ABCBA Pentablock Copolymers Consisting of Poly(l‐lactide) (PLLA: A), Poly(d‐lactide) (PDLA: B), and Poly(butylene succinate) (PBS: C): Effects of Semicrystalline PBS Segments on the Stereo‐Crystallinity and Properties

A new stereo pentablock copolymer consisting of poly(l ‐lactide) (PLLA: A), poly‐d ‐lactide (PDLA: B), and poly(butylene succinate) (PBS: C) is synthesized by two‐step ring‐opening polymerization of d ‐ and l ‐lactides in the presence of bis‐hydroxyl‐terminated PBS prepolymer that has been prepared by the ordinary polycondensation. The pentablock copolymers (PLLA‐PDLA‐PBS‐PDLA‐PLLA) as well as the triblock copolymers (PLLA‐PBS‐PLLA) obtained as the intermediates show different properties depending on the polymer compositions. In the pentablock copolymers, the direct connection of the PLLA and PDLA blocks allows easy formation of the stereocomplex crystals, while the introduction of the semicrystalline PBS block is effective not only for changing the crystallization kinetics but also for imparting an elastomeric property.

     

Morphology and Properties of Poly(L‐Lactide) (PLLA) Filled with Hollow Glass Beads

The morphology, crystalline behavior, and mechanical and thermal properties of poly(L ‐lactide)/hollow glass beads (PLLA/HGBs) composites were investigated. The incorporation of HGBs enhanced the crystallization rate and crystallinity of PLLA, but slightly decreased its elongation at break. In addition, HGBs acted as stress concentration points inducing the plastic deformation of PLLA, leading to increased Izod impact strength. Differential scanning calorimetry results show that annealed PLLA eliminated cold crystallization phenomenon in the region of 100–140 °C and presented a double melting peak around 150 °C. Moreover, annealing was demonstrated to be effective for the improvement of tensile modulus, strength, Izod impact strength and heat distortion temperature of the composites due to the increased crystallinity and more perfect crystals. Silane coupling agents can enhance the interfacial adhesion of the composites, and lead to better mechanical properties. Compared to neat PLLA, the HGBs filled PLLA composites did not exhibit an obvious increase of the density.

     

Synthesis and characterization of hyperbranched poly(silyl ester)s

Hyperbranched poly(silyl ester)s were synthesized via the A₂ + B₄ route by the polycondensation reaction. The solid poly(silyl ester) was obtained by the reaction of di‐tert‐butyl adipate and 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The oligomers with tert‐butyl terminal groups were obtained via the A₂ + B₂ route by the reaction of 1,5‐dichloro‐1,1,5,5‐tetramethyl‐3,3‐diphenyl‐trisi1oxane with excess amount of di‐tert‐butyl adipate. The viscous fluid and soft solid poly(silyl ester)s were obtained by the reaction of the oligomers as big monomers with 1,3‐tetramethyl‐1,3‐bis‐β(methyl‐dicholorosilyl)ethyl disiloxane. The polymers were characterized by ¹H NMR, IR, and UV spectroscopies, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The ¹H NMR and IR analysis proved the existence of the branched structures in the polymers. The glass transition temperatures (T_g's) of the viscous fluid and soft solid polymers were below room temperature. The T_g of the solid poly(silyl ester) was not found below room temperature but a temperature for the transition in the liquid crystalline phase was found at 42°C. Thermal decomposition of the soft solid and solid poly(silyl ester)s started at about 130°C and for the others it started at about 200°C. The obtained hyperbranched polymers did not decompose completely at 700°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3430–3436, 2006     

Zur Synthese und Funktionalisierung neuer Poly[(silylen)‐2,5‐thiophene]

Treatment of 2,5‐dilithiothiophene with (dimethylamino) methylsilylbis(triflates) gave poly[(dimethylamino‐silylene)‐2,5‐thiophene] 4 in high yield. The amino–silyl bond was cleaved selectively by triflic acid leading to triflate substituted poly[(silylene)‐2,5‐thiophene] 5 . Conversions of this polymers with nucleophiles gave other functionalized derivatives 6 – 9 . Hydrosilylation reaction between silicon–vinyl and silicon–hydrogen derivatives results in polymer networks which may serve as interesting preceramic materials. The structures of the polymers were proven by NMR spectroscopy (²⁹Si, ¹³C, ¹H).     

