Polyhydroxybutyrate/acrylonitrile‐g‐(ethylene‐co‐ propylene‐co‐diene)‐g‐styrene blends: Their morphology and thermal and mechanical behavior

Polyhydroxybutyrate (PHB) is a biodegradable bacterial polyester emerging as a viable substitute for synthetic, semicrystalline, nonbiodegradable polymers. An elastomer terpolymer of acrylonitrile‐g‐(ethylene‐co‐propylene‐co‐diene)‐g‐styrene (AES) was blended with PHB in a batch mixer and in a twin‐screw extruder to improve the mechanical properties of PHB. The blends were characterized with differential scanning calorimetry, dynamic mechanical analysis, scanning electron microscopy, and impact resistance measurements. Despite the narrow processing window of PHB, blends with AES could be prepared via the melting of the mixture without significant degradation of PHB. The blends were immiscible and composed of four phases: poly(ethylene‐co‐propylene‐co‐diene), poly(styrene‐co‐acrylonitrile), amorphous PHB, and crystalline PHB. The crystallization of PHB in the blends was influenced by the AES content in different ways, depending on the processing conditions. A blend containing 30 wt % AES presented impact resistance comparable to that of high‐impact polystyrene, and the value was about 190% higher than that of pure PHB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Higher‐molecular‐weight hyperbranched polyethylenes containing crosslinking structures as lubricant viscosity‐index improvers

As a new grade of polyethylene materials with unique chain architectures, hyperbranched polyethylenes synthesized by chain walking ethylene polymerization have great potential for industrial application as novel viscosity index (VI) improver in lubricant formulation. Although high‐molecular‐weight hyperbranched polyethylenes (weight‐average molecular weight of about 10⁵ g/mol) possess high shear stability, their viscosity thickening properties are compromised due to their compact chain architectures. In this work, we aim at improving their viscosity thickening property by increasing polymer molecular weight. A range of hyperbranched polymers of various enhanced molecular weights were synthesized by chain walking ethylene polymerization in the presence of small amounts of 1,4‐butanediol diacrylate as a difunctional crosslinker. The molecular weight dependences of viscosity thickening power and shear stability of these polymers containing crosslinking structures were evaluated. It is found that, with the increase of molecular weight via crosslinking, these polymers showed consistently enhanced viscosity thickening power, but with the reduced shear stability. However, their shear stability was still significantly better compared to linear polymers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Crystallization of poly(3‐hydroxybutyrate) with stereocomplexed polylactide as biodegradable nucleation agent

Crystallization kinetics behavior and morphology of poly(3‐hydroxybutyrate) (PHB) blended with of 2–10 wt% loadings of poly(L ‐ and D ‐lactic acid) (PLLA and PDLA) stereocomplex crystallites, as biodegradable nucleating agents, were studied using differential scanning calorimetry, polarizing‐light optical microscopy (POM), and wide‐angle X‐ray diffraction (WAXD). Blending PLLA with PDLA at 1:1 weight ratio led to formation of stereocomplexed PLA (sc‐PLA), which was incorporated as small crystalline nuclei into PHB for investigating melt‐crystallization kinetics. The Avrami equation was used to analyze the isothermal crystallization of PHB. The stereocomplexed crystallites acted as nucleation sites in blends and accelerated the crystallization rates of PHB by increasing the crystallization rate constant k and decreasing the half‐time (t_1/2). The PHB crystallization was nucleated most effectively with 10 wt% stereocomplexed crystallites, as evidenced byPOM results. The sc‐PLA complexes (nucleated PHB crystals) exhibit much small spherulite sizes but possess the same crystal cell morphology as that of neat PHB based on the WAXD result. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Initiator‐fragment incorporation radical polymerization of ethylene glycol dimethacrylate in the presence of 1,1‐diphenylethylene: synthesis and characterization of soluble hyperbranched polymer nanoparticles

