Aging behavior and mechanism of bio‐based engineering polyester elastomer nanocomposites

Bio‐based elastomers used in industry have attracted much attention. We prepared bio‐based engineering polyester elastomer (BEE) nanocomposites by mixing bio‐based engineering polyester elastomers with carbon (CB). The CB/BEE nanocomposites were exposed to an artificial weathering environment for different time periods. Both its aging behavior changes and aging mechanism were investigated in this article. The tensile strength retention rates were each above 90% after aging at 100°C and 125°C for 72 h. CB/BEE nanocomposites exhibited good anti‐aging properties. Furthermore, the chemical changes were detected by Fourier transform infrared spectroscopy and differential scanning calorimetry. The crosslink density changes during aging of BEE were determined as well. A plausible aging mechanism of BEE was proposed. It can be concluded that the thermal oxidation process gives priority to further crosslinking in the initial period of aging. As the aging time increases, chain scission becomes the dominant element in the subsequent thermal oxidation process. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40862.     

Poly(ethylene glycol) derivatives containing periodic side‐chain carboxyl groups: synthesis and characterization

The aim was the synthesis of chain‐extended poly(ethylene glycol) (PEG) derivatives containing periodic side‐chain carboxyl groups. The chain extension of PEG diols with pyromellitic dianhydride was performed in toluene or dimethylformamide solution and in bulk. The degree of chain extension (DoCE) was between 6 and 21, the highest value being recorded when the reaction was performed using low‐molecular‐weight PEG. The recorded limited increase of molecular weight could be at least partially attributed to the rather low reactivity of the aromatic dianhydride. To overcome this issue, a more reactive aliphatic dianhydride, ethylenediaminetetraacetic dianhydride (EA), was tested. However, the reaction of PEG with EA only afforded a DoCE of 2.5. Appreciably higher DoCE values were obtained when EA was reacted with bisamino‐terminated PEG. Independent of prepolymer and dianhydride structure, all chain‐extended products displayed less of a tendency to crystallization than the starting prepolymer, very likely due to interference by anhydride residues. The low in vitro cytotoxicity of the chain‐extended polymers and the presence of carboxyl groups point to their possible use in biomedical applications, particularly in controlled drug release and tissue engineering. © 2014 Society of Chemical Industry     

Preparation and properties of a novel bio‐based and non‐crystalline engineering elastomer with high low‐temperature and oil resistance

A series of poly(succinic acid/sebacic acid/itaconic acid/butanediol/propanediol) bio‐based and non‐crystalline engineering elastomers (BEE) were obtained by changing the molar ratio of succinic acid (SA) to sebacic acid (SeA) from 5:5 (BEE‐5) to 8:2 (BEE‐8). We prepared bio‐based engineering elastomer composites (BEE/CB) by mixing BEE with carbon black N330. The low‐temperature and oil resistance properties of the BEE/CB composites were investigated in terms of low‐temperature brittleness, coefficient of cold resistance under compression, oil resistance test at different temperatures, and tensile properties. The results showed that the low‐temperature brittleness temperature of the BEE/CB composites ranged from ?50 to ?60°C and the coefficient of cold resistance under compression was 0.18 high at ?60°C for BEE‐7/CB and 0.23 high at ?40°C for BEE‐8/CB. The oil resistance properties of BEE‐7/CB were higher than those of nitrile‐butadiene rubber N240S (NBR N240S), and the oil resistance properties of BEE‐8/CB were even as high as those of nitrile‐butadiene rubber N220S (NBR N220S). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42855.     

Mechanical and thermal properties of thermoplastic random copolyesters made from lipid‐derived Medium and long chain poly(ω‐hydroxyfatty acid)s

