Joanna Rydz

Polyester-Based (Bio)degradable Polymers as Environmentally Friendly Materials for Sustainable Development

This review focuses on the polyesters such as polylactide and polyhydroxyalkonoates, as well as polyamides produced from renewable resources, which are currently among the most promising (bio)degradable polymers. Synthetic pathways, favourable properties and utilisation (most important applications) of these attractive polymer families are outlined. Environmental impact and in particular (bio)degradation of aliphatic polyesters, polyamides and related copolymer structures are described in view of the potential applications in various fields.

NOVEL SYNTHESIS OF FUNCTIONALIZED POLY(3-HYDROXYBUTANOIC ACID) AND ITS COPOLYMERS

Novel feasibility of fuctionalized poly(3-hydroxybutanoic acid), PHB, and its copolymers synthesis via ring-opening of beta-butyrolactone (ROP) mediated by activated anionic initiators or enzymes in vitro is presented. Using these new synthetic approaches, PHB with defined chemical structure of the end groups as well as block, graft and random copolymers have been obtained and characterized by IR, NMR, ESI-MS and GPC techniques. The relationship between the structure and properties of the novel polymeric materials prepared is discussed.

Enzymatic synthesis of polyesters from hydroxyl acids

Abstract With porcine pancreatic lipase (PPL) as catalyst, aliphatic polyesters with hydroxyl and carboxyl end groups were synthesized through polycondensation of 3-hydroxybutyric acid (3-HBA) or 12-hydroxydodecanoic acid (12-HDA). The molecular weight ( M n , number average) of obtained polymers varies from several hundred to several thousand depending on monomer used and reaction conditions as well. Resultant polymers were characterized by IR, 1 H-NMR and GPC.

A preliminary study of the degradation of selected commercial packaging materials in compost and aqueous environments

A preliminary study of the degradation of selected commercial packaging materials in compost and aqueous environments The paper presents the results of the degradation of two commercial packaging materials CONS-PET and BioPlaneta in the compost and distilled water at 70°C. The materials containing polylactide (PLA), CONS-PET 13% and BioPlaneta 20%, aliphatic-aromatic copolyester terephthalic acid/adipic acid/1,4-butanediol (BTA) and commercial additives degraded under the industrial composting conditions (composting pile or container) and in distilled water at 70°C in the laboratory holding oven. Distilled water provided the conditions for the hydrolytic (abiotic) degradation of the materials. Weight loss, changes of molecular weight, dispersity monitored via the GPC technique and the macroscopic surface changes of the tested materials were monitored during the experiments. The investigated systems show similar trends of degradation, however on the last day of the incubation the decrease of the molecular weight was higher in water than under the industrial composting conditions. The results indicate that commercial packaging materials can be degraded both while composting ((bio)degradation) and during the incubation in distilled water at 70°C (abiotic hydrolysis).

Forensic Engineering of Advanced Polymeric Materials. Part 1 –Degradation Studies of Polylactide Blends with Atactic Poly[(R,S)-3-hydroxybutyrate] in Paraffin

Classical forensic polymer engineering concerns a study of failure in polymer products. This area of science comprises fracture of plastic products, or any other reason why such a product fails in service, or fails to meet its specification.1 So far, most of the reported case studies concern ex-post investigations of traditional polymeric materials such as PE, PP, PS, PVC, ABS or their thermoplastic composites. Little is known about forensic engineering of novel and advanced polymeric materials. Thus, there is a real gap in this area of knowledge. Furthermore, the ex-ante studies are needed to define and minimise the potential failure of novel polymer products before specific applications. Environmental stress cracking (ESC) is one of the most common causes of unexpected brittle failure of thermoplastic (especially amorphous) polymers. The rate of ESC is dependent on many factors, including, for example, the polymer’s chemical composition, bonding, crystallinity, surface roughness, molar mass and residual stress. It also depends on the chemical nature of liquid media and the temperature of the system. Thus, evaluation and understanding of the structure, properties and behaviour of advanced polymer materials for perspective practical applications is needed, especially in the field of compostable polymer packages of long-life products, such as cosmetics or household chemicals. Because of the slow environmental degradation of traditional packaging, the use of conventional plastics is accompanied by significant ecological problems. To reduce plastic waste from the packaging industry, biodegradable polymers have become interesting alternatives, for packages with a long shelf life.2 The most important environmentally friendly plastics are generally based on aliphatic polyesters, such as poly(lactic acid), poly(3-hyForensic Engineering of Advanced Polymeric Materials. Part 1 – Degradation Studies of Polylactide Blends with Atactic Poly[(R,S)-3-hydroxybutyrate] in Paraffin

Water-soluble L-alanine and related oligopeptide conjugates with poly[(R,S)-3-hydroxybutanoic acid] oligomers. Synthesis and structural studies by means of electrospray ionization multistage mass spectrometry

The reactions of (R,S) β-butyrolactone with L-alanine and related oligopeptides (Ala-Ala-Ala) were investigated. The resulting water-soluble oligomers were composed of poly[(R,S)-3-hydroxybutanoic acid] (a-PHB) covalently conjugated to L-alanine and Ala-Ala-Ala oligopeptide. The other chain end was of the carboxylic acid type. The structure of the obtained oligomers was assessed by electrospray ionization multistage mass spectrometry (ESI-MSn) and the respective structural information was completed by IR, NMR, and GPC analyses. The molecular weight and structure of the products could be controlled through reaction conditions. Using this new synthetic approach, a-PHB oligomers with well-defined end groups, as well as respective block copolymers, can be prepared via regioselective ring-opening oligomerization of (R,S)β-butyrolactone induced by amino acids under their zwitterionic form.

