Controlled release of chlorpheniramine maleate through IPN beads of sodium alginate‐g‐methylmethacrylate

Controlled release of chlorpheniramine maleate drug, through sodium alginate‐g‐methylmethacrylate (NaAlg‐g‐MMA) interpenetrating polymeric network beads, has been investigated. Beads were prepared by precipitating the viscous solution of NaAlg‐g‐MMA in acetone followed by cross‐linking with glutaraldehyde. The beads were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Different formulations of beads were developed by varying amounts of MMA, cross‐linking agent, and drug concentration. DSC thermograms of chlorpheniramine maleate drug‐loaded NaAlg‐g‐MMA beads confirmed the molecular level distribution of drug in the polymer matrix. FTIR of beads confirm the grafting and cross‐linking, SEM of the beads suggested the formation of spherical particles. Swelling experiments on the beads provided an important information on drug diffusion properties. Release data have been analyzed using an empirical equation to understand the nature of transport of drug containing solution through the polymeric matrices. The controlled release characteristics of the matrices for chlorpheniramine maleate was investigated in pH 7.4 media. Drug was released in a controlled manner upto 12 h. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

In vitro release study of diltiazem hydrochloride from poly(vinyl pyrrolidone)/sodium alginate blend microspheres

Polymeric blend microspheres of poly(vinyl pyrrolidone) (PVP) with sodium alginate (NaAlg) were prepared by cross‐linking with calcium ions and used to deliver a calcium channel blocker drug, diltiazem hydrochloride (DT). The prepared microspheres were characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Scanning electron microscopy confirmed the spherical nature of the particles. Preparation conditions for the microspheres were optimized by considering the percentage entrapment efficiency, particle size, and swelling capacity. Effects of variables such as PVP/NaAlg ratio, molecular weight of PVP, cross‐linker concentration, and drug/polymer ratio on the release of DT were discussed at two different pH values (1.2, 6.8) at 37°C. It was observed that DT release from the microspheres decreased with increasing molecular weight of PVP and extent of cross‐linking. However, DT release increased with increasing PVP content and drug/polymer ratio (d/p) of the blend microspheres. The highest DT release percentage was obtained as 99% for PVP/NaAlg ratio of 1/2 with d/p ratio of 1/2 at the end of 4 h. It was also observed from release results that DT delivery from the microspheres through the external medium are much higher at low pH (1.2) value than that of high pH (6.8) value. The drug release from the microspheres mostly followed Fickian transport. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cibacron Blue F3GA‐attached magnetic poly(2‐hydroxyethyl methacrylate) beads for human serum albumin adsorption

An affinity dye ligand, Cibacron Blue F3GA, was covalently attached onto magnetic poly(2‐hydroxyethyl methacrylate) (mPHEMA) beads for human serum albumin (HSA) adsorption from both aqueous solutions and human plasma. The mPHEMA beads, in the size range of 80 to 120 µm, were prepared by a modified suspension technique. Cibacron Blue F3GA molecules were incorporated on to the mPHEMA beads. The maximum amount of Cibacron Blue F3GA attachment was obtained as 68.3 µmol g^?1. HSA adsorption onto unmodified and Cibacron Blue F3GA‐attached mPHEMA beads was investigated batchwise. The non‐specific adsorption of HSA was very low (1.8 mg g^?1). Cibacron Blue F3GA attachment onto the beads significantly increased the HSA adsorption (94.5 mg g^?1). The maximum HSA adsorption was observed at pH 5.0. Higher HSA adsorption was observed from human plasma (138.3 mg HSA g^?1). Desorption of HSA from Cibacron Blue F3GA‐attached mPHEMA beads was obtained by using 0.1 M Tris/HCl buffer containing 0.5 M NaSCN. High desorption ratios (up to 98% of the adsorbed HSA) were observed. It was possible to re‐use Cibacron Blue F3GA‐attached mPHEMA beads without any significant decreases in their adsorption capacities. Copyright © 2004 Society of Chemical Industry     

Controlled release formulations of carbaryl based on copper alginate,barium alginate,and alginic acid beads