The physical properties of novel thermoplastic random copolyesters [‐(CH₂)_n‐COO‐/‐(CH₂)_n‐COO‐]_x made of long (n = 12) and medium (n = 8) chain length ω‐hydroxyfatty esters [HO‐(CH₂)_n‐COOCH₃] derived from bio‐based vegetable oil feedstock are described. Poly(ω‐hydroxy tridecanoate/ω‐hydroxy nonanoate) P(?Me13?/?Me9?) random copolyesters (M_n = 11,000–18,500 g/mol) with varying molar ratios were examined by TGA, DSC, DMA and tensile analysis, and WAXD. For the whole range of P(?Me13?/?Me9?) compositions, the WAXD data indicated an orthorhombic polyethylene‐like crystal packing. Their melting characteristics, determined by DSC, varied with composition suggesting an isomorphic cocrystallization behavior. TGA of the P(?Me13?/?Me9?)s indicated improved thermal stability determined by their molar compositions. The glass transition temperature, investigated by DMA, was also found to vary with composition. The crystallinities of P(?Me13?/?Me9?)s however, were unaffected by the composition. The stiffness (Young's modulus) of these materials was found to be related to their degrees of crystallinity. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40492.     

Recyclable bio‐based crosslinked polyurethanes with self‐healing ability

We report the synthesis of a linear bio‐based polyurethane (bio‐PU) containing furan ring by using renewable polylactide copolymer diol and 2,5‐furandimethanol as a soft segment and chain extender, respectively, in which the reversible crosslinked covalent bonds between hard segments were incorporated via Diels–Alder (D‐A) reaction between the furan ring of the chain extender and bismaleimide (BM) crosslinker. By simply controlling the amount of BM, mechanical properties of the obtained crosslinked bio‐PUs (CBPUs) were varied widely. In particular, the CBPU100 sample shows the highest tensile strength of 10.8 MPa, Young's modulus of 193 MPa, and an elongation of 155%. The differential scanning calorimetry experiments verify the recycle property of the CBPUs by the D‐A/retro‐D‐A reaction at the proper temperature. The thermal recyclability and remolding ability of these materials are demonstrated by two kinds of polymer processing methods, i.e., solution casting and hot‐compression molding. The recycled CBPUs display almost identical elongation and slightly decreased tensile strength compared to the as‐synthesized samples. Furthermore, the CBPUs also exhibit excellent self‐healing ability. Therefore, the resulting CBPUs possess tunable mechanical properties, good thermal recyclability, re‐mending, and self‐healing ability, which makes the bio‐based materials more eco‐friendly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46272.     

Synthesis and characterization of bio‐based thermosetting resins from lactic acid and glycerol

A bio‐based thermoset resin has been synthesized from glycerol reacted with lactic acid oligomers of three different chain lengths (n): 3, 7, and 10. Lactic acid was first reacted with glycerol by direct condensation and the resulting branched molecule was then end‐functionalized with methacrylic anhydride. The resins were characterized by Fourier‐transform infrared spectroscopy (FT‐IR), by ¹³C‐NMR spectroscopy to confirm the chemical structure of the resin, and by differential scanning calorimetry and dynamic mechanical thermal analysis (DMTA) to obtain the thermal properties. The resin flow viscosities were also measured using a rheometer with different stress levels for each temperature used, as this is an important characteristic of resins that are intended to be used as a matrix in composite applications. The resin with a chain length of three had better mechanical, thermal, and rheological properties than the resins with chain lengths of seven and 10. Also, its bio‐based content of 78% and glass transition temperature of 97°C makes this resin comparable to commercial unsaturated polyester resins. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40488.     

Synthesis and solar cells applications of EO‐PF‐DTBT polymer

Poly{[2,7‐(9,9‐bis‐(1‐(2‐(2‐methoxyethoxy)ethoxy)ethyl)‐fluorene)]‐alt‐[5,5‐(4,7‐di‐2′‐thienyl‐2,1,3‐benzothiadiazole)]} (EO‐PF‐DTBT) was synthesized by Suzuki coupling reaction. The polymer is soluble in common organic solvent, such as toluene, THF, and chloroform, and it also shows solubility in polar solvent, such as cyclopentanone. Solar cells based on EO‐PF‐DTBT and PC₆₁BM show maximum power conversion efficiency of 2.65% with an open circuit voltage (V_OC) of 0.86 V, a short circuit current density (J_SC) of 6.10 mA/cm², and a fill factor of 51% under AM 1.5G illumination at 100 mW/cm², which is the best results for fluorene and 4,7‐di‐2‐thienyl‐2,1,3‐benzothiadiazole copolymers and PC₆₁BM blend. The 1,8‐diiodooctane can work well to reduce the over‐aggregated phase structure in polymer solar cells. Our results suggest that the introducing high hydrophilic side chain into conjugated polymer donor materials can tune the aggregation structure and improve the solar cells performances. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40478.     

