decreased the onset temperature (T_onset) of thermal degradation, whereas it was raised upon augmenting the heating rate. From Kissinger plots, the observed trend of the degradation activation energy, E_d, was attributed to polymer-particle surface interactions and the agglomeration of Ag₂S. The thermal degradation rate constant, k, was linearly related to the Ag₂S loading in PHB. Thus, the Ag₂S nanoparticles effectively catalyzed the thermal degradation of PHB in the Ag₂S/PHB nanocomposites. Differential scanning calorimetry (DSC) data also supported the catalytic property of Ag₂S.     

Interpolymer complexation in hydrolysed poly(styrene-co-maleic anhydride)/poly(styrene-co-4-vinylpyridine)

Complexation between hydrolysed poly(styrene-co-maleic anhydride) (HSMA) copolymers containing 28% and 50% maleic anhydride and a poly(styrene-co-4-vinylpyridine), St4VP32 copolymer with 32% of 4-vinylpyridine content has been investigated. Formation of interpolymer complexes from 1,4-dioxane solutions is observed, over the entire composition range and the stoichiometry of these complexes has been determined from elemental analysis.Quantitative FTIR study of the system HSMA50/StV4Py32 shows that the ideal complex composition leads to 2:1 unit mole ratio of interacting component. FTIR results are in good agreement with DSC and TGA ones, since this complex composition gives the maximum value of the glass transition temperature and the best thermic stability.For the systems investigated, the T_g versus composition curve do not follow any of the commonly accepted models proposed for polymer blends. A new model proposed by Cowie [Cowie JMG, Garay MT, Lath D, McEwen IJ. Br Poly J 1989;21:81] is used to fit the T_g data and found to reproduce the experimental results more closely.     

Preparation and thermal properties of a novel flame retardant copolymer

A monomer, acryloxyethyl phenoxy phosphorodiethyl amidate (AEPPA), was synthesized and characterized using Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance spectroscopy (¹H NMR) and ³¹P NMR. The copolymer with various amounts of styrene (St) was obtained by the free radical bulk polymerization between AEPPA and St, and characterized using ¹H NMR. The thermal properties of the copolymers were investigated with thermogravimetric analysis (TGA) in air and nitrogen atmosphere, and differential scanning calorimetry (DSC). The TGA results in air indicated the copolymers with AEPPA show higher thermal stability than those without AEPPA. However, the TGA results in nitrogen showed that the decomposition temperature decreased and the char residue increased with the increase of AEPPA. The glass transition temperature (T_g) of the copolymers from DSC indicated that a inverse proportion was observed between T_g and the amount of AEPPA incorporated. The flammability of the copolymers was evaluated by microscale combustion calorimeter (MCC). The MCC results showed that AEPPA can decrease the peak heat release rate (PHRR) and the heat release capacity (HRC), and the sample CP10 shows the lowest PHRR and HRC.     

含氟两亲接枝共聚物的制备及其结晶行为

采用大分子单体技术合成了一系列以聚乙二醇为支链、甲基丙烯酸六氟丁酯为主链的含氟两亲接枝共聚物(PHFMA-g-PSPEG)。用1HNMR和凝胶色谱(GPC)对制备的大分子单体和两亲接枝共聚物的结构进行了表征。利用示差扫描量热法(DSC)、X射线衍射(XRD)和偏光显微镜(POM)测试技术对含氟两亲接枝共聚物的结晶行为进行了研究。DSC和XRD结果表明,随着共聚物中含氟链段质量分数的增加,其结晶温度(Tc)和结晶度(Xc)均降低,而结晶熔融温度(Tm)先减小后增加。POM发现,随着共聚物中含氟链段质量分数的增加,其结晶速度减慢,共聚物形成清晰球晶的能力减弱,当共聚物中含氟链段质量分数为57%时,含氟两亲接枝共聚物已不能形成清晰的球晶。     

聚对二氧环己酮/聚乙二醇多嵌段共聚物的合成与表征

首先合成双端羟基的聚对二氧环己酮预聚物(PPDO)和双端羧基的聚乙二醇预聚物(PEG),然后以丁二酸酐/二环己基碳二亚胺(DCC)将PPDO与PEG偶联共聚,得到PPDO/PEG多嵌段共聚物.通过1H-NMR和GPC表征了聚合物的结构和分子量.采用差示扫描量热法(DSC)和热重分析(TGA)研究了共聚物的结晶性能和热稳定性.用透析法制备了共聚物纳米粒子,并用动态光散射(DLS)表征了共聚物纳米粒子的粒径及分散度,结果表明,随着共聚物亲水链段PEG含量的增加,其纳米粒子更易形成,粒子粒径随共聚物分子量增大而增大.     

Amphiphilic PEG‐grafted poly(ester‐carbonate)s: Synthesis and diverse nanostructures in water

Novel biodegradable amphiphilic graft copolymers containing hydrophobic poly(ester‐carbonate) backbone and hydrophilic poly(ethylene glycol) (PEG) side chains were synthesized by a combination of ring‐opening polymerization and “click” chemistry. First, the ring‐opening copolymerization of 5,5‐dibromomethyl trimethylene carbonate (DBTC) and ε‐caprolactone (CL) was performed in the presence of stannous octanoate [Sn(Oct)₂] as catalyst, resulting in poly(DBTC‐co‐CL) with pendant bromo groups. Then the pendant bromo groups were completely converted into azide form, which permitted “click” reaction with alkyne‐terminated PEG by Huisgen 1,3‐dipolar cycloadditions to give amphiphilic biodegradable graft copolymers. The graft copolymers were characterized by proton nuclear magnetic resonance (¹H NMR), Fourier transform infrared spectra and gel permeation chromatography measurements, which confirmed the well‐defined graft architecture. These copolymers could self‐assemble into micelles in aqueous solution. The size and morphologies of the copolymer micelles were measured by transmission electron microscopy and dynamic light scattering, which are influenced by the length of PEG and grafting density. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.