Synthesis and Characterization of Some Novel Poly(nitroarylates)

Various types of poly(nitroarylates) ( 8 – 17 ) were prepared using interfacial polycondensation (IPC) and solution polycondensation (SPC) of 5-nitroiso-phthaloyl chloride ( la ) and 2-nitroterephthaloyl chloride ( 2a ) with different bisphenols: hydroquinone ( 3 ), resorcinol ( 4 ), 4.4′-dihydroxydiphenyl ( 5 ), 2,2-bis(4-hydroxyphenyl) propane ( 6 ) and bis(4-hydroxyphenyl) sulfone ( 7 ). A nitro group was introduced in the polymeric chain in order to improve the properties, solubility and thermal stability of these polymers. Some of the factors affecting the IPC were studied, such as the effect of concentration of the initial components and the role of the solvent. The structures of the poly(nitroarylates) ( 8 – 17 ) were confirmed by elemental analysis, infrared and proton magnetic resonance spectrometry. Thermomechanical analysis (TMA) and thermogravimetric analysis (TGA) of the synthesized polymers were also studied.     

Highly enhanced accelerating effect of melt‐recrystallized stereocomplex crystallites on poly(L‐lactic acid) crystallization: effects of molecular weight of poly(D‐lactic acid)

The effects of the molecular weight of poly(D ‐lactic acid) (PDLA), which forms stereocomplex (SC) crystallites with poly(L ‐lactic acid) (PLLA), and those of processing temperature T_p on the acceleration (or nucleation) of PLLA homocrystallization were investigated using PLLA films containing 10 wt% PDLA with number‐average molecular weight (M_n) values of 5.47 × 10⁵, 9.67 × 10⁴ and 3.67 × 10⁴ g mol^–1 (PDLA‐H, PDLA‐M and PDLA‐L, respectively). For the PLLA/PDLA‐H and PLLA/PDLA‐M films, the SC crystallites that were ‘non’‐melted and those that were ‘completely’ melted at T_p values just above their endset melting temperature and recrystallized during cooling were found to act as effective accelerating (or nucleation) agents for PLLA homocrystallization. In contrast, SC crystallites formed from PDLA‐L, having the lowest M_n, were effective accelerating agents without any restrictions on T_p. In this case, the accelerating effects can be attributed to the plasticizer effect of PDLA‐L with the lowest M_n. The accelerating effects of SC crystallites in the PLLA/PDLA‐H and PLLA/PDLA‐M films was dependent on crystalline thickness for T_p values below the melting peak temperature of SC crystallites, whereas for T_p values above the melting peak temperature the accelerating effects are suggested to be affected by the interaction between the SC crystalline regions and PLLA amorphous regions.     

Poly(amide‐ester)s derived from dicarboxylic acid and aminoalcohol

A series of alternating aliphatic poly(amide‐ester)s, derived from dicarboxylic acid and aminoalcohols, were obtained by polycondensation in melt. All poly(amide‐ester)s were characterized by FTIR and ¹H/¹³C‐NMR spectroscopies. The synthesized polymers showed an inherent viscosity ranging from 0.4 to 1.0 dL g^?1. Thermal analysis showed melting points within the range 100–115°C and glass transition within the range 30–60°C. Decomposition temperatures were more than 200°C higher than the corresponding melting temperatures. The polymers can thus be processed from the melt. The processed polymers were partially crystalline with good thermal stability. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 362–368, 2005     