The polymerization of ethylene glycol dimethacrylate (EGDMA) as crosslinker was carried out at 70 and 80 °C in benzene using dimethyl 2,2′‐azobisisobutyrate (MAIB) as initiator at concentrations as high as 0.50–0.70 mol l^?1 in the presence of 1,1‐diphenylethylene (DPE), where the concentrations of EGDMA and DPE were 0.50–0.70 and 0.25–0.50 mol l^?1, respectively. The polymerization proceeded homogeneously, without gelation, to give soluble polymers. The yield and molecular weight of the resulting polymers increased with time. The homogeneous polymerization system involved ESR‐observable DPE‐derived radicals of considerably high concentration (3.6–5.3 × 10^?5 mol l^?1). The methoxycarbonylpropyl groups as MAIB‐fragments were incorporated as a main constituent (35–50 mol%) into the polymers (initiator‐fragment incorporation radical polymerization). The polymers also contained DPE units (15 mol%) and EGDMA units with double bonds (10–25 mol%) and without double bonds (20 mol%). Results from gel permeation chromatography (GPC)–multiangle laser light scattering (MALLS), transmission electron microscopy (TEM) and viscometric measurements revealed that the individual polymer molecules were formed as hyperbranched nanoparticles. Copyright © 2004 Society of Chemical Industry     

Improvement of thermal properties of biodegradable polymer poly(3‐hydroxybutyrate) by modification with acryloyloxyethyl isocyanate

Poly(3‐hydroxybutyrate) (PHB) is one type of polyhydroxyalkanoates often used as a biomedical material due to its biodegradable and biocompatible nature. However, the mechanical and thermal properties of PHB must be improved before it can be used in a wider variety of biomedical applications. To improve the thermal properties of biodegradable PHB, various reaction conditions were studied. Results demonstrate that reacting PHB with acryloyloxyethyl isocyanate (AOI), a monomer with dual functional groups, produces a modified PHB material with markedly improved thermal properties. The 10% thermal decomposition temperature for PHB modified with 5% AOI was 297°C, which was 26.8°C higher than original PHB. The T_g also increased from 4°C to around 30°C for AOI‐modified materials. Additionally, due to the poly(ester‐urethane) structure and hydrogen bonding of polymer materials, the mechanical properties also improved. Thus, this modified PHB biodegradable polymer may have greater application as a biomedical material due to its enhanced thermal and mechanical properties. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Environmental degradation and biofouling of ‘green’ plastics including short and medium chain length polyhydroxyalkanoates

Biopolymers derived from natural resources are potential alternatives to recalcitrant synthetic plastics; however, studies investigating the degradability of these biopolymers in natural environments are relatively few. This study compares the environmental degradation of polymers described as ‘green plastics’ in garden soil in terms of weight loss, topographical changes and biofilm attachment. Poly(3‐hydroxybutyrate) (PHB) and poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] (P(HB‐co‐8HV)), (copolymer containing 8 mol% HV) films degraded rapidly, losing 50% of their initial weight in 50 days. In contrast, after burial for 380 days, the medium chain length polyhydroxyoctanoate (PHO) lost 60% of its weight, poly(D ,L ‐lactide) (PDLL) 18% and poly[(D ,L ‐lactide)‐co‐glycolide] (PDLLG) 35%. Polystyrene (PS) and ethyl cellulose (EC) showed no significant degradation. Both weight loss and biofouling occurred in the following sequence: P(HB‐co‐8HV) = PHB > PHO > PDLLG > PDLL > PS = EC. The surface rugosity and surface areas of PHB and P(HB‐co‐8HV) increased three‐ and twofold, respectively, during degradation, indicating surface erosion. The surface rugosity of PHO increased twofold and the surface area increased by 25%. This in situ study demonstrates a quantifiable relationship between biofilm attachment, surface rugosity and polymer degradation. PHB and P(HB‐co‐8HV) showed greater biofouling and increased surface rugosity, and degraded significantly faster than the other polymers studied. Copyright © 2009 Society of Chemical Industry     

Isothermal degradation of poly(3‐hydroxybutyrate)/organically modified montmorillonite nanocomposites

Polymer nanocomposites consisted of biodegradable poly(3‐hydroxybutyrate) (PHB) and organically modified montmorillonite Cloisite25A (OMMT), prepared by the solution‐casting method, were isothermally degraded for 120 min at 230, 235, 240, and 245°C in the nitrogen atmosphere. The addition of OMMT increases the thermal stability of PHB, and the most pronounced effect has the addition of 7 wt% of OMMT. Kinetic analysis was performed using reduced time plots and model‐free isoconversional methods. The empirical kinetic triplets (E, A, and g(α)) for the isothermal degradation of pure PHB and PHB/OMMT nanocomposites were determined. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Preparation and characterization of hyperbranched polyacrylate copolymers by self‐condensing vinyl copolymerization (SCVCP)