A controlled release system for reducing environmental impact was produced by encapsulating the pesticide carbaryl (Carb) in the alginate beads. The various bead formulations were prepared by using sodium alginate (NaAlg) as a polymer, CuCl₂, BaCl₂ as a crosslinking agent, and HCl as a linking agent. The surface morphology of prepared beads was characterized with scanning electron microscopy (SEM). SEM confirmed the spherical nature and surface morphology of the particles. Bead characteristics, such as Carb entrapment efficiency, particle size, swelling degree, and Carb release kinetics, were determined. The effects of crosslinker or linker concentration, type, and carbaryl/sodium alginate (Carb/NaAlg) ratio on Carb release from the beads were investigated for 20 days at 25°C. It was observed that Carb release from the beads increased with the increase of Carb/NaAlg ratio whereas decreased with the increase of crosslinker concentration. At the end of 20 days, the Carb release from alginic acid beads was found to be higher than that of copper alginate (Cu‐Alg) and barium alginate (Ba‐Alg) beads. The swelling measurements of the beads supported the release results. Release kinetics were described by Fickian and non‐Fickian approaches. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4245–4253, 2006     

Release behavior of freeze‐dried alginate beads containing poly(N‐isopropylacrylamide) copolymers

Beads composed of alginate, poly(N‐isopropylacrylamide) (PNIPAM), the copolymers of N‐isopropylacrylamide and methacrylic acid (P(NIPAM‐co‐MAA)), and the copolymers of N‐isopropylacrylamide, methacrylic acid, and octadecyl acrylate (P(NIPAM‐co‐MAA‐co‐ODA)), were prepared by dropping the polymer solutions into CaCl₂ solution. The beads were freeze‐dried and the release of blue dextran entrapped in the beads was observed in distilled water with time and pH. The degree of release was in the order of alginate bead < alginate/PNIPAM bead ≈ alginate/P(NIPAM‐co‐MAA) bead < alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead. On the other hand, swelling ratios reached steady state within 20 min, and the values were 200–800 depending on the bead composition. The degree of swelling showed the same order as that of release. Among the beads, only alginate/P(NIPAM‐co‐MAA‐co‐ODA) bead exhibited pH‐dependent release. At acidic condition, inter‐ and intraelectrostatic repulsion is weak and P(NIPAM‐co‐MAA‐co‐ODA) could readily be assembled into an aggregate due to the prevailing hydrophobic interaction of ODA. Thus, it could block the pore of bead matrix, leading to a suppressed release. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Phase behavior of temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) in dilute aqueous solution

Several different composition temperature‐ and pH‐sensitive poly(acrylic acid‐g‐N‐isopropylacrylamide) (P(AA‐g‐NIPAM)) graft copolymers were synthesized by free‐radical copolymerization utilizing macromonomer technique. The phase behavior and conformation change of P(AA‐g‐NIPAM) in aqueous solutions were investigated by UV–vis transmittance measurements, fluorescence probe, and fluorescence quenching techniques. The results demonstrate that the P(AA‐g‐NIPAM) copolymers have temperature‐ and pH‐sensitivities, and these different composition graft copolymers have different lower critical solution temperature (LCST) and critical phase transition pH values. The LCST of graft copolymer decreases with increasing PNIPAM content, and the critical phase transition pH value increases with increasing Poly(N‐isopropylacrylamide) (PNIPAM) content. At room temperature (20°C), different composition of P(AA‐g‐NIPAM) graft copolymers in dilute aqueous solutions (0.001 wt %) have a loose conformation, and there is no hydrophobic microdomain formation within researching pH range (pH 3 ～ 10). In addition, for the P(AA‐g‐NIPAM) aqueous solutions, transition from coil to globular is an incomplete reversible process in heating and cooling cycles. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication and drug release properties of poly(5‐benzyloxy‐trimethylene‐co‐glycolide) microspheres

Poly(5‐benzyloxy‐trimethylene carbonate‐co‐glycolide) random copolymers were synthesized through the ring‐opening polymerization of 5‐benzyloxy‐trimethylene carbonate and glycolide (GA). The copolymers with different compositions, PBG‐1 with 17% GA units and PBG‐2 with 45% GA units, were obtained. Using these copolymers, microsphere drug delivery systems with submicron sizes were fabricated using an “ultrasonic assisted precipitation method.” The in‐vitro drug release from these microspheres was investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thiol–ene addition enables tailored synthesis of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) copolymers for binder jetting 3D printing

