Ivan S. Ristić

Novel Microwave-Assisted Synthesis of Poly(D,L-lactide): The Influence of Monomer/Initiator Molar Ratio on the Product Properties

Poly(D,L-lactide) synthesis using tin(II) 2-ethylhexanoate initiated ring-opening polymerization (ROP) takes over 30 hours in bulk at 120 °C. The use of microwave makes the same bulk polymerization process with the same initiator much faster and energy saving, with a reaction time of about 30 minutes at 100 °C. Here, the poly(lactide) synthesis was done in a microwave reactor, using frequency of 2.45 GHz and maximal power of 150 W. The reaction temperature was controlled via infra-red system for in-bulk-measuring, and was maintained at 100 °C. Different molar ratios of monomer and initiator, [M]/[I], of 1,000, 5,000 and 10,000 were used. The achieved average molar masses for the obtained polymers (determined by gel permeation chromatography) were in the interval from 26,700 to 112,500 g/mol. The polydispersion index was from 2.436 to 3.425. For applicative purposes, the obtained material was purified during the procedure of microsphere preparation. Microspheres were obtained by spraying a fine fog of polymer (D,L-lactide) solution in tetrahydrofuran into the water solution of poly(vinyl alcohol) with intensive stirring.

Synthesis and Characterisation of Polyester Based on Isosorbide and Butanedioic Acid

Copolyesters based on isosorbide and butanedioic acid in combination with monomers such as adipic acid and dimethyl terephthalate, poly(isosorbide-co-butanedioic acid) (and -co-adipic acid) and poly(isosorbide-co-butanedioic acid-co-dimethyl terephthalate), were synthesized and characterized. Linear OH-functionalized polyesters were obtained via melt polyesterification of dicarboxylic acids with OH-functional monomers. The type of end-group was controlled by the monomer stoichiometry and hydroxyl functional group is formed in time. Average molecular masses of synthesised polyesters were measured by gel permeation chromatography. The glass transition temperatures and thermal stability of the obtained polyesters were effectively adjusted by varying polymer composition and molar mass. Addition of adipic acid or dimethyl terephthalate increased glass transition temperatures of obtained polyesters. Thermal stability of obtained polyester slightly increases by the increasing of dimethyl terephthalate content. Molecular structures of obtained polyester were assessed by Fourier transform infrared spectra and 1H NMR spectroscopy.

Structural Differences Between Lignin Model Polymers Synthesized from Various Monomers

In a plant cell wall, lignin is synthesized from several monomeric precursors, combined in various ratios. The variation in monomer type and quantity enables multifunctional role of lignin in plants. Thus, it is important to know how different combinations of lignin monomers impact variability of bond types and local structural changes in the polymer. Lignin model polymers are a good model system for studies of relation between variations of the starting monomers and structural variations within the polymer. We synthesized lignin model polymers from three monomers, CF—based on coniferyl alcohol and ferulic acid in monomer proportions 5:1 and 10:1 (w/w), CP—based on coniferyl alcohol and p-coumaric acid in proportion 10:1 (w/w) and CA—based on pure coniferyl alcohol. We studied structural modifications in the obtained polymers, by combining fluorescence microscopy and spectroscopy, FT-IR and Raman spectroscopy, in parallel with determination of polymers’ molecular mass distribution. The differences in the low Mw region of the distribution curves of the 10:1 polymers in comparison with the CA polymer may be connected with the increased content of C=C bonds and decreased content of condensed structures, as observed in FT-IR spectra and indicated by the analysis of fluorescence spectra. The 5:1 CF polymer contains a different type of structure in comparison with the 10:1 CF polymers, reflected in its simpler Mw distribution, higher homogeneity of the fluorescence emitting structures and in the appearance of a new high-wavelength emission component. We propose that this component may originate from π-conjugated chains, which are longer in this polymer. The results are a contribution to the understanding of the involvement of structural variations of lignin polymers in the cell wall structural plasticity.

