New soybean oil–styrene–divinylbenzene thermosetting copolymers. II. Dynamic mechanical properties

A variety of new polymeric materials ranging from soft rubbers to hard, tough, and brittle plastics were prepared from the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and divinylbenzene initiated by boron trifluoride diethyl etherate (BF₃ · OEt₂) or related modified initiators. The relationship between the dynamic mechanical properties of the various polymers obtained and the stoichiometry, the types of soybean oils and crosslinking agents, and the different modified initiators was investigated. The room‐temperature storage moduli ranged from 6 × 10⁶ to 2 × 10⁹ Pa, whereas the single glass‐transition temperatures (T_g) varied from approximately 0 to 105 °C. These properties were comparable to those of commercially available rubbery materials and conventional plastics. The crosslinking densities of the new polymers were largely dependent on the concentration of the crosslinking agent and the type of soybean oil employed and varied from 74 to 4 × 10⁴ mol/m³. The T_g increased and the intensity of the loss factor decreased irregularly with an increase in the logarithmic crosslinking densities of the polymers. Empirical equations were established to describe the effect of crosslinking on the loss factor in these new polymeric materials. The polymers based on conjugated LoSatSoy oil, styrene, and divinylbenzene possessed the highest room‐temperature moduli and T_g 's. These new soybean oil polymers appear promising as replacements for petroleum‐based polymeric materials. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2721–2738, 2000     

New soybean oil‐styrene‐divinylbenzene thermosetting copolymers. III. Tensile stress–strain behavior

The tensile stress–strain behavior and fracture properties of some new soybean oil based polymeric materials were investigated at room temperature. These materials were prepared by the cationic copolymerization of regular soybean oil, low saturation soybean oil (LoSatSoy oil), or conjugated LoSatSoy oil with styrene and the diene comonomers divinylbenzene, norbornadiene, or dicyclopentadiene in a process initiated by boron trifluoride diethyl etherate (BF₃ · OEt₂) or related modified initiators. These new polymeric materials exhibited tensile stress–strain behavior ranging from soft rubbers through ductile to relatively brittle plastics. The Young's moduli of these polymers varied from 3 to 615 MPa, the ultimate tensile strengths varied from 0.3 to 21 MPa, and the elongation at break varied from 1.6 to 300%. These properties are obviously related to their crosslink densities. The conjugated LoSatSoy oil polymers had higher mechanical properties than the corresponding LoSatSoy oil and regular soybean oil polymers with the same stoichiometry. Some conjugated LoSatSoy oil polymers with appropriate stoichiometries showed yielding behavior in the tensile test process. A variety of new polymer materials can thus be prepared by varying the stoichiometry, the type of soybean oil, and the crosslinking agent. These soybean oil based polymers possessed mechanical properties comparable to those of commercially available rubbery materials and conventional plastics and thus may serve as replacements in many applications. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 60–77, 2001     

Linseed oil‐based reactive diluents preparation to improve tetra‐functional epoxy resin properties

Two kinds of bio‐resourced reactive diluents have been synthesized from linseed oil. The prepared epoxidized linseed oil (ELO) and the cyclocarbonated linseed oil (CLO) were separately blended with a petroleum‐based tetra‐functional epoxy resin (TGDDM) to improve its processability and to overcome the brittleness of the thermoset network therefrom. The linseed oil modifications were spectrally established, and processability improvement of the resin blends was rheologically confirmed. The curing of samples was studied by differential scanning calorimetry, and their mechanical properties (ie, tensile, flexural, fracture toughness, and adhesion) were investigated as well. Scanning electron microscopy images were obtained to reconfirm the toughness improvement of the modified thermosets. In contrast of the epoxidized soybean oil (ie, the most conventionally studied bio‐based reactive diluent), ELO and CLO had no negative effects on the thermoset material characteristics. They improved properties such as tensile strength (up to 43.2 MPa), fracture toughness (1.1 MPa m^1/2), and peel‐adhesion strength (4.5 N/25 mm). It was concluded that ELO and CLO were efficient reactive diluents to be used in formulations of polymer composites, surface coatings, and structural adhesives based on epoxy resins.     