Synthesis and characterization of thermoplastic poly(ester–siloxane)s

Two series of thermoplastic poly(ester–siloxane)s, based on poly(dimethylsiloxane) (PDMS) as the soft segment and poly(butylene terephthalate) as the hard segment, were synthesized by two‐step catalyzed transesterification reactions in the melt. Incorporation of soft poly(dimethylsiloxane) segments into the copolyester backbone was accomplished in two different ways. The first series was prepared based on dimethyl terephthalate, 1,4‐butanediol and silanol‐terminated poly(dimethylsiloxane) (PDMS‐OH). For the second series, the PDMS‐OH was replaced by methyl diesters of carboxypropyl‐terminated poly(dimethylsiloxane)s. The syntheses were optimized in terms of both the concentration of catalyst, tetra‐n‐butyl‐titanate (Ti(OBu)₄), and stabilizer, N,N′‐diphenyl‐p‐phenylene‐diamine, as well as the reaction time. The reactions were followed by measuring the inherent viscosities of the reaction mixture. The molecular structures of the synthesized poly(ester–siloxane)s were verified by ¹H NMR spectroscopy, while their thermal properties were investigated using differential scanning calorimetry. © 2001 Society of Chemical Industry     

Poly(D,L‐lactide‐co‐glycolide)/poly(ethylenimine) blend matrix system for pH sensitive drug delivery

Poly(D ,L ‐lactide‐co‐glycolide) (PLGA) and poly(ethylenimine) (PEI) were blended and found to form a homogeneous pH sensitive matrix for drug release. Differential scanning calorimetry (DSC) studies of the PLGA/PEI blends showed a single glass transition temperature at all compositions. Fourier transform infrared spectroscopy (FTIR) demonstrated that the PLGA carbonyl peak at 1760 cm^?1 shifted to 1666 cm^?1 as a result of amide bond formation between the two polymers. This was confirmed by ¹³C nuclear magnetic resonance studies. A PLGA/PEI matrix of 90/10 weight ratio was chosen for evaluation for controlled drug release. Both hydrophobic β‐lapachone and hydrophilic rhodamine B showed pH dependent release profiles with faster release kinetics at lower pH values. The observed pH sensitive drug release was mainly attributed to two factors, pH dependent swelling and protonation of the PEI‐PLGA matrix. These results demonstrate utility of a PLGA/PEI matrix and its potential application in pH responsive drug delivery. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 89–96, 2006     

Thermal Property and Hydrogen Bonding in Blends of Poly(vinylphenol) and Poly(hydroxylether of Bisphenol A)

The thermal property and hydrogen bonding in polymer blends of poly(vinylphenol) (PVPh) and poly(hydroxylether of bisphenol A) (phenoxy) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (NMR). This PVPh/phenoxy blend shows single composition-dependent glass transition temperature over the entire compositions, indicating that the hydrogen bonding exists between the hydroxyl of PVPh and hydroxyl of phenoxy. The negative T _g deviation of the PVPh/phenoxy blend indicates the strong intermolecular hydrogen-bonding interaction. The inter-association constant for the PVPh/phenoxy blend is significantly higher than self-association constants of PVPh and phenoxy, revealing that the tendency toward hydrogen bonding between PVPh and phenoxy is more favorable than the intra-hydrogen bonding of the PVPh and phenoxy in the blend.     

Synthesis and characterization of organosoluble poly(arylate‐imide)s prepared from direct polycondensation of bis(trimellitimide)‐diacids and various bisphenols

Three diimide‐diacids, 2,2‐bis[4‐(4‐trimellitimidophenoxy)phenyl]hexafluoropropane ( I‐A ), 2,2‐bis[4‐(4‐trimellitimidophenoxy)phenyl]propane ( I‐B ), and 5,5′‐bis[4‐ (4‐trimellitimidophenoxy)phenyl]hexahydro‐4,7‐methanoindan ( I‐C ), were prepared by the azeotropic condensation of trimellitic anhydride with three analogous diamines. Three series of alternating aromatic poly(arylate‐imide)s, having inherent viscosities of 0.41–0.82 dL/g, were synthesized from these diimide‐diacids ( I‐A , I‐B , and I‐C ) with various bisphenols by direct polycondensation using diphenyl chlorophosphate and pyridine as condensing agents. All of the polymers were readily soluble in a variety of organic solvents such as N‐methyl‐2‐pyrrolidone, N,N‐dimethylacetamide, and even in the less polar tetrahydrofuran. These polymers could be cast into transparent and tough films, which had strength at break values ranging from 73 to 98 MPa, elongation at break from 6 to 11%, and initial modulus from 1.6 to 2.2 GPa. The softening temperatures of the polymers were recorded at 145–248°C. They had 10% weight loss at a temperature above 450°C and left 35–51% residue even at 800°C in nitrogen. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3818–3825, 2003     