Synthesis and properties of novel star-shaped polyesters based on l -lactide and castor oil

The topology of biodegradable polyesters can be adjusted by incorporating multifunctional polyols into the polyester backbone to obtain branched polymers. The aim of this study was to prepare the biodegradable-branched polyester polyols based on l-lactide and castor oil using the trifluoromethanesulfonic acid as a catalyst. FTIR and 1H NMR spectroscopy measurements were used to estimate the molecular structure of the novel materials. The polyester polyol was synthesized by ‘‘core-first” method which involves a polymerization of l-lactide by using a castor oil as multifunctional initiator. Molar masses estimated by gel permeation chromatography and vapor pressure osmometry were in good correlation with calculated values based on hydroxyl number of obtained polymers. DSC measurements confirmed high crystallinity degree of the synthesized material. It was assessed that the molar masses of obtained polymers-influenced glass transition temperature significantly. The thermal stability was investigated by TG analysis, and the results have shown the dependence of weight loss on the arm length of the star-shaped polyesters. The thermal stability of star-shaped polyesters significantly decreased with degradation of polyester polyol obtained in acid solution.

Antimicrobial nanomaterials for food packaging applications

Food packaging industry presents one of the fastest growing industries nowadays. New trends in this industry, which include reducing food as well as packaging waste, improved preservation of food and prolonged shelf-life together with substitution of petrochemical sources with renewable ones are leading to development of this industrial area in diverse directions. This multidisciplinary challenge is set up both in front of food and material scientists. Nanotechnology is recently answering to these challenges, with different solutions-from improvements in materials properties to active packaging solutions, or both at the same time. Incorporation of nanoparticles into polymer matrix and preparation of hybrid materials is one of the methods of modification of polymer properties. Nano scaled materials with antimicrobial properties can act as active components when added into polymer, thereby leading to prolonged protective function of pristine food packaging material. This paper presents a review in the field of antimicrobial nanomaterials for food packaging in turn of technology, application and regulatory issues.

Thermal Analysis of Polyurethane Dispersions Based on Different Polyols

Water-based polyurethane dispersions (PUD) are a rapidly growing segment of polyurethane (PU) coatings industry due to environmental legislations such as the clean air act and also due to technological advances that made them an effective substitute for the solvent-based analogs. Water-based or waterborne PUD have gained increasing importance in a range of applications, due in large part to properties such as adhesion to a range of substrates, resistance to chemicals, solvents and water, abrasion resistance and flexibility. Water-based PUD show very good mechanical and chemical properties and match the regulatory pressures for low volatile organic compound (VOC) containing raw paints. The continuous reduction in costs and the control of VOC emissions are increasing the use of water-based resins, motivating the development of PU dispersed in water. PU obtained from water-based PUD have superior properties when compared with similar materials obtained from organic media. Water-based PUD are used in many application areas to coat a wide range of substrates for example footwear adhesives, wood lacquers for flooring and furniture, leather finishings, plastic coatings, printing inks and automotive base coats (Rothause et al., 1987; Kim et al., 1994; Ramesh et al., 1994).

The influence of montmorillonite modification on the properties of composite material based on poly(methacrylic acid)

In this work a new class of functional composites was prepared based on the organically modificated montmorillonite and methacrylic acid. In the first step, the native montmorillonite was mixed with poly(ethylenimine) monomer to promote the intercalation process. In the second step, the methacrylic acid and initiator (potassium persulfate) were added and polymerization was carried out at 80°C for 2 hours. Characterization of the obtained composite material was performed by Fourier transform infrared spectroscopy. The change in interlamellar spacing of montmorillonite after polymer composite preparation was determined by X-ray diffraction. In prepared composite samples the existence of two crystalline phases was estimated by X-ray measurements. In the first, the poly(methacrylic acid) chains are intercalated within the montmorillonite layers, and in the second, they are dispersed in the polymer matrix. The influence of montmorillonite on the thermal properties of the obtained composites was measured using the combined thermogravimetry and differential scanning calorimetry method. The porosity of the prepared samples was determined by isotherm adsorption and the desorption of nitrogen (Brunauer–Emmett–Teller method). It was assessed that a certain amount of polymer is deposited on the montmorillonite and thus covering of the micropores and partially covering of the mesopores was achieved.