Bio‐based nanocomposites composed of photo‐cured epoxidized soybean oil and supramolecular hydroxystearic acid nanofibers

A mixture of epoxidized soybean oil (ESO), (R)‐12‐hydroxystrearic acid (HSA) and a photoinitiator for cationic polymerization in the ESO/HSA weight ratio 10/1 was heated to 100 °C and gradually cooled to room temperature to give bio‐based gelatinous material. The photo‐curing of the gel afforded a nanocomposite composed of crosslinked ESO and supramolecular HSA nanofibers. The transmission electron microscopy observation of the photo‐cured ESO/HSA revealed that dendritic clusters of HSA nanofibers are formed in the crosslinked ESO matrix. In the differential scanning calorimetry chart of the ESO/HSA, a thermal transition from the mesophase composed of supramolecular nanofibers to isotropic state was observed at 67 °C (ΔH = 22.6 J/g‐HSA), while the T_m of crystalline HSA is 77.7 °C (ΔH_m = 159 J/g‐HSA). Tensile strength at 20 °C of the ESO‐HSA was ～80% higher than that of photo‐cured ESO without HSA. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 669–673, 2009     

Carbonyldiimidazole‐accelerated efficient cure of epoxidized soybean oil with dicyandiamide

This study investigates the curing of epoxidized soybean oil (ESO) using dicyandiamide (DICY) and combinations of DICY with several accelerators as curing agents. The differential scanning calorimetry (DSC) results indicated that carbonyldiimidazole (CDI) is a highly efficient accelerator for the ESO‐DICY curing system. CDI accelerated ESO‐DICY curing system can gel within a short period of 13 min at 190 °C. The activation energies of the ESO‐DICY curing systems with and without CDI are 95 and 121 kJ mol^?1, respectively. Similar acceleration effect was observed in the ESO‐diglycidyl ether of biphenyl A (DGEBA) blending formulations. When the molar part of the glycidyl epoxy groups of DGEBA was equal to the internal epoxy groups of ESO in the mixture, gelation of the DICY curing system accelerated by CDI was achieved in 3 min at 160 °C. Furthermore, the DSC results with FTIR analysis suggest that the stoichiometric curing molar ratio was 3 ESO epoxy units per 1 DICY molecule. Two epoxy units reacted with DICY to give secondary alcohols, while the other one linked to the nitrile group. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 375–382     

The oxidation‐treated interface on tribological properties of carbon fibers‐reinforced PTFE composite under oil‐lubricated condition

The effect of air oxidation and ozone surface treatment of carbon fibers (CF) on tribological properties of CF reinforced polytetrafluoroethylene (PTFE) composites under oil‐lubricated condition was investigated. Experimental results revealed that ozone treated CF reinforced PTFE (CF–PTFE) composite had the lowest friction coefficient and wear under various applied loads and sliding speeds compared with untreated and air‐oxidated composites. X‐ray photoelectron spectroscopy (XPS) study of carbon fiber surface showed that, after ozone treatment, oxygen concentration was obviously increased, and the amount of oxygen‐containing groups on CF surfaces was largely increased. The increase in the amount of oxygen‐containing groups enhanced interfacial adhesion between CF and PTFE matrix. With strong interfacial adhesion of the composite, stress could be effectively transmitted to carbon fibers; carbon fibers were strongly bonded with PTFE matrix and large scale rubbing‐off of PTFE was prevented, therefore, the tribological properties of the composite were improved. Copyright © 2009 John Wiley & Sons, Ltd.     

