Evaluation of biodegradability of poly(ε-caprolactone)/poly(ethylene terephthalate) blends

The results of an investigation aimed at evaluation of the biodegradability of blends of poly(-caprolactone) (PCL) with poly(ethylene terephthalate) (PET) as the major component are reported. Specimens of the blends, as melt extruded films and/or powders, were submitted to degradation tests under different environmental conditions including full-scale composting, soil burial, bench-scale accelerated aerobic degradation, and exposure to axenic cultures and esterolytic enzymes. Indications have been gained that blending in the melt gives rise to insertion of PCL segments in the PET chain. Copolymers thus attained acted as macromolecular compatibilizers, allowing for a complete miscibility of PCL and PET. The biodegradation detected on the blend samples was, however, well below the values expected from chemical composition and behavior of individual homopolymers under the same environmental conditions. The presence of PET as the major component in PET/PCL blends apparently reduces the propensity of PCL to be degraded, at least in the investigated composition range. The degradation data collected under different environmental conditions indicate that the full-scale composting system is the most efficient among the tested degradation procedures.     

Physical state and biodegradation behavior of starch-polycaprolactone systems

The biodegradation behavior of insoluble crystalline polymers depends on both chemical structure and physical state. The physical state is strongly affected by the molding conditions; moreover the presence of natural hydrophylic substances such as starch can further influence the biodegradation process. This paper examines the biotic and abiotic degradation of thick injection-molded parts, made of pure poly--caprolactone (PCL) at different molecular weights, and of PCL in the presence of starch in the case of a commercial grade of Mater-Bi, produced by Novamont. The abiotic degradation was studied at 25 and 50°C, whereas the biotic degradation was followed in conditions of SCAS (semicontinuous activated sludges) at 25 and 50°C, soil burial, and controlled composting. The physical-chemical modifications provoked at the surface and in the bulk of the samples by the different types of degradation were determined by differential scanning calorimetry, viscometric and gravimetric analysis, scanning electron microscopy, and dynamic mechanical analysis. The mechanical modifications induced by the different environments were followed by tensile tests. It was demonstrated that the presence of starch significantly increases the apparent biodegradation rate of PCL, making even thick parts of ZI01U compatible with the composting process.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

Synthesis and environmental degradation of polyesters based on poly (ε-caprolactone)

Poly (-caprolactone) (PCL), poly (-valerolactone) (PVL), poly (-caprolactone-co--valerolactone) [P(CL-co-VL)], and poly (-caprolactone-co-ethylene oxide-co--caprolactone) (PCL-PEO-PCL) were synthesized by ring-opening and diol-initiated polymerization of -caprolactone and -valerolactone. The degradation of the samples by chemical hydrolysis and in a soil burial test was evaluated. It was found that PCL, PVL, and P(CL-co-VL) degrade mainly enzymatically. The rate of degradation depends on their molecular weight, chemical structure, composition, and morphology. PCL-PEO-PCL block copolymers exhibit a repelling effect to the microorganisms in the soil, which depends on the molecular weight and relative amount of PEO block in the copolymer.     

Distribution of Poly(β-propiolactone) Aerobic Degrading Microorganisms in Different Environments

The distribution of degading microorganisms of high molecular weight poly(-propiolactone) (PPL), whose individual structural units are similar to those of poly(-hydroxybutyrate) (PHB) and poly(€-caprolactone) (PCL), was examined. Despite the fact that PPL is a chemosynthetic polymer, many kinds of PPL-degrading microorganisms were found to be distributed as resident populations widely in natural environments. A total of 77 strains of PPL-degrading microorganisms was isolated. From standard physiological and biochemical tests, at least 41 strains were referred to as Bacillus species. Microbial degradation of fibrous PPL proceeded rapidly in some enrichment cultures but was not as complete as that of PHB. Most of the isolated PPL-degrading microorganisms were determined to be PCL degraders and/or PHB degraders. Therefore, it can be assumed that mostly PPL is recognized by the microorganisms as PHB or another natural substrate of the same type as which PCL is regarded. Microbial degradation of PPL was confirmed by some Bacillus strains from type culture collections. The similarity of microbial degradation between PPL and PCL was found to be very close.     