Bio‐composites for structural applications: Poly‐l‐lactide reinforced with long sisal fiber bundles

Fully bio‐based and biodegradable composites were compression molded from unidirectionally aligned sisal fiber bundles and a polylactide polymer matrix (PLLA). Caustic soda treatment was employed to modify the strength of sisal fibers and to improve fiber to matrix adhesion. Mechanical properties of PLLA/sisal fiber composites improved with caustic soda treatment: the mean flexural strength and modulus increased from 279 MPa and 19.4 GPa respectively to 286 MPa and 22 GPa at a fiber volume fraction of V_f = 0.6. The glass transition temperature decreased with increasing fiber content in composites reinforced with untreated sisal fibers due to interfacial friction. The damping at the caustic soda‐treated fibers‐PLLA interface was reduced due to the presence of transcrystalline morphology at the fiber to matrix interface. It was demonstrated that high strength, high modulus sisal‐PLLA composites can be produced with effective stress transfer at well‐bonded fiber to matrix interfaces. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40999.     

Chain extension of polybutylene adipate and polybutylene succinate with adipoyl‐ and terephthaloyl‐biscaprolactamate

HO‐terminated polybutylene adipate (HO‐PBA‐OH) with molecular weight from 1040 to 3540 and HO‐terminated polybutylene succinate (HO‐PBS‐OH) with intrinsic viscosity of 0.37 dL/g were synthesized through melt condensation polymerization from adipic acid or succinic acid with excess of butanediol. Chain extension of HO‐PBA‐OH or HO‐PBS‐OH with adipoyl biscaprolactamate and terephthaloyl biscaprolactamate was carried out at 200–240°C under reduced pressure. At the optimal conditions, chain‐extended PBA with M_n up to 50,700, and M_w up to 125,700 was synthesized, and the chain‐extended PBS with intrinsic viscosity of 1.25 dL/g was obtained. Meanwhile, p‐toluenesulfonic acid, SnCl₄ and zinc acetylacetonate catalyzed chain‐extending reaction of HO‐PBA‐OH and HO‐PBS‐OH was also studied. The chain‐extended polyesters were characterized by IR spectra, ¹H‐NMR spectra, and differential scanning calorimetry (DSC). The chain extension proceeds through the elimination of caprolactam rings in the chain‐extenders, the adipoyl groups or the terephthaloyl groups couple the hydroxyl‐terminated polyesters together and make the molecular weight of PBA or PBS increased, whether the acid catalyst such as p‐toluenesulfonic acid was present or not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis,chemical, and thermoelectric properties of n‐type π‐conjugated polymer composed of 1,2,4‐triazole and pyridine rings and its metal complexes

A soluble n‐type π‐conjugated polymer ( polymer 1 ) composed of a 1,2,4‐triazole ring substituted by a 4‐n‐octylphenyl subunit at the 4‐position of the 1,2,4‐triazole ring and pyridine‐2,5‐diyl rings was synthesized by Ni(cod)₂ (cod = 1,5‐cyclooctadiene) promoted dehalogenation polycondensation of 3,5‐bis(2‐bromopyridyl)‐4‐n‐octylphenyl‐1,2,4‐triazole ( monomer 1 ). A polymer complex ( polymer‐BiCl₃ ) was synthesized by the reaction of polymer 1 with BiCl₃. The UV–vis spectrum of polymer 1 exhibited an absorption maximum (λ_max value) at a longer wavelength than that exhibited by monomer 1 revealing that its π‐conjugation system was expanded along the polymer chain. Polymer 1 was electrochemically active in film, and the electrochemical reaction was accompanied with electrochromism. Thermoelectoric properties of polymer 1 and polymer‐BiCl₃ were investigated. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39928.     