Amphiphilic conetworks. IV. Poly(methacrylic acid)‐l‐polyisobutylene and poly(acrylic acid)‐l‐polyisobutylene based hydrogels prepared by two‐step polymer procedure. New pH responsive conetworks

This article describes the synthesis and characterization of new amphiphilic polymer conetworks containing hydrophilic poly(methacrylic acid) (PMAA) or poly(acrylic acid) (PAA) and hydrophobic polyisobutylene (PIB) chains. These conetworks were prepared by a two‐step polymer synthesis. In the first step, a cationic copolymer of isobutylene (IB) and 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate (IDI) was prepared. The isocyanate groups of the IB–IDI random copolymer were subsequently transformed in situ to methacrylate (MA) groups in reaction with 2‐hydroxyethyl methacrylate (HEMA). In the second step, the resulting MA‐multifunctional PIB‐based crosslinker, PIB(MA)_n, with an average functionality of approximately four methacrylic groups per chain, was copolymerized with methacrylic acid (MAA) or acrylic acid (AA) by radical mechanism in tetrahydrofuran giving rise to amphiphilic conetworks containing 31–79 mol % of MAA or 26–36 mol % of AA. The synthesized conetworks were characterized with solid‐state ¹³C‐NMR spectroscopy and differential scanning calorimetry. The amphiphilic nature of the conetworks was proven by swelling in both aqueous media with low and high pH and n‐heptane. The effect of varying pH on the swelling behavior of the synthesized conetworks is presented. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1284–1291, 2009     

Synthesis and properties of the polythiourethanes obtained by the cationic ring‐opening polymerization of cyclic thiourethanes

The cationic ring‐opening polymerization of a five‐membered thiourethane [3‐benzyl‐1,3‐oxazolidine‐2‐thione (BOT)] with boron trifluoride etherate afforded the corresponding polythiourethane with a narrow molecular weight distribution in an excellent yield. The molecular weight of the polymers could be controlled by the feed ratio of the monomer to the initiator. A kinetic study of the polymerization revealed that the polymerization rate of BOT (1.3 × 10^?2 L mol^?1 min^?1) was two times larger than that of the six‐membered thiourethane [3‐benzyltetrahydro‐1,3‐oxazolidine‐2‐thione (BTOT); 6.8 × 10^?3 L mol^?1 min^?1], and the monomer conversion obeyed the first‐order kinetic equation. These observations, along with the successful results in the two‐stage polymerization, supported the idea that this polymerization proceeded in a controlled manner. Block copolymerizations of BOT with BTOT were also carried out to afford the corresponding di‐ and triblock copolymers with narrow molecular weight distributions. The order of the 5% weight loss temperatures was as follows: poly(3‐benzyltetrahydro‐1,3‐oxazolidine‐2‐thione) [poly(BTOT)] > poly(BTOT₅₄‐b‐BOT₄₆) > poly(3‐benzyl‐1,3‐oxazolidine‐2‐thione) [poly(BOT)]. This indicated that an increase in the BTOT unit content raised the decomposition temperature. The order of the refractive indices was poly(BOT) > poly(BTOT₅₄‐b‐BOT₄₆) > poly(BTOT₅₄‐b‐BOT₄₆‐b‐BTOT₅₀) > poly(BTOT); this was in accord with the order of the sulfur content in the polymer chain. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4795–4803, 2006     

Dewatering of crude oil emulsions 1. Rheological behaviour of the crude oil—water interface

Rheological properties of Buchan crude oil—water interfaces have been determined using a biconical bob rheometer. The effects of temperature and the presence of surface-active demulsifiers on film characteristics have been evaluated. Free oscillation and creep modes have been used, depending on the relative viscoelastic behaviour of the films. Film ageing is particularly significant, whilst temperature and the nature and concentration of any demulsification chemicals also contribute significantly. Further detailed understanding of interfacial film rheology is considered to be desirable for a complete appreciation of the stability of water-in-crude oil emulsions.     