Mechanical Properties and Lipase-Catalyzed Biodegradation of α-Methyl, ε-Caprolactone/ ε-Caprolactone Copolymers Obtained by Chemical Modification of Poly(ε-caprolactone)

Novel (-caprolactone)-based copolymers of different compositions were synthesized by allowing methyl iodide to react with the polycarbanion that resulted from the action of lithium diisopropylamide on poly(-caprolactone) in THF at –70°C under argon atmosphere. The copolymers were characterized by various techniques, namely ¹H nuclear magnetic resonance, size exclusion chromatography, differential scanning calorimetry, x-ray diffraction and viscoelasticimetry. They were submitted to hydrolytic and lipase-catalyzed enzymatic degradation in comparison with genuine PCL. The Young modulus depended on the degree of methylation. In contrast, loss angle and glass transition temperature did not depend on this parameter. It is shown that the lipase-catalyzed degradation of methylated PCL is much slower than in the case of genuine PCL.     

Soybean-Oil-Based Polyisocyanurate Rigid Foams

Polyisocyanurate foams were prepared from polymeric 4,4-diphenylmethane diisocyanate (MDI), soy polyol and polypropylene oxide polyol by varying isocyanate index from 110 to 350. The higher isocyanate index produced polyisocyanurate foams with higher thermal stability, improved flame resistance, tensile strength, higher modulus, and higher glass transition. Soy-based foams displayed better thermal stability, lower flammability, higher rigidity (modulus) and higher compression strength than those based on the propylene oxide polyols of the same molecular weight and functionality.     

The Effect of UV-B Irradiation on the Biodegradability of Poly-β-Hydroxybutyrate (PHB) and Poly-ɛ-Caprolactone (PCL)

The biodegradability of poly--hydroxybutyrate and poly--caprolactone in soil compostage before and after irradiation of the polymers for 192, 425, and 600 h in a Weather-Ometer was examined. The biodegradability tests were done in soil compostage at pH 7.0, 9.0, and 11.0 to assess the influence of this parameter on degradation. The rate of degradation was directly proportional to the soil alkalinity. Poly--hydroxybutyrate showed the greatest weight loss and aging in a Weather-Ometer did not significantly increase the biodegradation, except when the polymer was aged for 425 h and buried in soil compostage of pH 11.0.     

Radiation Effects on Blends of Poly(ε-Caprolactone) and Diatomites

Poly(-caprolactone) (PCL) was blended with diatomaceous earth (diatomite) and irradiated with -rays to introduce cross-linking between PCL molecules or both components. The unwashed diatomite containing a little of a volatile component showed high efficiency of introduction of cross-linking, whereas that with no volatile component showed low efficiency of introduction of cross-linking. Elongational viscosity, melt viscosity, and modulus of PCL/diatomite blend irradiated at various doses were significantly improved. Enzymatic degradation of the PCL/diatomite blend became faster than that of the PCL, though that of the blend irradiated became slower.     

Kinetics of Aerobic Polymer Degradation in Soil by Means of the ASTM D 5988-96 Standard Method

The standard test method ASTM D 5988-96 for determining the degree and rate of aerobic biodegradation of plastic materials in contact with soil was applied to poly(3-hydroxybutyrate) and poly(-caprolactone). The method proved to be reliable and supplied reproducible measurements of CO₂ production, provided potassium (instead of barium) hydroxide was used as a trapping solution. The trends of CO₂ evolution, as a function of time, observed for the degradation of polymer powders in soil are similar to those predicted by simple first order kinetics in solution. The experimental data are described by a Michaelis–Menten type model, which accounts for the heterogeneity of the polymer-soil system. The kinetic equation deduced predicts the degradation rate to the proportional to the exposed polymer surface area.     

Distribution of poly(β-hydroxybutyrate) and poly(ε-caprolactone)aerobic degrading microorganisms in different environments

To assess the capacity of the natural environment for degrading plastics, the populations of poly(-hydroxybutyrate)(PHB)-and poly(-caprolactone)(PCL)-degrading aerobic microorganisms and their ratios to the total number of microorganisms in soil samples were estimated by the plate count method with agar medium containing emulsified PHB or PCL. The numbers of the degrading microorganisms were determined by counting colonies that formed clear zones on the plate. It was found that PHB- and PCL-degrading (depolymerizing) microorganisms are distributed over many kinds of material, including landfill leachate, compost, sewage sludge, forest soil, farm soil, paddy soil, weed field soil, roadside sand, and pond sediment. Of total colony counts, the percentages of PHB and PCL degrading microorganisms were 0.2–11.4 and 0.8–11.0%, respectively. The results suggest that many kinds of degrading microorganisms are present in each environment and that specific consortia differing in biodegradation capacity are constructed.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