A series of hyperbranched polyacrylate copolymers have been synthesized by self‐condensing vinyl copolymerization (SCVCP) of 2‐(2‐bromopropionyloxy)‐ethyl acrylate (BPEA) and methyl acrylate (MA) in the presence of CuBr and bipyridine. The structures and properties of the polymers obtained are characterized by NMR and SEC/RALLS/DV/RI measurements. The effects of reaction conditions on molecular weight (MW), molecular weight distribution (MWD) and degree of branching (DB) are investigated. © 2002 Society of Chemical Industry     

Preparation of hyperbranched polymers through ATRP of in situ formed AB* monomer

The self‐condensing vinyl polymerization of an AB* monomer formed in situ by atom transfer radical addition from divinylbenzene (DVB) and (1‐bromoethyl)benzene (BEB) using atom transfer radical polymerization technique was studied. The catalyst concentration has a dramatic effect on polymerization. To study the polymerization mechanism and to achieve high molecular weight polymer, the polymerization was carried out in bulk with a catalyst to monomer ratio, 2,2′‐bipyridine to DVB, of 0.2 at 90°C. Proton nuclear magnetic resonance (¹H NMR) spectroscopy and size‐exclusion chromatography coupled with multiangle laser light scattering were used to analyze the polymerization aliquots and the obtained polymer. The intrinsic viscosities of the prepared polymers were also measured. Experimental results, from the comparison of the apparent molecular weights measured by size‐exclusion chromatography with the absolute values measured by multiangle laser light scattering as well as viscosity measurements, indicate the existence of hyperbranched structures in the prepared polymers. In sharp contrast to hyperbranched polymers from AB* monomer preprepared, hyperbranched ploy(divinylbenzene) prepared at equimolar amount of DVB and BEB has numerous residual pendant vinyl groups rather than only one double bond at its focal point. The hyperbranched polymers show relatively narrow molecular weight distribution (2.13–3.77) and exhibit excellent solubility in common organic solvents such as acetone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 850–856, 2006     

Dielectric properties and solubility of multilayer hyperbranched polyimide/polyhedral oligomeric silsesquioxane nanocomposites

Multilayer hyperbranched polyimide/polyhedral oligomeric silsesquioxane (POSS) nanocomposites were synthesized by the reaction of a bromide‐hyperbranched polyether/POSS and a main‐chain polyimide containing hydroxyl‐functional groups. The first layer was formed through the direct reactions of the main‐chain hydroxyl groups with monochloroisobutyl polyhedral oligomeric silsesquioxane (POSS–Cl). The second and third layers were prepared by the repeated reactions of bromine ether branches that incorporated POSS–Cl with 3,5‐dihydroxybenzyl alcohol. Regardless of the fixed amount of POSS, the higher layers yielded lower dielectric constants. Even when the amount of the POSS loading was reduced 4‐fold, the third layer still had the lowest dielectric constants. The lowest dielectric constant of 2.54 was found in the third layer of the hyperbranched polyimide/POSS nanocomposite because of the large free volume and loose polyimide structures. The densities of the hyperbranched polyimide/POSS nanocomposite corresponded to the dielectric constants. The lower the density was, the higher the free volume was and the lower the dielectric constant was. The experimental results indicated that the hyperbranched polyimide/POSS nanocomposite exhibited increased solubility in comparison with pure polyimide. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electron transport properties of polyaniline composite films containing poly(3‐hydroxybutyric acid)

Polyaniline (PANI) composites containing poly(3‐hydroxybutyric acid) (PHB) were synthesized via in situ deposition technique. The oxidative polymerization of aniline hydrochloride was carried out by dissolving different weight percentages (10 wt%, 20 wt%, 30 wt%, 40 wt%, and 50 wt%) of PHB using ammonium persulfate as an oxidant. The as‐synthesized composites were characterized using Fourier‐transform infrared spectroscopy and X‐ray diffraction pattern. The surface morphology of the resulting composites was studied using transmission electron microscopy. The temperature‐dependent direct current conductivity of the synthesized composite films was measured, and the activation energy responsible for the conductivity was examined. Incorporation of the biodegradable polymer, PHB, during the preparation of new PANI composites significantly increased the conductivity of the resulting composites. POLYM. COMPOS., 34:1655–1662, 2013. © 2013 Society of Plastics Engineers     