Cellulose‐based macroinitiator for crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) oil‐absorbing materials by SET‐LRP

Cellulose produced from cotton fibers was used as substrate for synthesis of oil‐absorbing materials by single electron transfer‐living radical polymerization. The cellulose macroinitiator was prepared by esterification of hydroxyl group with 2‐bromoisobutyryl bromide (BiBB), followed by grafting with butyl methacrylate (BMA) and pentaerythritol triacrylate (PETA) to render a three‐dimensional architecture. The polymerization was catalyzed by Cu(0) powder/hexamethylenetetramine (HMTA) and performed in N,N‐dimethylformamide (DMF). Effects of cellulose, catalyst, reaction temperature, and time were investigated in detail. The maximum oil absorption to chloroform and toluene could reach 29.0 and 15.4 g·g^?1, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Structure and properties of halogenated and nonhalogenated soy‐based polyols

Four polyols intended for application in polyurethanes were synthesized by oxirane ring opening in epoxidized soybean oil with hydrochloric acid, hydrobromic acid, methanol, and hydrogen. The structures of the polyols were characterized by spectroscopic, chemical, and physical methods. The brominated polyol had 4.1 hydroxy groups, whereas the other three polyols had slightly lower functionality. The densities, viscosities, viscous‐flow activation energies, and molecular weights of the polyols decreased in the following order: brominated > chlorinated > methoxylated > hydrogenated. All the polyols were crystalline solids below their melting temperature, displaying multiple melting peaks. The methoxylated polyol was liquid at room temperature, whereas the other three were waxes. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3900–3910, 2000     

Synthesis of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,characterization, and crosslinking of novel stars comprising eight poly(isobutylene‐azeotropic‐styrene) copolymer arms with allyl or hydroxyl termini. I. Living azeotropic copolymerization of isobutylene and styrene

The overall objective of this research is the creation of novel star polymers consisting of well‐defined stable cores out of which radiate multiple poly(isobutylene‐co‐styrene) [P(IB‐co‐St)] arms whose glass‐transition temperature (T_g) can be controlled over a wide range (?73 to +100 °C) and whose arm termini are fitted with multipurpose (e.g., crosslinkable) functionalities. The first article of this series relates the synthesis and characterization of azeotropic IB/St copolymers [P(IB‐aze‐St)], which are to be subsequently used as end‐functional arms of the target stars. The P(IB‐aze‐St)s are models for statistical IB/St copolymers. The azeotropic composition is 21/79 (mol/mol) IB/St, and NMR, Fourier transform infrared, and gel permeation chromatography techniques demonstrate copolymer compositional homogeneity over the 12–96% conversion range. Conditions were developed for living azeotropic IB/St copolymerization. The livingness of the azeotropic copolymerization was proven by kinetic investigations. P(IB‐aze‐St)s with number‐average molecular weights of up to 24,000 g/mol and polydispersity indices (weight‐average molecular weight/number‐average molecular weight) less than 1.5 were prepared. The copolymerization reactivity ratios were determined: r_IB = 3.41 ± 0.23 and r_St = 1.40 ± 0.26. The effect of the P(IB‐aze‐St) molecular weight on T_g was studied by DSC. T_g increases linearly with the number‐average molecular weight and reaches a plateau at 62 °C at 24,000 g/mol. The heat stability of P(IB‐aze‐St) was investigated by thermogravimetric analysis, and a 5% weight loss was found at 250 °C in air. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1515–1524, 2001     

Textile‐Compatible Substrate Electrodes with Electrodeposited ZnO—A New Pathway to Textile‐Based Photovoltaics

A strategy is presented to realize textile‐based photovoltaic cells motivated by developments of textile‐based electronics and their demand of grid‐independent energy supply. Beyond this, a development of textile‐based photovoltaics also represents an attractive pathway towards very flexible and rugged solar cells. The need for compatibility of an appropriate photovoltaic technology with the physical limitations of textiles is stressed. Electrodeposition from aqueous solutions is presented as a successful strategy to realize semiconductor structures on textiles and detailed control and influence of the deposition conditions is discussed. The role of microelectrode effects, options of forced convection, deposition under pulsed potential, alternative deposition baths and different substrate metals are emphasized. An active electrode material is presented which reaches a conversion efficiency close to the 1 % limit under AM 1.5 illumination conditions and thereby opens the door for a further optimization towards devices of technical interest.     

