Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Enzymatic Degradation and Aminolysis of Microbial Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) Single Crystals

Solution-grown single crystals of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3HB-co-4HB)] were hydrolyzed by polyhydroxybutyrate (PHB) depolymerase from Ralstonia pickettii T1. Enzymatic degradation proceeded from the edges of lamellar crystals, yielding serrated contour and small crystal fragments. Gel permeation chromatography analysis revealed that the molecular weights of the crystals decreased during enzymatic degradation, suggesting that the enzymatic hydrolysis of chain-folding regions at the crystal surfaces occurred in addition to the enzymatic degradation at crystal laterals or edges. After P(3HB-co-4HB) single crystals were aminolysed in 20% aqueous methylamine solution to remove the folded-chain regions and enzymatic degradation by lipase from Rhizopus oryzae to remove 4HB components at crystal surfaces of single crystal aminolyzed, it was found that a small amount (up to ca. 2 mol%) of 4HB component can be incorporated into the P(3HB) mother crystal lattice irrespective of the 4HB content.     

Infrared and nuclear magnetic resonance evidence of degradation in thermoplastics based on forest products

The degradation of lignin-(1-phenylethylene) graft copolymers (lignin-styrene graft copolymers) by white rot basidiomycete fungi was followed by monitoring aromatic absorption bands by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (NMR) spectroscopy. The FTIR of the graft copolymers shows a series of characteristic absorbance peaks from multi-substituted aromatic rings and a strong poly(1-phenylethylene) (polystyrene) absorbance peak from monosubstituted aromatic rings. Subtraction of copolymer spectra taken before incubation from spectra taken after 50 days of incubation with the four tested fungi shows the loss of functional groups from the copolymer. NMR spectra also show reduction of aromatic ring resonances from the copolymer and incorporation of peaks from fungi as a result of incubation with fungi. The biodegradation tests were run on lignin-(1-phenylethylene) graft copolymers which contained 10.3, 32.2, and 50.4% of lignin. The polymer samples were incubated with the white rot fungiPleurotus ostreatus, Phanerochaete chrysosporium, andTrametes versicolor, and the brown rot fungusGleophyllum trabeum. White rot fungi degraded the plastic samples at a rate that increased with increasing lignin content in the copolymer sample. Both poly(1-phenylethylene) and lignin components of the copolymer were readily degraded. Observation by scanning electron microscopy of incubated copolymers showed a deterioration of the plastic surface. The brown rot fungus did not affect any of these plastics, nor did any of the fungi degrade pure poly(1-phenylethylene).Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Properties and biodegradability of chain-extended copoly(succinic anhydride/ethylene oxide)

Chain-extension reactions were carried out using titanium-iso-propoxide (TIP) as a catalyst for a series of polyesters or copolyesterethers with low molecular weights (M _n =1500–10,000) synthesized by the ring-opening copolymerization of succinic anhydride (SA) with ethylene oxide (EO). The copolymers having aM _n from 25,000 to 50,000 of different properties were obtained. Both the melting point (T _m ) and the fusion heat (H), which indicate the crystallinity of the copolymers, rose with an increase in SA content in the copolymers. Semitransparent films were prepared by compression molding of the copolymers. The biodegradation of the copolymer films was evaluated by enzymatic hydrolysis by lipases and by an aerobic gas evolution test in standard activated sludge. The hydrolyzability of these copolymers by three kinds of lipases was affected by their copolymer composition SA/EO, form, andM _n . The copolyesterether (SA/EO=43/57,M _n =48,900) was more easily biodegraded by standard activated sludge compared to the polyester (SA/EO=47/53,M _n =36,300).Presented at the Pacifichem-95, December 17–22, 1995, Honolulu, Hawaii.     