Synthesis of triazole ring‐containing pentol chain extender and its effect on the properties of hyperbranched polyurethane‐urea coatings

This article describes the synthesis and property evaluation of different hyperbranched polyurethane‐urea (HBPUU) coatings based on a newly synthesized triazole ring‐based pentol chain extender. For this initially, the chain extender was synthesized using acetylene azide click reaction and the structure of the intermediate compounds were confirmed by ¹H‐, ¹³C‐NMR, FTIR, and ESI‐mass spectrometry. In the further steps, the required HBPUU coatings were prepared by a systematic three‐step reaction process. In the first step, a isocyanate terminated prepolymer resin was synthesized at NCO/OH ratio of 1.2 : 1, while the second and third step involves the partially chain extension followed by moisture curing. The excess NCO content in the prepolymer was calculated by standard dibutylamine titration method and partially (10, 20, 30, 50, and 70% of the excess NCO content) chain extended with the pentol chain extender and remaining was moisture cured. The structure property relation of different HBPUU coating films were analyzed by FTIR peak deconvulation technique using Gaussian curve fitting procedure while, their viscoelastic and thermo‐mechanical properties were measured by dynamic mechanical thermal analysis, thermo gravimetric analysis, differential scanning calorimetric, and universal testing machine instruments. These results showed that thermal stability, glass transition temperature (T_g), elongation at break increases but the storage and tensile modulus decreases with increasing the percent loading of the triazole chain extender. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Production of polyols and waterborne polyurethane dispersions from biodiesel‐derived crude glycerol

This study investigated the preparation of polyols and waterborne polyurethane dispersions (CG‐WPUDs) from biodiesel‐derived crude glycerol. The polyols were produced from biodiesel‐derived crude glycerol via a thermochemical conversion process, which converted crude glycerol components such as glycerol, free fatty acids, and methyl esters of fatty acids (FAMEs) into polyols under optimized reaction conditions. CG‐WPUDs with different hard segments (41.0% to 63.2 wt %) were prepared from the crude glycerol‐based polyols produced. PU coating films cast from CG‐WPUDs showed increasing glass transition temperatures (T_g) from 63°C to 81°C when hard segment content increased from 41.0% to 63.2% and had good thermal stability up to 240°C. CG‐WPUD‐based coatings showed excellent adhesion to steel panel surfaces, pencil hardness as high as F, but relatively low flexibility. This study demonstrated the potential of biodiesel‐derived crude glycerol for the production of bio‐based polyols and WPUDs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41425.     

Sophorolipid‐induced dimpling and increased porosity in solvent‐cast short‐chain polyhydroxyalkanoate films: Impact on thermomechanical properties

Sophorolipids (SL; microbial glycolipids) were used as additives in solvent‐cast short‐chain polyhydroxyalkanoate (sc‐PHA) films to enhance surface roughness and porosity. Poly‐3‐hydroxybutyrate (PHB), poly‐(6%)‐3‐hydroxybutyrate‐co‐(94%)‐3‐hydroxyvalerate (PHB/V), and poly‐(90%)‐3‐hydroxybutyrate‐co‐(10%)‐3‐hydroxyhexanoate (PHB/HHx) films were evaluated with up to 43 wt % of SL. Sophorolipid addition caused surface dimples with maximum diameters of 131.8 µm (PHB), 25.2 µm (PHB/V), and 102.8 µm (PHB/HHx). A rise in the size and number of pores in the polymer matrix also occurred in PHB and PHB/V films. Surface roughness and film porosity were visualized by scanning electron microscopy and quantitated using confocal microscopy by correlating the surface area (A′) to the scanned area (A) of the films. The phenotypic alterations of the films caused a gradual decline in tensile strength and modulus and increased the elongation to break. Reductions in the enthalpies of fusion (ΔH_f) in both the PHB (41% reduction) and PHB/HHx (36% reduction) films implied diminished crystallinity as SL concentrations increased. Over the same SL concentrations the Tan δ maxima shifted from 4 to 30°C and from 2 to 20°C in these respective films. These results provide a novel means by which sc‐PHA properties can be controlled for new/improved applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40609.     