Synthesis and thermal,mechanical, and optical properties of A–B–A or A–B block copolymers containing poly(norbornene‐co‐1‐octene)

A–B–A block copolymers which consist of poly(norbornene‐co‐1‐octene) and atactic polypropylene (PP) segments were synthesized by using ansa‐fluorenylamidotitanium complex as a catalyst varying the ratio of norbornene, 1‐octene, and propylene. The copolymer was obtained quantitatively with high molecular weight (>100,000) and narrow molecular weight distribution (polydispersity index, <1.5). A–B block copolymers of poly(norbornene‐co‐1‐octene) and poly(methyl methacrylate) (PMMA) was also obtained by the same procedure. Mechanical and optical properties of these copolymer films, which were obtained by solution casting process, were also investigated. Introduction of PP soft segment greatly improved mechanical properties, keeping their high transparency. Introduction of PMMA block also increased the tensile strength. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 267–271     

Synthesis and evaluation of some polymeric surfactants for treating crude oil—Part II. Destabilization of naturally occurring water‐in‐oil emulsions by polyalkylphenol formaldehyde amine resins

In the present work, three polymeric surfactants were prepared and used as demulsifiers; polyalkyl phenol formaldehyde monoethanol amine ethoxylate, eo, 136(D1), polyalkyl phenol formaldehyde diethanol amine ethoxylate, eo, 37(D2) and polyalkyl phenol formaldehyde triethanol amine ethoxylate, eo, 21.5(D3). Their demulsification potency in breaking water‐in‐crude oil emulsions was investigated. In this respect, two naturally occurring Egyptian water‐in‐oil (w/o) emulsions, one of them was waxy and the other was asphaltenic, were used in order to study the demulsification power of these compounds. The data revealed that, the resolution of water from waxy crude emulsion was easier than asphaltenic crude emulsion. The demulsification efficiency increases with increasing demulsifier concentration, contact time and temperature. The interfacial tension (IFT) at the crude oil–water interface was measured, it was found that the concentration of demulsifiers required to cause a minimum IFT are always less than these indicating a maximum demulsification efficiency. All the results were discussed in relation to emulsifier chemical structure and crude oil composition. Copyright © 2002 John Wiley & Sons, Ltd.     

Synthesis,characterization, and preceramic properties of π‐conjugated polymers based on Ni(II) complexes of goedken's macrocycle

Nickel(II) complexes of Goedken's macrocycle bearing alkyne substituents were copolymerized with 2,7‐dibromo‐9,9‐dihexylfluorene, 2,5‐dibromo‐3‐hexylthiophene, and 1,4‐dibromo‐2,5‐bis(hexyloxy)benzene via microwave‐induced Sonogashira cross‐coupling reactions to produce copolymers 6F , 6T , and 6B . The spectroscopic and electrochemical properties of the copolymers were examined and compared to model compounds. Specifically, each polymer exhibited a nickel‐based absorption centered at about 589 nm and two π → π* transitions between 272 and 387 nm. While the copolymers did not exhibit extended π conjugation, the nature of the organic spacer did affect the high energy transitions. Furthermore, each copolymer underwent two ligand‐based one‐electron oxidations at potentials of about 0.24 V and about 0.75 V relative to the ferrocene/ferrocenium redox couple. Postpolymerization functionalization of the alkyne group in 6F with Co₂(CO)₈ afforded a novel heterobimetallic copolymer that yielded amorphous nanomaterials containing Ni/Co when pyrolyzed at 800 °C for 3 h under an atmosphere of N₂/H₂ (95:5). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3257–3266     

Amphiphilic conetworks. II. Novel two‐step synthesis of poly[2‐(dimethylamino)ethyl methacrylate]–polyisobutylene,poly(N‐isopropylacrylamide)–polyisobutylene,and poly(N,N‐dimethylacrylamide)–polyisobutylene hydrogels