Preparation and characterization of poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones

The two poly(silyl ester)s containing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones have been prepared via polycondensation reaction of di‐tert‐butyl adipate and di‐tert‐butyl fumarate with 2,2‐bis(p‐chloro dimethylsiloxy‐phenyl)propane to give tert‐butyl chloride as the condensate. The polymerizations were performed under nitrogen at 110°C for 24 h without addition of solvents and catalysts to obtain the poly(silyl ester)s with weight average molecular weights typically ranging from 5000 to 10,000 g/mol. Characterization of the poly(silyl ester)s included ¹H NMR and ¹³C NMR spectroscopies, infrared spectroscopy, ultraviolet spectroscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), gel permeation chromatography, and Ubbelohde viscometer. The glass transition temperatures (T_g) of the obtained polymers were above zero because of the introducing 2,2‐bis(p‐dimethylsiloxy‐phenyl)propane units in the polymer backbones. The TGA/DTG results showed that the obtained poly(silyl ester)s were stable up to 180°C and the residual weight percent at 800°C were 18 and 9%, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1937–1942, 2006     

An investigation of the effect of silane water‐crosslinking on the properties of poly(L‐lactide)

A silane‐grafting water‐crosslinking approach was developed to crosslink poly(L ‐lactide) (PLLA) by grafting vinylalkoxysilane onto PLLA using dicumyl peroxide, followed by silane hydrolysis to form siloxane linkages between PLLA chains. The degree of silane grafting onto PLLA was qualitatively characterized using Fourier transform infrared spectroscopy and quantitatively determined using inductively coupled plasma mass spectrometry. Crosslinked PLLA films were obtained by curing of silane‐grafted PLLA in hot water. Gel fractions were evaluated in order to calculate the crosslinking reaction kinetics and crosslinking density. Various techniques were used to investigate the effect of silane water‐crosslinking on the thermomechanical properties, hydrolysis resistance and biodegradation of PLLA. In addition to an improvement in thermal stability and mechanical properties, hydrolysis resistance was significantly enhanced as a result of silane water‐crosslinking of PLLA. Moreover, the biodegradation of silane water‐crosslinked PLLA was retarded compared with neat PLLA. Copyright © 2010 Society of Chemical Industry     

In vitro Degradation of Poly[(L‐lactide)‐co‐(trimethylene carbonate)] Copolymers and a Composite with Poly[(L‐lactide)‐co‐glycolide] Fibers as Cardiovascular Stent Material

TMC/LLA copolymers with several TMC/LLA ratios are synthesized and a composite is obtained by reinforcing with short PLGA fibers. In vitro degradation is studied at 37 °C in pH = 7.4 buffer and compared with a PLLA homopolymer. The degradation of the copolymers appears slower than that of PLLA, showing that TMC units are more resistant to hydrolysis than LLA. Compositional changes indicate a preferential degradation of LLA units as compared to TMC ones. Morphological changes with crystallization of degradation by‐products are observed. The composite degrades much faster than the neat copolymer and PLLA because the faster degradation of PLGA fibers speeds up the degradation of the matrix. The composite appears promising for the fabrication of totally bioresorbable stents.