Synthesis of polyrotaxanes from acetyl-β-cyclodextrin

Polyrotaxanes are intermediary products in the synthesis of topological gels. They are created by inclusion complex formation of hydrophobic linear macromolecules with cyclodextrins or their derivatives. Then, pairs of cyclodextrin molecules with covalently linkage were practically forming the nodes of the semi-flexible polymer network. Such gels are called topological gels and they can absorb huge quantities of water due to the net flexibility allowing the poly(ethylene oxide) chains to slide through the cyclodextrin cavities, without being pulled out altogether. For polyrotaxane formation poly(ethylene oxide) was used like linear macromolecules. There are hydroxyl groups at poly(ethylene oxide) chains, whereby the linking of the voluminous molecules should be made. To avoid the reaction of cyclodextrin OH groups with stoppers, they should be protected by, e.g., acetylation. In this work, the acetylation of the OH groups of β-cyclodextrin was performed by acetic acid anhydride with iodine as the catalyst. The acetylation reaction was assessed by the FTIR and HPLC method. By the HPLC analysis was found that the acetylation was completed in 20 minutes. Inserting of poly(ethylene oxide) with 4000 g/mol molecule mass into acetyl-β-cyclodextrin with 2:1 poly(ethylene oxide) monomer unit to acetyl-β-cyclodextrin ratio was also monitored by FTIR, and it was found that the process was completed in 12 h at the temperature of 10°C. If the process is performed at temperatures above 10°C, or for periods longer than 12 hours, the process of uncontrolled hydrolysis of acetate groups was initiated.

The influence of the nanofiller on thermal properties of thermoplastic polyurethane elastomers

Hybrid materials based on renewable resources are under huge interest of scientist nowadays. Polymer-based hybrid materials with the addition of nanoparticles are very interesting because the addition of small amount of nanoparticles significantly improves final material’s properties. Group of polymers which is suitable for use for hybrid materials preparation are polyurethanes. Polyurethanes have wide spectra of commercial and industrial applications, but for their production petroleum-based derivative is used and big efforts are still making for changing it with components from renewable resources. Thermoplastic polyurethanes were synthesized using two types of isocyanates: isophorone diisocyanate and hexamethylene diisocyanate, and the possibility of using isosorbide, instead of butanediol, as chain extender for the synthesis of thermoplastic polyurethane elastomers was investigated. NCO/OH ratio was 1.15/1 and soft segment content 50% in all samples. Also, the influence of the addition of hydrophilic and hydrophobic silicon(IV)-oxide nanoparticles, in amounts of 0.5,1, 2, and 5%, on thermal properties of the obtained green polyurethanes is determined using DSC and TG analysis. It is shown that hydrophilic silicon(IV)-oxide nanoparticles have an influence on thermal properties of soft segment in polyurethane structure, while hydrophobic ones have the influence on hard polyurethane’s segment properties, increasing Tg values. Thermal stability of polyurethanes increased with increasing the amount of nanoparticles added. FT-IR analysis showed that there is no chemical reaction between polymer and nanoparticles.

Synthesis, spectroscopic and thermal characterization of new metal-containing isocyanate-based polymers

AbstractTo overcome the polyurethanes low heat resistance and obtain new PU-based materials, in continuation of our research in the synthesis of hybrid polymers, we report here the synthesis of metal-containing polyurethanes formed in the reaction of pyrazole-based coordination compounds [Cuampf(NO3)2MeOH]·MeOH and [CuampfCl2] where ampf denotes N,N′-bis(4-acetyl-5-methyl pyrazole-3-yl)formamidine ligand, and two isocyanates, 1,6-diisocyanatohexane (HDI) and Bayhydur 3100 (Bay, a hydrophilic linear polymer based on 1,6-diisocyanatohexane) using dibutyltin-dilaurate catalyst. The formed materials were characterized by FT-IR spectrometry and thermal methods. The formation of the new polymers, besides the corresponding FT-IR spectra, was proved by differential scanning calorimetry (DSC) determining their glass transition temperatures. The thermal decomposition of the materials was examined by simultaneous thermogravimetric (TG) and DSC measurement. For the evaluation of the decomposition mechanism, the data obtained by coupled TG–mass spectrometric (MS) measurements were used. The thermal stability of the hybrid materials based on HDI was found substantially higher than that of the pure 1,6-diisocyanatohexane and decomposition of hybrid materials was more complex, while in the reaction of the metal complexes with Bay the thermal properties of the obtained hybrid polymers were changed only slightly, referring to a small amount of incorporated complexes.