Synthesis of Polylactide-b-Poly (Dimethyl Siloxane) Block Copolymers and Their Blends with Pure Polylactide

The synthesis of polylactide (PLA)-b-poly (dimethyl siloxane) (PDMS) linear block copolymers and their use in blends with pure-PLA are described. PLA-b-PDMS linear block copolymers were obtained by the transesterification reaction in chloroform solution between poly(dimethyl siloxane) bis (2-aminopropyl ether) (molecular weight 2,000?Da) with PLA in the presence of stannous octoate. Molecular weights (Mw) of the block copolymers were varied from 53,800 to 63,600?Da while that of pristine PLA was 73,600?Da. The copolymers obtained were purified by fractional precipitation and then characterized by ¹H NMR, FTIR, GPC, viscometry and DSC techniques. Blends of pure PLA with PLA-b-PDMS block copolymers displayed improved elastic properties (elongation up to 140%) compared to pure PLA (elongation ~9%). Thermal, mechanical and morphological characterization of the blends were also conducted.     

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.     

The Relationship Between the Chemical Structure of Poly(alkylene glycol)s and Their Aerobic Biodegradability in an Aqueous Environment

The relationship between the chemical structure of poly(alkylene glycol)s (PAGs) and their biodegradability was studied using a set of polymeric fluids that included poly(ethylene glycol), poly(propylene glycol) (PPG), random copolymers of ethylene oxide (EO) and propylene oxide (PO) differing in the EO/PO ratio as well as PAGs capped with ether or acyl moieties. The PAGs that were tested had an average molecular weight (MW) in the range of 350–3,600 Da and differed in their polymer backbones by either linear (diol type) or branched (triol type) molecules. The ultimate biodegradability of the PAGs was determined according to ISO 14593 (CO₂ headspace test) with a non-pre-exposed (as in OECD 310 test) and pre-exposed (adapted) inoculum. PAGs with the structure of PPG and copolymers of EO/PO of diol or triol structures with average molecular weights lower than 1,000 Da can be considered as readily biodegradable. Their ultimate biodegradation exceeds the limit of 60 % (according to the criteria of the OECD 310 test). PAGs with a copolymer structure and MW values ranging between 1,000 and 3,600 Da are not readily biodegradable, but they can be considered as those of inherent ultimate biodegradability. The increased EO content in PAG structures and the acylation of the terminal hydroxyl groups with carboxylic acids favourably influenced their biodegradability. Capped PAGs containing terminal ether groups appeared to be resistant to biodegradation.     

Polymerization of l-lactide with SnCl2: A Low Toxic and Eco-friendly Catalyst

Polymerizations of l-lactide catalyzed either by neat SnCl₂ or by SnCl₂?+?difunctional cocatalysts were conducted in bulk at 180, 160 and 140 °C with variation of the Lac/Cat ratio and time. With neat SnCl₂ poly(L-lactide) having weight average molecular weights (uncorrected M_w’s) up to 190 000 g mol^?1 were obtained mainly consisting of linear chains. Addition of salicylic acid or 1,1-bisphenol yielded a higher fraction of cyclic polylactides but lower molecular weights. Furthermore, SnCl₂ was compared with Bu₂SnCl₂ and various other metal chlorides and the best results were obtained with SnCl₂. With ethyl L-lactate as initiator SnCl₂-catalyzed ROPs were performed at 120 °C and the lac/initiator ratio was varied. All these experiments were conducted under conditions allowing for comparison with ROPs catalyzed with neat Sn(II)-2-ethyhexanoate. Such a comparison was also performed with ε-caprolactone as monomer.

     

Thermal Properties and Crystallization Behavior of Novel Biodegradable Poly(hexamethylene succinate-<Emphasis Type="Italic">co</Emphasis>-6 mol% butylene succinate) and Poly(hexamethylene succinate)

In this research, the thermal properties and crystallization behavior of novel poly(hexamethylene succinate-co-6 mol% butylene succinate) (PHBS) and its homopolymer poly(hexamethylene succinate) (PHS) were extensively studied. With respect to PHS, the introduction of a small content of butylene succinate (BS) unit slightly reduces the melting point and equilibrium melting point but hardly influences the glass transition temperature of PHBS. Despite crystallization temperature, PHS and PHBS crystallize through the same crystallization mechanism. At the same crystallization temperature, PHBS crystallizes more slowly than PHS; furthermore, lowering crystallization temperature enhances the crystallization rates of PHBS and PHS. The spherulites morphologies were observed for both of them, with the spherulites nucleation density of the copolymer being smaller than that of the homopolymer. PHBS and PHS share the same crystal structures, indicative of the location of BS unit in the amorphous region.     