The continued interest in graft copolymer architectures arises from their unique solution properties and potential for a myriad of applications ranging from drug delivery to adhesives. Poly(vinyl pyrrolidone) (PVP) represents a popular amorphous, water‐soluble polymer used as a polymeric binder in binder jetting additive manufacturing, as fillers in cosmetic products, and for subcutaneous drug delivery systems. This report describes the synthesis of poly(2‐oxazoline) and PVP graft copolymers using a ‘grafting to’ methodology with an efficient thiol–ene ‘click’ reaction. Copolymerization of 2‐methyl‐2‐oxazoline and 2‐(3‐butenyl)‐2‐oxazoline introduced pendent vinyl grafting sites with a predictable absolute number‐average molecular weight. In parallel, reversible addition‐fragmentation chain‐transfer polymerization and subsequent aminolysis yielded well‐defined, oligomeric, thiol‐terminated PVP. Thiol–ene click chemistry enabled the formation of poly(2‐oxazoline)‐graft‐poly(vinyl pyrrolidone) (PMeOx‐g‐PVP) copolymers with varying mole percent grafting sites and PVP graft length. ¹H NMR spectroscopy, aqueous SEC with multiangle light scattering (SEC‐MALS), and bromine titrations confirmed chemical structure, and DSC with TGA elucidated thermal transitions. Aqueous SEC‐MALS and ¹H NMR spectroscopy also determined absolute number‐ and weight‐average molecular weights and average grafting levels, which revealed optimal reaction conditions. Zero‐shear viscosities of 5 and 10 wt% solutions in deionized water for each graft copolymer compared to their linear analogs demonstrated a significant (ca 31%) decrease in viscosity at the same number‐average molecular weight. This decrease in solution viscosity suggested PMeOx‐g‐PVP copolymers as exceptional alternatives to linear analogs for aqueous‐based, binder jetting additive manufacturing.     

Controlled degradation of polylactic acid grafting N‐vinyl pyrrolidone induced by gamma ray radiation

Polylactic acid (PLA) films were surface modified by gamma ray irradiation‐induced grafting of N‐vinyl pyrrolidone (NVP). The in vitro degradation behavior of polylactic acid grafting N‐vinyl pyrrolidone (PLA‐g‐PVP) copolymer was analyzed in terms of weight loss, molecular weight, and thermal properties. Grafting NVP significantly accelerated the degradation of PLA. The mass losses of the copolymers, which were less than that of pure PLA at the beginning of the degradation period, sharply accelerated with increasing degradation time. Moreover, the crystallization temperature decreased with increasing degradation time in the same graft ratio, and the degree of crystallinity increased. Cytotoxicity experiments and animal experiments in vivo were carried out to evaluate the biocompatibility of PLA‐g‐PVP copolymer. Varying graft ratios of PVP could control the degradation rate of copolymers, and thus broadening the applications of this material, such as in tissue engineering scaffolds, drug delivery, and prevention of postsurgical adhesion. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Temperature sensitive semi‐IPN microspheres from sodium alginate and N‐isopropylacrylamide for controlled release of 5‐fluorouracil

Semi‐interpenetrating network (IPN) of sodium alginate (NaAlg) and N‐isopropylacrylamide (NIPAAm) microspheres were prepared by water‐in‐oil (w/o) emulsification method. The microspheres were encapsulated with 5‐fluorouracil (5‐FU) and release patterns carried in 7.4 pH at temperatures of 25 and 37°C. The semi‐IPN microspheres were characterized by Fourier transform infrared spectroscopy (FTIR). Differential scanning calorimetry (DSC) and scanning electron microscopic studies were done on the drug‐loaded microspheres to confirm the polymorphism of 5‐FU and surface morphology of microspheres. These results indicated the molecular level dispersion of 5‐FU in the semi‐IPN microspheres. Particle size and size distribution were studied by laser light diffraction technique. Microspheres exhibited release of 5‐FU up to 12 h. The swelling studies were carried in 1.2 and 7.4 pH buffer media at 25 and 37°C. Drug release from NaAlg‐NIPAAm semi‐IPN microspheres at 25 and 37°C confirmed the thermosensitive nature by in vitro dissolution. The micro domains have released in a controlled manner due the presence of NIPAAm in the matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of poly(L‐lactide) membranes prepared by γ‐radiation‐induced grafting of N‐vinyl pyrrolidone