Synthesis of copolyesters containing poly(ethylene terephthalate) and poly(ε-caprolactone) units and their susceptibility toPseudomonas sp. lipase

Copolyesters containing poly(ethylene terephthalate) (PET) and poly(-caprolactone) (PCL) were synthesized from PET and PCL homopolymers by transesterification reaction at 270°C in the presence of catalyst. The copolyesters were characterized by¹³C-NMR and differential scanning calorimetry (DSC). The degradation behavior of PCL byPseudomonas sp. lipase in buffer solution (pH 7) and tetrahydrofuran (THF) was investigated by gel permeation chromatography (GPC) and¹H-NMR. From these experiments, it was found thatPseudomonas sp. lipase acted endoenzymatically on PCL. Using this lipase, degradation tests for PET/PCL copolyesters whose PCL content was below 50% by weight were also performed in buffer solution (pH 7). However, evenPseudomonas sp. lipase with high degradation activity on PCL did not easily degrade the PCL unit in PET/PCL copolyesters.     

Synthesis of Polyurethane and Characterization of its Composites Based on Alfa Cellulose Fibers

Polyurethane (PU) based on polycaprolactone (PCL) and 4,4′ diphenyl methylene diisocyanate (MDI) was synthesized using a two-step method. The PU obtained was then blended with various amounts of cellulose extracted from alfa stems to prepare composite materials. The influence of cellulose on the thermal and mechanical properties of different composites was demonstrated by means of several characterization techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), scanning electron microscopy (SEM)…     

In Vitro Biodegradation of Polyester-Based Plastic Materials by Selected Bacterial Cultures

A simple and rapid in vitro test was designed for the assessment of the biodegradation of polyester-based plastics by selected biodegrading bacterial strains. Variovorax paradoxus LMG 16137 was used for the degradation of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and Acidovorax avenae subsp. avenae LMG 17238 fo the synthetic-based polyesters poly(-caprolactone) (PCL), poly(butylene succinate-co-butylene adipate), and a starch-PCL blend. Degradation by the bacteria was studied in liquid medium with the plastics (films, granules, and injection-molded test bars) as sole sources of carbon. Degradation was followed through gravimetry, growth of the culture, and tensile testing. The effects of incubation time, inoculum density, aeration, incubation temperature, and pH of the medium on the mass loss were investigated and conditions optimized. The test allowed to obtain reproducible results on the mass loss of plastic samples in less than 3 weeks and yielded excellent partially degraded samples for further analysis.     

Preparation conditions and swelling equilibria of biodegradable hydrogels prepared from microbial poly(γ-glutamic acid) and poly(ε-lysine)

Biodegradable hydrogels prepared by -irradiation from microbial poly(amino acid)s are reviewed. pH-sensitive hydrogels were prepared by means of -irradiation of poly(-glutamic acid) (PGA) produced byBacillus subtilis IFO3335 and poly(-lysine) (PL) produced byStreptomyces albulus in aqueous solutions. The preparation conditions, swelling equilibria, hydrolytic degradation, and enzymatic degradation of these hydrogels were studied. A hydrogel with a wide variety of swelling behaviors has been produced by -irradiation from a mixture solution of PGA and PL.Paper presented at the 4th International Workshop on Biodegradable Plastics and Polymers, October 11–14, 1995, Durham, New Hampshire, USA.     

Influence of Short Central PEO Segment on Hydrolytic and Enzymatic Degradation of Triblock PCL Copolymers

Hydrolytic, enzymatic degradation and composting under controlled conditions of series of triblock PCL/PEO copolymers, PCEC, with central short PEO block (M _n 400 g/mol) are presented and compared with homopolymer (PCL). The PCEC copolymers, synthesized via ring-opening polymerization of ε-caprolactone, were characterized by ¹H NMR, quantitative ¹³C NMR, GPC, DSC and WAXS. The introduction of the PEO central segment (<?2 wt%) in PCL chains significantly affected thermal degradation and crystallization behavior, while the hydrophobicity was slightly reduced as confirmed by water absorption and moisture uptake experiments. Hydrolytic degradation studies in phosphate buffer after 8 weeks indicated a small weight loss, while FTIR analysis detected changes in crystallinity indexes and GPC measurements revealed bulk degradation. Enzymatic degradation tested by cell-free extracts containing Pseudomonas aeruginosa PAO1 confirmed high enzyme activity throughout the surface causing morphological changes detected by optical microscopy and AFM analysis. The changes in roughness of polymer films revealed surface erosion mechanism of enzymatic degradation. Copolymer with the highest content of PEO segment and the lowest molecular weight showed better degradation ability compared to PCL and other copolymers. Furthermore, composting of polymer films in a model compost system at 37 °C resulted in significant degradation of the all synthesized block copolymers.     