Synthesis and characterization of biodegradable lactic acid‐based polymers by chain extension

BACKGROUND: Poly(lactic acid) (PLA), coming from renewable resources, can be used to solve environmental problems. However, PLA has to have a relatively high molecular weight in order to have acceptable mechanical properties as required in many applications. Chain‐extension reaction is an effective method to raise the molecular weight of PLA. RESULTS: A high molecular weight biodegradable lactic acid polymer was successfully synthesized in two steps. First, the lactic acid monomer was oligomerized to low molecular weight hydroxyl‐terminated prepolymer; the molecular weight was then increased by chain extension using 1,6‐hexamethylene diisocyanate as the chain extender. The polymer was characterized using ¹H NMR analysis, gel permeation chromatography, differential scanning calorimetry and Fourier transform infrared spectroscopy. The results showed that the obtained polymer had a M_n of 27 500 g mol^?1 and a M_w of 116 900 g mol^?1 after 40 min of chain extension at 180 °C. The glass transition temperature (T_g) of the low molecular weight prepolymer was 47.8 °C. After chain extension, T_g increased to 53.2 °C. The mechanical and rheological properties of the obtained polymer were also investigated. CONCLUSION: The results suggest that high molecular weight PLA can be achieved by chain extension to meet conventional uses. Copyright © 2008 Society of Chemical Industry     

Thermal,mechanical, and shape‐memory properties of nanorubber‐toughened,epoxy‐based shape‐memory nanocomposites

Epoxy‐based shape‐memory polymers (ESMPs) are a type of the most promising engineering smart polymers. However, their inherent brittleness limits their applications. Existing modification approaches are either based on complicated chemical reactions or done at the cost of the thermal properties of the ESMPs. In this study, a simple approach was used to fabricate ESMPs with the aim of improving their overall properties by introducing crosslinked carboxylic nitrile–butadiene nanorubber (CNBNR) into the ESMP network. The results show that the toughness of the CNBNR–ESMP nanocomposites greatly improved at both room temperature and the glass‐transition temperature (T_g) over that of the pure ESMP. Meanwhile, the increase in the toughness did not negatively affect other macroscopic properties. The CNBNR–ESMP nanocomposites presented improved thermal properties with a T_g in a stable range around 100 °C, enhanced thermal stabilities, and superior shape‐memory performance in terms of the shape‐fixing ratio, shape‐recovery ratio, shape‐recovery time, and repeatability of shape‐memory cycles. The combined property improvements and the simplicity of the manufacturing process demonstrated that the CNBNR–ESMP nanocomposites are desirable candidates for large‐scale applications in the engineering field as smart structural materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45780.     

Catalyzed chain extension of poly(butylene adipate) and poly(butylene succinate) with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline)

Low‐molecular‐weight HOOC‐terminated poly(butylene adipate) prepolymer (PrePBA) and poly(butylene succinate) prepolymer (PrePBS) were synthesized through melt‐condensation polymerization from adipic acid or succinic acid with butanediol. The catalyzed chain extension of these prepolymers was carried out at 180–220°C with 2,2′‐(1,4‐phenylene)‐bis(2‐oxazoline) as a chain extender and p‐toluenesulfonic acid (p‐TSA) as a catalyst. Higher molecular weight polyesters were obtained from the catalyzed chain extension than from the noncatalyzed one. However, an improperly high amount of p‐TSA and a high temperature caused branching or a crosslinking reaction. Under optimal conditions, chain‐extended poly(butylene adipate) (PBA) with a number‐average molecular weight up to 29,600 and poly(butylene succinate) (PBS) with an intrinsic viscosity of 0.82 dL/g were synthesized. The chain‐extended polyesters were characterized by IR spectroscopy, ¹H‐NMR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis, wide‐angle X‐ray scattering, and tensile testing. DSC, wide‐angle X‐ray scattering, and thermogravimetric analysis characterization showed that the chain‐extended PBA and PBS had lower melting temperatures and crystallinities and slower crystallization rates and were less thermally stable than PrePBA and PrePBS. This deterioration of their properties was not harmful enough to impair their thermal processing properties and should not prevent them from being used as biodegradable thermoplastics. The tensile strength of the chain‐extended PBS was about 31.05 MPa. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and chain extension of poly(L‐lactic acid‐co‐succinic acid‐co‐1,4‐butene diol)