A copolymer, poly(L ‐lactide)‐g‐poly(N‐vinyl pyrrolidone) (PLLA‐g‐PVP) was prepared with poly(L ‐lactide) (PLLA) and N‐vinyl pyrrolidone in the presence of methanol as a solvent by γ‐ray irradiation. The structure of PLLA‐g‐PVP was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. The PLLA‐g‐PVP graft ratio calculated by the percentage increase in weight increased with the increase of absorbed dose, and the percentage crystallinity of PLLA‐g‐PVP decreased with increasing graft ratio. The introduction of the poly(N‐vinyl pyrrolidone) chain into PLLA resulted in a decrease in the contact angle of PLLA‐g‐PVP with increasing graft ratio. In vitro degradation testing showed that PLLA‐g‐PVP had a higher degradation rate both in the weight‐loss test and molecular weight measurement because of a lower crystalline percentage and higher hydrophilicity compared to PLLA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Controlled release study of carbaryl insecticide from calcium alginate and nickel alginate hydrogel beads

In this study, controlled release formulations for reducing environmental impact of pesticides have been produced by encapsulating as a model pesticide carbaryl (Carb) in the alginate beads. The various hydrogel bead formulations were prepared by the ionotropic crosslinking of sodium alginate (NaAlg) with calcium and nickel ions. The surface morphology of prepared beads was characterized with scanning electron microscopy (SEM). SEM confirmed the spherical nature and surface morphology of the particles. Bead characteristics, such as carbaryl entrapment efficiency, particle size, equilibrium swelling degree, and carbaryl release kinetics, were determined. The effects of the bead preparation conditions such as crosslinker concentration and type, carbaryl/sodium alginate (Carb/NaAlg) ratio and percentage of NaAlg on the carbaryl release from the calcium alginate (Ca‐Alg) and nickel alginate (Ni‐Alg) beads were investigated in distilled water at 25°C. It was observed that carbaryl release from the Ca‐Alg beads was slower than that of Ni‐Alg beads. The release results indicated that carbaryl release from both of the Ca‐Alg and Ni‐Alg beads decreases with the increasing crosslinker concentration, Carb/NaAlg ratio and percentage of NaAlg. The highest carbaryl release was found to be 100% for the Ni‐Alg beads at 3 days whereas the lowest carbaryl release was found to be 67% for the Ca‐Alg beads at 21 days. The swelling measurements of the beads were also in consistent with the carbaryl release results. The carbaryl release from most of the bead formulations followed Case II transport. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of attapulgite contents on release behaviors of a pH sensitive carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate composite hydrogel bead containing diclofenac

A series of pH‐sensitive composite hydrogel beads, carboxymethyl cellulose‐g‐poly(acrylic acid)/attapulgite/sodium alginate (CMC‐g‐PAA/APT/SA), were prepared by combining CMC‐g‐PAA/APT composite and SA, using Ca²⁺ as the ionic crosslinking agent and diclofenac sodium (DS) as the model drug. The effects of APT content and external pH on the swelling properties and release behaviors of DS from the composite hydrogel beads were investigated. The results showed that the composite hydrogel beads exhibited good pH‐sensitivity. Introducing 20% APT into CMC‐g‐PAA hydrogel could change the surface structure of the composite hydrogel beads, decrease the swelling ability, and relieve the burst release effect of DS. The drug cumulative release ratio of DS from the hydrogel beads in simulated gastric fluid was only 3.71% within 3 hour, but in simulated intestinal fluid about 50% for 3 hour, 85% for 12 hour, up to 90% after 24 hour. The obtained results indicated that the CMC‐g‐PAA/APT/SA hydrogel beads could be applied to the drug delivery system as drug carriers in the intestinal tract. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis of poly(epichlorohydrin‐g‐methyl methacrylate) and poly(epichlorohydrin‐g‐styrene) graft copolymers by a combination of cationic and photopolymerization methods