Amphiphilic polymer conetworks consisting of hydrophilic poly[2‐(dimethylamino)ethyl methacrylate], poly(N‐isopropylacrylamide), or poly(N,N‐dimethylacrylamide) and hydrophobic polyisobutylene chains were synthesized with a novel two‐step procedure. In the first step, a methacrylate‐multifunctional polyisobutylene crosslinker was prepared by the cationic copolymerization of isobutylene with 3‐isopropenyl‐α,α‐dimethylbenzyl isocyanate. In the second step, the methacrylate‐multifunctional polyisobutylene crosslinker, with a number‐average molecular weight of 8200 and an average functionality of approximately 4 per chain, was copolymerized radically with 2‐(dimethylamino)ethyl methacrylate, N‐isopropylacrylamide, or N,N‐dimethylacrylamide into transparent amphiphilic conetworks containing 42–47 mol % hydrophilic monomer. The synthesized conetworks were characterized with solid‐state ¹³C NMR spectroscopy and differential scanning calorimetry. The amphiphilic nature of the conetworks was proved by swelling in both water and n‐heptane. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6378–6384, 2006     

Preparation and characterization of novel PES‐(SiO2‐g‐PMAA) membranes with antifouling and hydrophilic properties for separation of oil‐in‐water emulsions

In the present study, modification of nanoparticles (NPs) was investigated to mitigate aggregation of SiO₂ nanoparticles and improve the polymeric membrane's performance. For this purpose, the surface of SiO₂ nanoparticles was activated with amine groups, and polymethacrylic acid (PMAA) was grafted on the surface of NPs by atom transfer radical polymerization. Modified NPs were characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) tests. Polyethersulfone (PES) membranes were fabricated with both SiO₂ and SiO₂‐g‐PMAA NPs via nonsolvent‐induced phase separation method. The fabricated membranes were characterized regarding their permeability, hydrophilicity, and porosity properties, and their separation efficiency was tested using the synthetic oil‐in‐water emulsion. The surface and cross‐sectional morphologies of membranes were observed by field emission scanning electron microscopy (FESEM). The experimental trials showed that modified NPs dispersed more uniformly in the structure of membranes and hydroxyl groups on the surface of NPs acted more effectively. Modification of NPs enhance the membrane performance in terms of permeate flux, hydrophilicity, and porosity. NPs modification improved the permeate flux about 46%. Oil rejection for all tested membranes was more than 98%, and modification of NPs did not reduce the rejection of membranes. The optimum concentration was obtained as 1 wt.% and 1.5 wt.% for SiO₂ and SiO₂‐g‐PMAA, respectively. Aggregation effect dominated at concentrations beyond the optimum values that decreased the permeate flux, consequently.     

Synthesis of biodegradable copolymers with low‐toxicity zirconium compounds. II. Copolymerization of glycolide with ϵ‐caprolactone initiated by zirconium(IV) acetylacetonate and zirconium(IV) chloride

The aim of this article is to show a new method of copolymerizing glycolide and caprolactone with the low‐toxicity zirconium(IV) acetylacetonate and zirconium(IV) chloride as initiators. Such initiators enabled us to obtain copolymers with very good efficiency and good mechanical properties. The reactivity of the initiators was defined, and the chain‐propagation process was examined. On the basis of an NMR examination and differential scanning calorimetry thermograms, we found that the samples obtained at 100 °C with the initiators were characterized by a segmental chain microstructure, which provided good mechanical properties. When the synthesis was carried out at 150 °C, a more randomized structure was obtained, which caused crucial changes in the properties of the copolymers and decreases in the mechanical properties. Because of their properties, the obtained copolymers could be successfully applied as degradable surgical implants or drug carriers. The results show that the copolymers obtained with zirconium(IV) acetylacetonate and chloride could successfully replace ones obtained in the presence of tin compounds as far as medical applications are concerned. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1379–1394, 2002