Syntheses of Biodegradable Functional Polymers by Radical Ring-Opening Polymerization of 2-Methylene-1,3,6-trioxocane

2-Methylene-1,3,6-trioxocane (MTC) was polymerized via ring-opening in the presence of a radical initiator and the obtained polyester was biodegradable. MTC could also copolymerize with various vinyl monomers such as styrene, vinyl acetate, methyl vinyl ketone, N-vinyl-2-pyrrolidone, N-isopropyl acrylamide, and maleic anhydride. By copolymerizing MTC with these vinyl monomers in the presence of a radical initiator, we could obtain various biodegradable polymers with ester group introduced into the backbone. In addition the obtained copolymers exhibit certain functionalities such as photolysis, water-solubility, thermosensitivity, detergent builder, and water-absorbability.     

Studies on the enzymatic and fungal degradation of cross-linked gelatin and its graft copolymers

Glutaraldehyde cross-linked gelatin was graft copolymerized with acrylic acid, acrylamide, vinyl acetate, methyl acrylate, and methyl methacrylate either individually or in combination. The enzymatic and fungal degradation of these graft copolymers with trypsin, pepsin, and mixed cultures ofAspergillus niger, Penicillium ochrochloron, Penicillium funiculosum, andTrichoderma viride was studied for short and extended periods. The weight loss suffered by the samples, the weight of biomass formed, the nitrogen content, and the pH of the culture medium were determined. With the help of these data, the extent of utilization of graft copolymers by fungi as a sole source of carbon was estimated. The samples with less than 100% grafting and with a ratio of polymethyl methacrylate content (L) to polyacrylic acid (H) content (L/H values) lower than 1.0 were readily and extensively degraded.IICT Communication No. 3375.     

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.     

Preparation and Application of PEG/PVP Copolymers

In this study, we produced a series of environmentally friendly multifunctional additives by polymerization of biodegradable polyethylene glycol (PEG) and N-Vinyl-2-pyrrolidone in different proportions. The copolymer molecular structure was confirmed by Fourier transform infrared spectroscopy, and the impact of the copolymers on dye absorption and dye interaction was investigated. The results showed that the series of copolymers produced displayed enhanced dye decolorization with increasing copolymer dose and time. Additionally, the PEG/polyvinylpyrrolidone (PVP) copolymers and dye molecules interacted; addition of copolymer enabled shifts of the dye λ_max toward shorter wavelengths and decreased the UV absorbance. The addition of copolymers reduced the overall Zeta potential of the dye and increased the particle sizes, facilitating dye decolorization. In particular, the dye decolorization effect was the best when the PEG/PVP molar ratio was 8:1.     

Solvent-Free Polymerization of l-Aspartic Acid in the Presence of d-Sorbitol to Obtain Water Soluble or Network Copolymers

l-Aspartic acid was thermally polymerized in the presence of d-sorbitol with the goal of synthesizing new, higher molecular weight water soluble and absorbent copolymers. No reaction occurred when aspartic acid alone was heated at 170 or 200 °C. In contrast, heating sorbitol and aspartic acid neat or with ammonium hydroxide gave a mixture of water soluble and insoluble copolymers of polysuccinimide and sorbitol. In the presence of phosphoric acid, sorbitol aspartate ester copolymers having both water soluble and highly swollen gel components were formed. These results indicate that polysaccharides such as sorbitol can readily react to form copolymer ester/amides with aspartic acid and such copolymers may have utility as biodegradable water soluble and swellable polyampholytes.     

