Jan Łukaszczyk

Synthesis of functional polycarbonates by copolymerization of carbon dioxide with allyl glycidyl ether

Functional aliphatic polycarbonate was synthesized by copolymerization of carbon dioxide and allyl glycidyl ether in the presence of a catalyst system based on ZnEt 2 and pyrogallol at a molar ratio of 2:1. The polycarbonate obtained was oxidized with m-chloroperbenzoic acid to give poly(epoxycarbonate). These polymers were degraded in an aqueous buffer of pH 7.4 at 37°C. Hydrolytic degradation was monitored by determination of the weight loss.

Investigation on synthesis and properties of isosorbide based bis-GMA analogue

The aim of this work was to synthesize and investigate properties of a novel dimethacrylic monomer based on bioderived alicyclic diol—isosorbide. Its potential as a possible substitute of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy)phenyl]propane (BISGMA), widely used in dental restorative materials and suspected for toxicity was assessed. The novel monomer was obtained in a three-step synthesis. First, isosorbide was etherified by a Williamson nucleophilic substitution and subsequently oxidized to isosorbide diglycidyl ether (ISDGE). A triphenyl phosphine catalyzed addition of methacrylic acid to ISDGE resulted in 2,5-bis(2-hydroxy-3-methacryloyloxypropoxy)- 1,4:3,6-dianhydro-sorbitol (ISDGMA). The monomer obtained was photopolymerized using camphorquinone/2-(dimethylamino)ethyl methacrylate initiating system. Next, compositions with triethylene glycol dimethacrylate (TEGDMA) were prepared and polymerized. Double bond conversion, polymerization shrinkage and water sorption of resulting polymers were determined. Selected mechanical (flexular strength and modulus, Brinell hardness) and thermomechanical (DMA analysis) properties were also investigated. BISGMA based materials were prepared as reference for comparison of particular properties.

Synthesis and Modification of Functional Polycarbonates with Pendant Allyl Groups

Functional aliphatic polycarbonates with pendant allyl groups were synthesised by copolymerization of carbon dioxide and allyl glycidyl ether (AGE) in the presence of a catalyst system based on ZnEt2 and pyrogallol at a molar ratio 2 : 1. The functionality of some polycarbonates was reduced by replacing a part of allyl ether with saturated glycidyl ether, i.e., butyl glycidyl ether (BGE) or isopropyl glycidyl ether (IGE). Polycarbonates obtained by the copolymerization of AGE and CO2 or by the terpolymerization of AGE, IGE and CO2 were oxidized with m-chloroperbenzoic acid to their respective poly(epoxycarbonate)s. The influence of the AGE/ΣGE ratio in the polycarbonates, the polymer concentration in the reaction solution and the duration of the reaction on the conversion of allyl groups into glycidyl ones was examined. A tendency to gelation of the initial and oxidized polycarbonates during storage was observed. The initial polycarbonates and their oxidized forms were degraded in aqueous buffer of pH = 7.4 at 37°C. The course of hydrolytic degradation was monitored by the determination of mass loss.

Influence of the parameters of encapsulation process and of the structure of diisocyanates on the release of codeine from resinate encapsulated in polyurea by interfacial water promoted polyreaction

Wet resinate beads consisting of carboxylic ion exchange resin and codeine have been coated with polyureas by use of interfacial water promoted polyreaction of various diisocyanates. Retardation of drug release from coated resinates was estimated based on the measurement of codeine concentration during elution in simulated gastric juice. It has been found that the rate of codeine release depends on the parameters of encapsulation process: type of diisocyanate used, content of water in resinate, duration of swelling of resinate with water, diisocyanate/resinate weight ratio, reaction time and temperature.

Studies on copolymerization of succinic anhydride and allyl glycidyl ether

Functional aliphatic polyesters were synthesised by melt copolymerization of succinic anhydride (SA) and allyl glycidyl ether (AGE) in the presence of benzyltrimethylammonium chloride (BTMAC) as a catalyst. The influence of the parameters of the process: AGE/SA feed ratio, duration of the reaction, amount of water and of the catalyst added on the reaction course and on characteristics of the products obtained has been examined. Tendency to gelation of the polyesters during some syntheses and increase of molecular weight after consumption of functional groups were observed.

Novel bioactive polyester scaffolds prepared from unsaturated resins based on isosorbide and succinic acid.

In this study new biodegradable materials obtained by crosslinking poly(3-allyloxy-1,2-propylene succinate) (PSAGE) with oligo(isosorbide maleate) (OMIS) and small amount of methyl methacrylate were investigated. The porous scaffolds were obtained in the presence of a foaming system consisted of calcium carbonate/carboxylic acid mixture, creating in situ porous structure during crosslinking of liquid formulations. The maximum crosslinking temperature and setting time, the cured porous materials morphology as well as the effect of their porosity on mechanical properties and hydrolytic degradation process were evaluated. It was found that the kind of carboxylic acid used in the foaming system influenced compressive strength and compressive modulus of porous scaffolds. The MTS cytotoxicity assay was carried out for OMIS using hFOB1.19 cell line. OMIS resin was found to be non-toxic in wide range of concentrations. On the ground of scanning electron microscopy (SEM) observations and energy X-ray dispersive analysis (EDX) it was found that hydroxyapatite (HA) formation at the scaffolds surfaces within short period of soaking in phosphate buffer solution occurs. After 3h immersion a compact layer of HA was observed at the surface of the samples. The obtained results suggest potential applicability of resulted new porous crosslinked polymeric materials as temporary bone void fillers.