Poly(epichlorohydrin‐g‐styrene) and poly (epichlorohydrin‐g‐methyl methacrylate) graft copolymers were synthesized by a combination of cationic and photoinitiated free‐radical polymerization. For this purpose, first, epichlorohydrin was polymerized with tetrafluoroboric acid (HBF₄) via a cationic ring‐opening mechanism, and, then, polyepichlorohydrin (PECH) was reacted ethyl‐hydroxymethyl dithio sodium carbamate to obtain a macrophotoinitiator. PECH, possessing photolabile thiuram disulfide groups, was used in the photoinduced polymerization of styrene or methyl methacrylate to yield the graft copolymers. The graft copolymers were characterized by ¹H‐NMR spectroscopy, differential scanning calorimetry, and gel permeation chromatography. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reactive mixing of PET and PET/PP blends with glycidyl methacrylate–modified styrene‐b‐(ethylene‐co‐olefin) block copolymers

Styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene (SEBS) and styrene‐b‐(ethylene‐co‐propylene) (SEP, SEPSEP) block copolymers with different styrene contents and different numbers of blocks in the copolymer chain were functionalized by melt radical grafting with glycidyl methacrylate (GMA) and employed as compatibilizers for PET‐based blends. Binary blends of PET with both functionalized (SEBS‐g‐GMA, SEP‐g‐GMA, SEPSEP‐g‐GMA) and neat (SEBS, SEP, SEPSEP) copolymers (75 : 25 w/w) and ternary blends of PET and PP (75 : 25 w/w) with various amounts (2.5–10 phr) of both modified and unmodified copolymers were prepared in an internal mixer, and their properties were evaluated by SEM, DSC, melt viscosimetry, and tensile and impact tests. The roles of the chemical structure, grafting degree, and concentration of the various copolymers on blend compatibilization was investigated. The blends with the grafted copolymers showed a neat improvement of phase dispersion and interfacial adhesion compared to the blends with nonfunctionalized copolymers. The addition of grafted copolymers resulted in a marked increase in melt viscosity, which was accounted for by the occurrence of chemical reactions between the epoxide groups of GMA and the carboxyl/hydroxyl end groups of PET during melt mixing. Blends with SEPSEP‐g‐GMA and SEBS‐g‐GMA, at concentrations of 5–10 phr, showed a higher compatibilizing effect with enhanced elongation at break and impact resistance. The effectiveness of GMA‐functionalized SEBS was then compared to that of maleic anhydride–grafted SEBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2201–2211, 2005     

Novel bioresorbable hydrogels prepared from chitosan‐graft‐polylactide copolymers

A series of biodegradable chitosan‐graft‐polylactide (CS‐g‐PLA) copolymers were prepared by grafting of poly(L ‐lactide) (PLLA) or poly(D ‐lactide) (PDLA) precursor to the backbone of chitosan using N,N′‐carbonyldiimidazole as coupling agent. The composition of the copolymers was varied by adjusting the chain length of PLA as well as the ratio of chitosan to PLA. The copolymers synthesized via this ‘graft‐onto’ method present interesting properties as shown by NMR and infrared spectroscopy, gel permeation chromatography and solubility tests. Hydrogels were prepared by mixing water‐soluble CS‐g‐PLLA and CS‐g‐PDLA solutions. Gelation was assigned to stereocomplexation between PLLA and PDLA blocks as evidenced by differential scanning calorimetry and wide‐angle X‐ray diffraction measurements. Thymopentin (TP5) was taken as a model drug to evaluate the potential of these CS‐g‐PLA hydrogels as drug carriers. An initial burst and a final release up to 82% of TP5 were observed from high‐performance liquid chromatography analysis. Copyright © 2011 Society of Chemical Industry     

Novel poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers through atom transfer radical polymerization