Bio)degradation studies of degradable polymer composites with jute in different environments

The introduction of new, environmentally friendly and sustainable plastics in the packaging and end-user industry is a solution to the problem of waste management. The degradation of polyesters in different environments could result from an enzymatic attack or simple hydrolysis, or both. The degree of degradation of blends containing polylactide and poly(3-hydroxybutyrate-co-4-hydroxybutyrate), PLA/P(3HB-co-4HB), and its composites with 20 %wt of jute incubated in distilled water at 70 ℃ (abiotic conditions) under industrial composting conditions (system KNEER) was investigated using a Zeiss optical microscope, an atomic force microscope, gel permeation chromatography, differential scanning calorimetry and thermal gravimetric analysis. PLA/P(3HB-co-4HB) was tested under laboratory composting conditions in order to verify whether biodegradation of this material occurs under industrial composting conditions. The addition of jute fibres did significantly reduce the disintegration of the composites during degradation.

Synthesis of aPHB-PEG Brush Co-polymers through ATRP in a Macroinitiator–Macromonomer Feed System and Their Characterization

A brush co-polymer composed of a biodegradable hydrophobic poly((R,S)-3-hydroxybutyrate) chain and biocompatible hydrophilic poly(ethylene glycol) brushes was designed as amphiphilic self-aggregating species with potential application in the health-care field. The co-polymer was prepared applying a three-step procedure: (i) ring-opening anionic polymerization of (R,S)-β-butyrolactone initiated by 2,2-bis(hydroxymethyl)butyric acid tetrabutyl ammonium salt yielding polyester with two hydroxyl functionalities at one chain terminus, (ii) synthesis of PHB-derived microinitiator species and (iii) ATRP of polyethylene glycol methyl ether methacrylate yielding an amphiphilic co-polymer. Chain structures and/or end-group functionalization were proven by 1H- and 13C-NMR spectroscopy of the products at each step of the synthetic procedure. The molecular weight and structure of the end-product were close to the expected values. The self-aggregation behavior of the brush co-polymer in an aqueous medium was evidenced by optical absorption probe technique and dynamic/static light scattering measurements.

Forensic engineering of advanced polymeric materials Part IV: Case study of oxo-biodegradable polyethylene commercial bag – Aging in biotic and abiotic environment

The public awareness of the quality of environment stimulates the endeavor to safe polymeric materials and their degradation products. The aim of the forensic engineering case study presented in this paper is to evaluate the aging process of commercial oxo-degradable polyethylene bag under real industrial composting conditions and in distilled water at 70°C, for comparison. Partial degradation of the investigated material was monitored by changes in molecular weight, thermal properties and Keto Carbonyl Bond Index and Vinyl Bond Index, which were calculated from the FTIR spectra. The results indicate that such an oxo-degradable product offered in markets degrades slowly under industrial composting conditions. Even fragmentation is slow, and it is dubious that biological mineralization of this material would occur within a year under industrial composting conditions. The slow degradation and fragmentation is most likely due to partially crosslinking after long time of degradation, which results in the limitation of low molecular weight residues for assimilation. The work suggests that these materials should not be labeled as biodegradable, and should be further analyzed in order to avoid the spread of persistent artificial materials in nature.

Forensic Engineering of Advanced Polymeric Materials—Part V: Prediction Studies of Aliphatic–Aromatic Copolyester and Polylactide Commercial Blends in View of Potential Applications as Compostable Cosmetic Packages

The main aim of the present study was to determine the behavior of the specimens from Ecovio, in the form of dumbbell-shaped samples and films, during degradation in selected cosmetic ingredients such as water and paraffin. The (bio)degradation test of the prototype cosmetic package (sachet) made from a PBAT (poly[(1,4-butylene adipate)–co–(1,4-butylene terephthalate)]) and PLA (polylactide) blend was investigated under industrial composting conditions, and compared with the sample behavior during incubation in cosmetic media at 70 °C. During the degradation tests, the changes of the samples were evaluated using optical microscopy, 1H NMR (proton nuclear magnetic resonance) and GPC (gel permeation chromatography) techniques. The structures of the degradation products were investigated using ESI-MSn (mass spectrometry with electrospray ionization on positive and negative ions) analysis. The thermal properties of selected materials were determined by DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) analysis. It was concluded that the PBAT and PLA blend studied had a good stability during aging in cosmetic media, and could be recommended for long-shelf-life compostable packaging of cosmetics, especially with oily ingredients.