Preliminary studies on the hydrolytic degradation and biocompatibility of poly(3-allyloxy-1,2-propylene succinate).

In the present paper the synthesis and selected properties of functional aliphatic poly(3-allyloxy-1,2-propylene succinate) (PSAGE) are described. This polyester was synthesized by melt co-polymerization of succinic anhydride and allyl glycidyl ether in the presence of benzyltrimethylammonium chloride as catalyst. The chain structure of PSAGE and its end-groups was characterized by MALDI-TOF mass spectrometry. It was found that PSAGE undergoes hydrolytic degradation in phosphate buffer solution (pH 7.41) at 37°C and, unexpectedly, the dependence of mass loss on immersion time turned out to be linear in the first 12 weeks, similar to hydrophobic polyanhydrides. The polysuccinate of 3600 Da was tested on rat alveolar macrophage cell line using the MTT assay to determine its cytotoxicity, as well as the NO production level, which is an indicator of cell activation. The data obtained show that PSAGE is non-toxic, and that the viability of cells ranges from 86 to 100%. The obtained results reveal the potential applicability of PSAGE as a component of biomaterials or as polymeric drug carrier.

Synthesis and Characteristics of Biodegradable Epoxy-Polyester Resins Cured with Glutaric Anhydride

Biodegradable epoxy-polyester resins were synthesized in two steps: (1) the synthesis of the polyesters with allyl pendant groups, and (2) the epoxidation of the allyl groups in the polyesters. Polyesters with allyl pendant groups were synthesized by the melt copolymerization of succinic anhydride (SA) and allyl glycidyl ether (AGE) in the presence of benzyltrimethylammonium chloride (BTMAC) as the catalyst. The functionality of some polyesters was reduced by replacing a part of AGE with butyl glycidyl ether (BGE). The epoxidation of the polyesters obtained was carried out using m-chloroperben- zoic acid (MCPBA). The multifunctional epoxy-polyester resins were cured with different amounts of glutaric anhydride (GA). The course of the curing process was monitored using DSC method. The following parameters of the process were determined: heat of curing, onset, maximal and end temperatures. Glass transition temperatures (T g s) of the cured resins were determined by dynamic mechanical thermal analysis (DMTA). The influence of the composition of the initial resins and amount of GA on the properties of the cured products, such as density, hardness, T g values, swelling and water sorption, were examined. Epoxy-polyester resins were subjected to the test of accelerated hydrolytic degradation in an aqueous phosphate buffer of pH = 7.4 at 70 °C.

Novel injectable biomaterials for bone augmentation based on isosorbide dimethacrylic monomers

Drawbacks with the commonly used PMMA-based bone cements, such as an excessive elastic modulus and potentially toxic residual monomer content, motivate the development of alternative cements. In this work an attempt to prepare an injectable biomaterial based on isosorbide-alicyclic diol derived from renewable resources was presented. Two novel dimethacrylic monomers ISDGMA - 2,5-bis(2-hydroxy-3-methacryloyloxypropoxy)-1,4:3,6-dianhydro-sorbitol and ISETDMA - dimethacrylate of ethoxylated isosorbide were synthesized and used to prepare a series of low-viscosity compositions comprising bioactive nano-sized hydroxyapatite in the form of a two-paste system. Formulations exhibited a non-Newtonian shear-thinning behavior, setting times between 2.6 min and 5.3 min at 37°C and maximum curing temperatures of 65°C. Due to the hydrophilic nature of ISDGMA, cured compositions could absorb up to 13.6% water and as a result the Youngs modulus decreased from 1,429 MPa down to 470 MPa. Both, poly(ISDGMA) and poly(ISETDMA) were subjected to a MTT study on mice fibroblasts (BALB/3T3) and gave relative cell viabilities above 70% of control. A selected model bone cement was additionally investigated using human osteosarcoma cells (SaOS-2) in an MTS test, which exhibited concentration-dependent cell viability. The preliminary results, presented in this work reveal the potential of two novel dimethacrylic monomers in the preparation of an injectable biomaterial for bone augmentation, which could overcome some of the drawbacks typical for conventional acrylic bone cement.

Preliminary Studies on the Properties of Novel Polymeric Composite Materials Based on Polysuccinates

This study aimed to prepare novel biodegradable polymeric composites based on poly(3-allyloxy-1,2-propylene) succinate (PSAGE). These composite materials are composed of poly(ester-anhydride) (PEA) microspheres embedded in polyester matrix prepared by crosslinking PSAGE with oligo(1,2-propylene maleate) and methacrylic monomers. Methyl methacrylate and one of hydrophilic oligo(ethylene glycol) dimethacrytes with different length of oligooxyethylene chains were used as polymerizable solvents. Incorporation of microspheres that degrade faster than crosslinked polyester matrices enables formation of porous structure. The obtained materials are liquid before curing and harden in several minutes with moderate exothermic effect. The effect of the composition of polyester matrices and kind of PEA microspheres used on selected properties, such as water sorption, mechanical strength, porosity, and hydrolytic degradation behavior, was investigated. The morphology of the cured composite materials subjected to hydrolytic degradation was evaluated by SEM.