Poly(methyl methacrylate)‐block‐polyurethane‐block‐poly(methyl methacrylate) tri‐block copolymers have been synthesized successfully through atom transfer radical polymerization of methyl methacrylate using telechelic bromo‐terminated polyurethane/CuBr/N,N,N,N″,N″‐pentamethyldiethylenetriamine initiating system. As the time increases, the number‐average molecular weight increases linearly from 6400 to 37,000. This shows that the poly methyl methacrylate blocks were attached to polyurethane block. As the polymerization time increases, both conversion and molecular weight increased and the molecular weight increases linearly with increasing conversion. These results indicate that the formation of the tri‐block copolymers was through atom transfer radical polymerization mechanism. Proton nuclear magnetic resonance spectral results of the triblock copolymers show that the molar ratio between polyurethane and poly (methyl methacrylate) blocks is in the range of 1 : 16.3 to 1 : 449.4. Differential scanning calorimetry results show T_g of the soft segment at ?35°C and T_g of the hard segment at 75°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Toughening of polyamide 6 with a maleic anhydride functionalized acrylonitrile–butadiene–styrene copolymer

Maleic anhydride functionalized acrylonitrile–butadiene–styrene (ABS‐g‐MA) copolymers were prepared via an emulsion polymerization process. The ABS‐g‐MA copolymers were used to toughen polyamide 6 (PA‐6). Fourier transform infrared results show that the maleic anhydride (MA) grafted onto the polybutadiene phase of acrylonitrile–butadiene–styrene (ABS). Rheological testing identified chemical reactions between PA‐6 and ABS‐g‐MA. Transmission electron microscopy and scanning electron microscopy displayed the compatibilization reactions between MA of ABS‐g‐MA and the amine and/or amide groups of PA‐6 chain ends, which improved the disperse morphology of the ABS‐g‐MA copolymers in the PA‐6 matrix. The blends compatibilized with ABS‐g‐MA exhibited notched impact strengths of more than 900 J/m. A 1 wt % concentration of MA in ABS‐g‐MA appeared sufficient to improve the impact properties and decreased the brittle–ductile transition temperature from 50 to 10°C. Scanning electron microscopy results show that the shear yielding of the PA‐6 matrix was the major toughening mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Shape‐memory behaviors of biodegradable poly(L‐lactide‐co‐ϵ‐caprolactone) copolymers

A series of biodegradable poly(L ‐lactide‐co‐?‐caprolactone) (PCLA) copolymers with different chemical compositions are synthesized and characterized. The mechanical properties and shape‐memory behaviors of PCLA copolymers are studied. The mechanical properties are significantly affected by the copolymer compositions. With the ?‐caprolactone (?‐CL) content increasing, the tensile strength of copolymers decreases linearly and the elongation at break increases gradually. By means of adjusting the compositions, the copolymers exhibit excellent shape‐memory effects with shape‐recovery and shape‐retention rate exceeding 95%. The effects of composition, deformation strain, and the stretching conditions on the recovery stress are also investigated systematically. A maximum recovery stress around 6.2 MPa can be obtained at stretching at T_g ? 15°C to 200% deformation strain for the PCLA70 copolymer. The degradation results show that the copolymers with higher ?‐CL content have faster degradation rates and shape‐recovery rates, meanwhile, the recovery stress can maintain a relative high value after 30 days in vitro degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

The synthesis of PHA‐g‐(PTHF‐b‐PMMA) multiblock/graft copolymers by combination of cationic and radical polymerization

A new and promising method for the diversification of microbial polyesters based on chemical modifications is introduced. Poly(3‐hydroxy alkanoate)‐g‐(poly(tetrahydrofuran)‐b‐poly(methyl methacrylate)) (PHA‐g‐(PTHF‐b‐PMMA)) multigraft copolymers were synthesized by the combination of cationic and free radical polymerization. PHA‐g‐PTHF graft copolymer was obtained by the cationic polymerization of THF initiated by the carbonium cations generated from the chlorinated PHAs, poly(3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) (PHBV), and poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHBHx) in the presence of AgSbF₆. Therefore, PHA‐g‐PTHF graft copolymers with hydroxyl ends were produced. In the presence of Ce⁺⁴ salt, these hydroxyl ends of the graft copolymer can initiate the redox polymerization of MMA to obtain PHA‐g‐(PTHF‐b‐PMMA) multigraft copolymer. Polymers obtained were purified by fractional precipitation. In this manner, their γ‐values (volume ratio of nonsolvent to the solvent) were also determined. Their molecular weights were determined by GPC technique. The structures were elucidated using ¹H‐NMR and FTIR spectroscopy. Thermal analyses of the products were carried out using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009