Degradation of poly(3-hydroxybutyrate), PHB,by bacteria and purification of a novel PHB depolymerase fromComamonas sp.

Bacteria capable of growing on poly(3-hydroxybutyrate), PHB, as the sole source of carbon and energy were isolated from various soils, lake water, activated sludge, and air. Although all bacteria utilized a wide variety of monomeric substrates for growth, most of the strains were restricted to degrade PHB and copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate, P(3HB-co-3HV). Five strains were also able to decompose a homopolymer of 3-hydroxyvalerate, PHV. Poly(3-hydroxyoctanoate), PHO, was not degraded by any of the isolates. One strain, which was identified asComamonas sp., was selected, and the extracellular depolymerase of this strain was purified from the medium by ammonium sulfate precipitation and by chromatography on DEAE-Sephacel and Butyl-Sepharose 4B. The purified PHB depolymerase was not a glycoprotein. The relative molecular masses of the native enzyme and of the subunits were 45,000 or 44,000, respectively. The purified enzyme hydrolyzed PHB, P(3HB-co-3HV), and—at a very low rate—also PHV. Polyhydroxyalkanoates, PHA, with six or more carbon atoms per monomer or characteristic substrates for lipases were not hydrolyzed. In contrast to the PHB depolymerases ofPseudomonas lemoignei andAlcaligenes faecalis T₁, which are sensitive toward phenylmethylsulfonyl fluoride (PMSF) and which hydrolyze PHB mainly to the dimeric and trimeric esters of 3-hydroxybutyrate, the depolymerase ofComamonas sp. was insensitive toward PMSF and hydrolyzed PHB to monomeric 3-hydroxybutyrate indicating a different mechanism of PHB hydrolysis. Furthermore, the pH optimum of the reaction catalyzed by the depolymerase ofComamonas sp. was in the alkaline range at 9.4.     

Anti-biofilm Activity of Solvent-Cast and Electrospun Polyhydroxyalkanoate Membranes Treated with Lysozyme

Biofilms consist of groups of microorganisms that adhere to surfaces, such as wound and implant surfaces, making it difficult to prevent or remove their formation by antibiotic treatment, due to the innate resistance of the biofilm. Effective treatments of medical biofilms are limited. Polyhydroxyalkanoate (PHA) is a biodegradable and biocompatible polymer that is a suitable alternative to petroleum based polymers for use as a raw material for medical applications. In this study, membranes of the copolymer poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(HB-co-HHx)] containing different HHx monomer contents were used due to its porosity and flexibility, and different sheets were prepared by solvent-casting and electrospinning methods. The sheets were loaded with lysozyme in order to measure the maximum amount of protein adsorption and to examine the ability of immobilized enzyme to inhibit biofilm formation and detach previously established biofilms. Our results have shown maximum loading of 16.1 µg enzyme per 9.5 mm³ discs, and these sheets are effective for inhibiting biofilm formation. Also, lysozyme loaded, eletrospun sheets were observed to more effectively inhibit biofilm formation, as compared to solvent-cast sheets. Based on this study, P(HB-co-HHx) sheets are a suitable material for being used as a potential raw material for fabrication of wound dressings to be used in anti-biofilm treatments.     

Biodegradation of an Epoxy-Based Thermoplastic Polyester, Poly(Hydroxy Ester Ether) in a Laboratory-Scale Compost System