     

Synthesis and characterization of Ti(Tbse)2 and its application as a catalyst for ROP of rac‐Lactide

A novel bis(3,5‐di‐ tert‐butylsalicylaldehyde‐co‐ethanolamine) titanium(IV) complex (Ti(Tbse)₂) was synthesized and structurally characterized. The X‐ray diffraction results showed that the titanium ion was bonded with two 3,5‐di‐tert‐butylsalicylaldehyde‐co‐ethanolamine ligands (Tbse ligands) in O,N,O‐tridentate mode. Experimental results revealed that the Ti(Tbse)₂ complex could efficiently catalyze the ring‐opening polymerization (ROP) of rac‐lactide and showed a well‐controlled manner at 160 °C, and the polymers obtained had a controlled molecular weight and low polydispersity indices. Kinetic studies showed that the polymerization reaction was second order in monomer concentration and first order in catalyst concentration, and the apparent activation energy (E_a = 77.0 kJ mol^?1) and frequency factor (A = 3.3 × 10¹¹) were obtained according to the Arrhenius equation. ¹³C nuclear magnetic resonance spectra and thermogravimetric and differential scanning calorimetry analysis indicated that the polylactide was essentially a heterotactic and thermally stable polymer. Copyright © 2012 Society of Chemical Industry     

Synthesis and characterization of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Biodegradable polyesters such as poly(butylene succinate) (PBS), poly(propylene succinate) (PPS), and poly(butylene succinate‐co‐propylene succinate)s (PBSPSs) were synthesized respectively, from 1,4‐succinic acid with 1,4‐butanediol and 1,3‐propanediol through a two‐step process of esterification and polycondensation in this article. The composition and physical properties of both homopolyesters and copolyesters were investigated via ¹H NMR, DSC, TGA, POM, AFM, and WAXD. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), crystallinity (X), and thermal decomposition temperature (T_d) of these polyesters decreased gradually as the content of propylene succinate unit increased. PBSPS copolyesters showed the same crystal structure as the PBS homopolyester. Besides the normal extinction crosses under the polarizing optical microscope, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermosensitive nanoparticles prepared from poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) and its blend with poly(lactide‐co‐glycolide) for efficient drug delivery system

Temperature‐responsive polymers have become increasingly attractive as carrier for the injectable drug delivery systems. In the present work, we have studied the preparation of poly(N‐isopropylacrylamide‐acrylamide‐vinilpyrrolidone) (NIPAAm‐AAm‐VP terpolymer) nanoparticulated terpolymer and its blend with poly(lactide‐co‐glycolide, PLGA; molar ratio of lactide/glycolid 1/3). Thermosensitive terpolymer, poly(NIPAAm‐AAm‐VP) was prepared by free‐radical polymerization in aqueous solution. The nanoparticles of poly(NIPAAm‐AAm‐VP) and its blend with PLGA containing naltrexone were prepared using the evaporation and w/o emulsion‐solvent evaporation methods, respectively. Nanoparticles prepared from terpolymer‐PLGA blend at low polymer concentration (5%) shows larger particle size (>300 nm) and higher drug content%. Various types of nanoparticles showed a burst release of less than 10% after 24 h . The results suggest that by regulating different variables, desired release profiles of naltrexone can be achieved using a blend of PLGA‐poly(NIPAAm‐AAm‐VP) nanoparticulate system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Characterization of biaxial strain of poly(l‐lactide) tubes

Poly(l ‐lactide) in its l ‐form has promising mechanical properties. Being a semicrystalline polymer, it can be subjected to strain‐induced crystallization at temperatures above T_g and can thereby become oriented. Following a simultaneous (SIM) biaxial strain process or a sequential (SEQ) biaxial strain process, the mechanical properties of biaxially strained tubes can be further improved. This study investigated these properties in relation to their morphology and crystal orientation. Both processes yield the same mechanical strength and modulus, yet exhibit different crystal orientation. Through further wide angle X‐ray scattering analysis it was found that the SEQ biaxial strain yields larger interplanar spacing and distorted crystals and looser packing of chains. However, this does not influence the mechanical properties negatively. A loss of orientation in SEQ biaxially strained samples at high degrees of strain was detected, but was not seen for SIM biaxial strain and did not correlate with mechanical performance in either case. However, post‐annealing reduced the orientation to the same level in both cases, and the modulus and strength decreased for both SIM and SEQ biaxial strain. It is therefore concluded that mechanical properties after biaxial strain are related to strain‐induced amorphous orientation and the packing of crystals, rather than strain‐induced crystallinity. © 2015 Society of Chemical Industry