Miscibility,melting, and crystallization behavior of poly(hydroxybutyrate) and poly(D,L‐lactic acid) blends

Melting behavior and crystal morphology of poly(3‐hydroxybutyrate)‐poly(D ,L ‐lactic acid) (PHB‐RPLA) blends with various compositions have been investigated by modulated temperature differential scanning calorimetry (mt‐DSC), polarized optical thermomicroscopy (POTM), modulated force thermomechanometry (mf‐TM), and small angle X‐ray scattering (SAXS). Thermal properties were investigated after fast cooling crystallization treatment. Multiple melting peak behavior was observed for all polymers. mt‐DSC data revealed that PHB‐RPLA blends undergo melting‐recrystallization‐remelting during heating, as evidenced by exothermic peaks in the nonreversing heat capacity. A decrease in degree of crystallinity due to significant melt‐recrystallization was observed for blends. PHB‐RPLA showed different crystal morphologies for various compositions. POTM results showed that the crystallization rates and sizes of spherulites were significantly reduced as RPLA content increased. mf‐TM results confirmed miscibility of these two polymers. SAXS data provided evidence of lamella thickness of blends, which increased with increasing RPLA content. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Preparation and properties of blends from poly(3‐hydroxybutyrate) with poly(vinyl acetate)‐modified starch

This research used the ceric ion to initiate the graft‐polymerization of vinyl acetate (VAc) to a soluble potato starch. Fourier transform infrared spectra confirmed the formation of starch graft copolymer. After 4 h of reaction at 50°C, total monomer conversion, grafting efficiency, and grafting ratio were measured as 91%, 12.5%, and 0.223, respectively. The synthesized PVAc‐modified starch was then blended with poly(3‐hydroxybutyrate) (PHB). Structures, thermal and mechanical properties of the prepared blends were examined. The results showed the PHB and PVAc‐modified starch were miscible in all compositions. In addition, thermal gravimetric analysis revealed that the addition of PVAc‐modified starch increased the thermal stability of the PHB component. Further evidence also showed that the addition of PVAc‐modified starch reduced the extent of decrease in molecular weight of PHB in a melt‐mixer. PHB/PVAc‐modified starch blends exhibit higher toughness than pure PHB because of increased compatibility and the leathery PVAc‐modified starch. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Synthesis of new amphiphilic water‐stable hyperbranched polycarbosilane polymers

New amphiphilic hyperbranched polymers possessing hydrophobic skeletons and hydrophilic terminal groups have been prepared and characterized. The synthetic strategy involved the formation of a new stable matrix with aromatic units within a carbosilane backbone, as well as the use of a classical polycarbosilane matrix. Both of them with allyl groups on the surface have narrow polydispersity values. Molecular weight and polydispersity of the hyperbranched polymers were obtained using gel permeation chromatography with multi‐angle light scattering, and determination of the average number of functional groups present on the surface was achieved using ¹H NMR spectroscopy. The introduction of ionic groups was carried out via thiol–ene reactions with various thiol derivatives. The thermal properties of the polymers were also analysed using differential scanning calorimetry and zeta potential measurements. © 2013 Society of Chemical Industry     

Effect of modified montmorillonite on biodegradable PHB nanocomposites

Polymer nanocomposites, based on a bacterial biodegradable thermoplastic polyester, poly(hydroxybutyrate) (PHB), and two commercial montmorillonites (MT), Na-M (MT) and 30B-M (organically modified MT), were prepared by melt-mixing technique at 165 °C. Both clays minerals were characterized by morphology, crystallochemical parameters, and thermal stability. Lower specific surface area (determined by adsorption methods) values were found for 30B-M. The apparent particle size from light scattering measurements, scanning electron microscopy observations, and crystallite size (determined from XRD patterns) of 30B-M indicated a higher degree of particles exfoliation than of Na-M.The nanocomposites PHBNa and PHB30B were characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM), X-ray diffraction (XRD), transmission electron microscopy (TEM), mechanical properties, and burning behaviour. Intercalation/exfoliation observed by TEM and XRD was more pronounced for PHB30B than PHBNa, indicating the better compatibility of 30B-M with the PHB matrix. An increase in crystallization temperature and a decrease in spherullites size were observed for PHB30B. The intercalation/exfoliation observed by TEM and structure XRD increased the moduli of the nanocomposites. The burning behaviour of PHB30B was influenced by the aggregation of the clay mineral particles.     