L ‐Lactic acid (LA) was copolymerized with succinic acid (SA) and 1,4‐butenediol (1,4‐BED) in bulk state with titanium(IV) butoxide as a catalyst to produce poly(LA‐co‐SA‐co‐1,4‐BED) (PLASBED). Poly(L ‐lactic acid) (PLLA) homopolymer obtained from a direct condensation polymerization of LA had weight average molecular weight (M_w) less than 4.1 × 10⁴ and was too brittle to prepare specimens for the tensile test. Addition of SA and 1,4‐BED to LA produced PLASB with M_w as high as 1.4 × 10⁵ and exhibited tensile properties comparable to a commercially available high‐molecular‐weight PLLA. Chain extension by intermolecular linking reaction through the unsaturated 1,4‐BED units in PLASBED with benzoyl peroxide further increased the molecular weight and made PLASBED more ductile and flexible to show elongation at break as high as 450%. Biodegradability of PLASBED measured by the modified Sturm test was nearly independent of the 1,4‐BED content. Gel formation during the chain extension did not exert any significant influence on the biodegradability either. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1116–1121, 2005     

Bio‐oil from whole‐tree feedstock in resol‐type phenolic resins

Renewable chemicals are of growing importance in terms of opportunities for environmental concerns over fossil‐based chemicals. Lignocellulosic biomass can be converted into energy and chemicals via thermal and biological processes. Among all the transformation processes available, fast pyrolysis is the only one to produce a high yield of a liquid‐phase product called bio‐oil or pyrolysis oil. Bio‐oil is considered to be a promising substitute for phenol in phenol formaldehyde (PF) resin synthesis. In this work, bio‐based phenolic resins have been formulated, partially substituting phenol by bio‐oils from two Canadian whole‐tree species. The new resins are produced by replacing 25, 50, and 75% of phenol with bio‐oil for each species (three bioresins per species). The aim of this study is to synthesize renewable resins with competitive price and satisfactory quality. The results obtained have shown that substitution degree up to 50% provided reactivity and performance equal or superior to the pure PF resin. They also present a good storage stability, improved shear strength, and thermal stability comparable to the pure PF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40014.     

Design of highly tough poly(l‐lactide)‐based ternary blends for automotive applications

Technical renewable poly(l ‐lactide) (PLA)‐based blends represent an elegant way to achieve attractive properties for engineering applications. Recently, the miscibility between PLA and poly(methyl methacrylate) (PMMA) gave rise to new formulations with enhanced thermo‐mechanical properties but their high brittleness still remains a challenge to be overcome. This work here focuses on rubber‐toughened PLA/PMMA formulations for injection‐molding processes upon the addition of a commercially available ethylene‐acrylate impact modifier (BS). The miscibility between PLA and PMMA is not altered by the presence of BS but the incorporation of BS (17% by weight) into a PLA/PMMA matrix could enhance both ductility and toughness of PLA/PMMA blends for PMMA content up to 50 wt %. An optimum range of particle sizes (d_n ～0.5 µm) of the dispersed domains for high impact toughness is identified. These bio‐based ternary blends appear as promising alternatives to petro‐sourced blends such as ABS‐based blends in engineering injection‐molding parts. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43402.     

Poly‐3‐hydroxyalkanoates‐co‐polyethylene glycol methacrylate copolymers for pH responsive and shape memory hydrogel

Multifunctional hydrogels combining the capabilities of cellular pH responsiveness and shape memory, are highly promising for the realization of smart membrane filters, controlled drug released devices, and functional tissue‐engineering scaffolds. In this study, lipase was used to catalyze the synthesis of medium‐chain‐length poly‐3‐hydroxyalkanoates‐co‐polyethylene glycol methacrylate (PHA‐PEGMA) macromer, which was used to prepare pH‐responsive and shape memory hydrogel via free radical polymerization. Increasing the PEGMA fraction from 10 to 50% (mass) resulted in increased thermal degradation temperature (T_d) from 430 to 470°C. Highest lower critical solution temperature of 37°C was obtained in hydrogel with 50% PEGMA fraction. The change in PEGMA fraction was also found to highly influence the hydrogel's hydration rate (r) from 2.8 × 10^?5 to 7.6 × 10^?5 mL·s^?1. The hydrogel's equilibrium weight swelling ratio (q_e), protein release and its diffusion coefficient (D_m) were all found to be pH dependent. Increasing the phosphate buffer pH from 2.4 to 13 resulted in increased q_e from 2 to 16 corresponding to the enlarging of network pore size (ξ) from 150 to 586 nm. Different types of crosslinker for the hydrogel influenced its flexibility and ductility. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41149.