An epoxy-based thermoplastic polyester, poly(hydroxy ester ether), was incubated under aerobic conditions in a laboratory-scale compost system for 168 days to evaluate its potential for biodegradation. Radiolabeled test polymer [uniformly ¹⁴C ring-labeled, poly(hydroxy ester ether)] was incorporated into a mature compost and a sludge-amended compost at a loading of 3 mg test polymer/g compost. ¹⁴C-Cellulose was used as the positive control and a biologically inhibited control reactor was used to assess abiotic degradation of the test polymer. Degradation of the test polymer was assessed by measuring the amount of ¹⁴C-CO₂ from each of the test reactors. In addition, at selected time intervals subsamples of the compost were collected and serially extracted with water, methanol, and dimethylformamide to monitor degradation of the ¹⁴C-test polymer and provide a partial characterization of the degradation intermediates. Extensive degradation of ¹⁴C-poly(hydroxy ester ether) was observed in the test reactors with degradation half-life of the parent polymer (t _1/2) of approximately 32 days. By the end of the study, only 2% of the total ¹⁴C activity in the test reactors was attributed to intact polymer, with most of the measurable ¹⁴C activity converted to either ¹⁴C-CO₂ (26% of total ¹⁴C activity) or nonextractable products (accounting for 60% of the total activity). In contrast to the test reactors, only 3% of the ¹⁴C-poly(hydroxy ester ether) added to the biologically inhibited control reactor was mineralized to ¹⁴C-CO₂. The results obtained from the microbially active and biologically inhibited compost systems indicate that the poly(hydroxy ester ether) polymer was degraded, at least in part, by a biologically mediated process.     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

The Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactide) Prepared by Different Synthesis Procedure

Different synthesis methods were applied to determine optimal conditions for polymerization of (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (l-lactide), in order to obtain poly(l-lactide) (PLLA). Bulk polymerizations (in vacuum sealed vessel, high pressure reactor and in microwave field) were performed with tin(II) 2-ethylhexanoate as the initiator. Synthesis in the vacuum sealed vessel was carried out at the temperature of 150 °C. To reduce the reaction time second polymerization process was carried out in the high pressure reactor at 100 °C and at the pressure of 138 kPa. The third type of rapid synthesis was done in the microwave reactor at 100 °C, using frequency of 2.45 GHz and power of 150 W at the temperature of 100 °C. The temperature in this method was controlled via infrared system for in-bulk measuring. The solution polymerization (with trifluoromethanesulfonic acid as initiator) was possible even at the temperature of 40 °C, yielding PLLA with narrow molecular weight distribution in a very short period of time (less than 6 h). The obtained polymers had the number-average molecular weights ranging from 43,000 to 178,000 g mol⁻¹ (polydispersity index ranging from 1 to 3) according to the gel permeation chromatography measurements. The polymer structure was characterized by Fourier transform infrared and NMR spectroscopy. Thermal properties of the obtained polymers were investigated using thermogravimetry and differential scanning calorimetry.     

Synthesis of a block copolymer of poly(3-hydroxybutyrate) and poly(ethylene glycol) and its application to biodegradable polymer blends

A block copolymer {P[(R,S)-HB-b-EG]} of atactic poly[(R,S)-3-hydroxybutyrate] {P[(R,S)-HB]} and poly(ethylene glycol) (PEG) was prepared by the ring-opening polymerization of -butyrolactone in the presence of a macroinitiator (PEG/ZnEt₂/H₂O) which had been produced by the reaction of ,-dihydroxy PEG ( _n=3000) with ZnEt₂/H₂O (1/0.6) catalyst. The block copolymer ( _n=10,500, _w/ _n=1.2) was an A-B-A triblock copolymer comprising atactic P[(R,S)-HB] (A) and PEG (B) segments. The miscibility, physical properties, and biodegradability of binary blends of microbial poly[(R)-3-hydroxybutyrate] {P[(R)-HB]} with the block copolymer P[(R,S)-HB-b-EG] has been studied. The glass-transition temperature (T _g) data showed that the P[(R)-HB]/P[(R,S)-HB-b-EG] blend was miscible in the amorphous state. The P[(R)-HB] film became flexible and tough by means of blending with P[(R,S)-HB-b-EG] block copolymer. The enzymatic degradation of blend films was carried out at 37°C and pH 7.4 in a 0.1M phosphate solution of an extracellular PHB depolymerase fromAlcaligenes faecalis. The enzymatic degradation took place solely on the surface of the blend films.