Synthesis and characterization of a thermotropic liquid crystalline hyperbranched polyester

BACKGROUND: Hyperbranched polymers have received increasing attention in the fields of medicine, homogeneous catalysis and materials science. Hydroxyl‐functional aliphatic polyesters are one of the most widely investigated families of hyperbranched polymers. The research reported here is based on the preparation of a novel hyperbranched polyester and the modification of its terminal hydroxyl groups by biphenyl mesogenic units. RESULTS: 2,2,6,6‐Tetramethylolcyclohexanol as a core and 8‐[4′‐propoxy(1,1‐biphenyl)yloxy]octanoic acid as a mesogenic unit were synthesized. A hyperbranched polyester (HPE) was synthesized in one step and subsequently substituted by reaction of its terminal hydroxyl groups with the biphenyl mesogenic units to yield a novel liquid crystalline hyperbranched polyester (HPE‐LC). The chemical structures of all compounds were confirmed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopy. The thermal behavior and the mesogenic properties of the biphenyl mesogenic unit and HPE‐LC were investigated using differential scanning calorimetry, polarized optical microscopy and wide‐angle X‐ray diffraction. The results demonstrated that the degree of branching of the HPE is ca 0.63. Both HPE‐LC and the biphenyl mesogenic unit exhibit mesomorphic properties, but HPE‐LC has a lower isotropic transition temperature and a wider transition temperature range than the biphenyl mesogenic unit. CONCLUSION: A novel liquid crystalline hyperbranched polyester was successfully synthesized, which exhibits mesomorphic properties. This polymer has good solubility in highly polar solvents and good thermal stability. Copyright © 2009 Society of Chemical Industry     

Plasma polymerization‐modified bacterial polyhydroxybutyrate nanofibrillar scaffolds

The design and the development of novel scaffold materials for tissue engineering have attracted much interest in recent years. Especially, the prepared nanofibrillar scaffold materials from biocompatible and biodegradable polymers by electrospinning are promising materials to be used in biomedical applications. In this study, we propose to produce low‐cost and cell‐friendly bacterial electrospun PHB polymeric scaffolds by using Alcaligenes eutrophus DSM 545 strain to PHB production. The produced PHB was characterized by Nuclear Magnetic Resonance (NMR) and Fourier Transform Infrared Spectroscopy (FTIR). Nanofibrous scaffolds were fabricated via electrospinning method that has a fiber diameter approximately 700–800 nm. To investigate cell attachment, cell growth, and antioxidant enzyme activity on positively and negatively charged PHB scaffold, PHB surface was modified by plasma polymerization technique using polyethylene glycol (PEG) and ethylenediamine (EDA). According to the results of superoxide dismutase (SOD) activity study, PEG‐modified nanofibrillar scaffolds indicated more cellular resistance against oxidative stress compared to the EDA modification. As can be seen in cell proliferation results, EDA modification enhanced the cell proliferation more than PEG modification, while PEG modification is better as compared with nonmodified scaffolds. In general, through plasma polymerization technique, surface modified nanofibrillar structures are effective substrates for cell attachment and outgrowth. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Cure characterization of soybean oil—Styrene—Divinylbenzene thermosetting copolymers

Bio‐based resins are an alternative to petroleum‐based resins in the production of fiber‐reinforced polymers (FRPs) by processes such as pultrusion. A detailed understanding of the cure behavior of the resin is essential to determine the process variables for production of FRPs. In this work, the cure kinetics of soybean oil‐styrene‐divinylbenzene thermosetting polymers is characterized by differential scanning calorimetry (DSC) measurements. By varying the concentration of the cationic initiator from 1 to 3 weight percent (wt %), the most viable resin composition for pultrusion is identified. The ability of phenomenological reaction models to describe the DSC measurements for the optimum resin composition is tested and kinetic equations, which can be used to determine the degree of cure at any temperature and time, are determined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009