Characterization and enzymatic degradation of a cross-linked bacterial polyester

The bacterial polyester, poly(-hydroxybutyrate-co--hydroxyvalerate) (PHB/V), was cross-linked with 1, 5, 7, 10, 20, and 30 wt% benzoyl peroxide by thermal decomposition reactions. Solvent extractions were carried out to determine the cross-linked fractions of the films. The sol/gel data were used to estimate cross-link densities. Films of PHB/V cross-linked with 10% benzoyl peroxide were placed in contact with purified depolymerase A secreted byP. lemoignei. These samples exhibited weight loss rates which were half that of un-cross-linked PHB/V, but the network was degraded completely by the enzyme. The results of this study suggest that anendo-type enzymatic degradation may occur, in addition to theexo-type activity, which is normally presumed to occur with theP. lemoignei depolymerase system.     

Influence of Processing Additives on the Degradation of Melt-Pressed Films of Poly(ε-Caprolactone) and Poly(Lactic Acid)

Melt-pressed films of polycaprolactone (PCL) and poly(lactic acid) (PLA) with processing additives, CaCO₃, SiO₂, and erucamide, were subjected to pure fungal cultures Aspergillus fumigatus and Penicillium simplicissimum and to composting. The PCL films showed a rapid weight loss with a minor reduction in the molecular weight after 45 days in A. fumigatus. The addition of SiO₂ to PCL increased the rate of (bio)erosion in A. fumigatus and in compost. The use of a slip additive, erucamide, was shown to modify the properties of the film surface without decreasing the rate of bio(erosion). Both the rate of weight loss and the rate of molecular weight reduction of PCL increased with decreasing film thickness. The addition of CaCO₃ to PLA significantly reduced the thermal degradation during processing, but it also reduced the rate of the subsequent (bio)degradation in the pure fungal cultures. PLA without additives and PLA containing SiO₂ exhibited the fastest (bio)degradation, followed by PLA with CaCO₃. The degradation of the PLA films was initially governed by chemical hydrolysis, followed by an acceleration of the weight change and of the molecular weight reduction. PLA film subjected to composting exhibits a rapid decrease in molecular weight, which then remains unchanged during the measurement period, probably because of crystallization.     

Development and Application of Green Composites: Using Coffee Ground and Bamboo Flour

Environmental degradation and global warming are increasing as a result of the use of petroleum. Therefore, many industries are seeking more eco-friendly materials that will decrease the level of environmental contamination and economic cost. Recently, the level of coffee consumption has increased rapidly. Therefore, the amount of coffee grounds discarded is increasing. In this study, polylactic acid, coffee grounds and bamboo flour were compounded for green composites. Coffee grounds are used in the recycling of food waste. In addition, 4,4-methylene diphenyl diisocyanate (MDI) was used as a coupling agent. The mechanical strength of green composites decreased with increasing natural filler content. However, mechanical and thermal properties were increased by the addition of MDI as a coupling agent. The hydroxyl groups of natural fillers reacted with the isocyanate group of MDI, and a urethane linkage was created between the polymer and natural fillers.     

Enzymatic degradation of poly([R,S] β-hydroxybutyrate)

The synthetic analogue of a bacterially produced polyester, poly(-hydroxybutyrate) (PHB) was synthesized from racemic -butyrolactone using anin situ trimethyl aluminum-water catalyst. The polymer was fractionated into samples differing in molecular weight and isotactic diad content. The latter was closely related to degree of crystallinity. The biodegradation of these fractions were examined by monitoring mass loss over time in the presence of anAlcaligenes faecalis T1 extracellular bacterial poly(-hydroxybutyrate) depolymerase. The fraction with high isotactic diad tacticity content showed little or no degradation over a 50 hour incubation period, whereas the fraction of intermediate isotactic diad content degraded in a continuous steady fashion at a rate that was less than that for bacterial PHB. The low isotactic diad fraction underwent a rapid initial degradation, followed by no further mass loss. The presence of stereoblocks in the polymer structure of the various fractions was an influence on the degree of susceptibility towards degradation and is related to sample crystallinity.