Synthesis and processability into textile structures of radiopaque,biodegradable polyesters and poly(ester‐urethanes)

Radiopaque biodegradable polymers have been synthesized by ring‐opening polymerization of l /dl ‐lactide and caprolactone with the iodine‐containing starter molecule 2,2‐bis(hydroxymethyl)propane‐1,3‐diyl bis(2,3,5‐triiodobenzoate) followed by chain elongation with a diacid chloride or diisocyanates. The resulting polyesters and poly(ester‐urethanes) exhibited a radiopacity of 60?124% relative to an aluminium sample of the same thickness. The polymers were processed into monofilament fibres by melt‐spinning and into fibre meshes by electrospinning. All polymers were biodegradable in simulated body fluid medium under in vitro conditions and showed an excellent in vitro cytocompatibility even after several months of hydrolytic degradation. A current drawback is the relatively low tensile strength of the polymer monofilaments, which needs to be improved for applications as textile structures. Nevertheless, the new radiopaque and biodegradable polymers are promising candidates in fields of application where radiopacity of implants is an important parameter.     

Migration resistant glucose esters as bioplasticizers for polylactide

Environmental and sustainability issues have catalyzed efforts to replace traditional polymer additives with biobased alternatives. Glucose pentaacetate (GPA) and sucrose octaacetate (SOA) as model commercial saccharide esters and three synthesized glucose hexanoate esters (GHs) were evaluated as bioplasticizers for polylactide (PLA). For the GHs different reaction times were utilized to reach plasticizers with different number of hexanoate groups to establish how the degree of substitution influences miscibility and migration resistance of the plasticizers. The synthesized GHs, GPA, and SOA all showed good miscibility with PLA. Largest improvements in strain at break were observed for the PLA films containing GH plasticizers. These films also exhibited simultaneous increase in stress at break as compared to plain PLA. The GH plasticizers had low tendency to migrate during aging in water and this migration resistance increased with increasing degree of substitution. The GHs are, thus, promising plasticizer alternatives for bioplastics as they also retain the biodegradable nature of these biobased materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41928.     

Photooxidative stability provided by condensed tannin additives in acrylic-based surface coatings on exterior exposure

Condensed tannins, also known as proanthocyanidins, have been added as functional additives to acrylic-based clear coatings to promote polymer coating longevity and also stabilize timber color on accelerated and exterior weathering. When added at <?0.5% w/w content, native tannins and tannins modified with maleate groups extended coating performance >?20% compared to commercial hindered amine light stabilizers (HALS) and phenolic stabilizers used at comparable coating loadings. Other tannin chemical modifications such as methylcarboxylate groups were also associated with greater coating longevity beyond that achieved with the synthetic UV and antioxidant additives. This study has also revealed that tannin addition to acrylic coatings can act to photostabilize timber coloring on exterior exposure. While tannin use can contribute color to coatings, any color was rapidly bleached on UV exposure with a dependency on tannin content, degree of modification, and coating formulation pH. Moreover, through manipulating tannin addition levels, this tannin decolorization could offset typical wood darkening associated with UV exposure to provide low or no wood color change over longer exposure periods. With the photooxidative stability efficacy of tannins established on exterior exposure, condensed tannins in native and modified form offer potential as sustainable functional additives for the coatings sector.     

Intensity enhancement of photoluminescent polyesters by photocrosslinking

A series of polyesters with alkylated triazole heterocyclic rings at the branches were designed and synthesized via the polycondensation reaction. The synthesized polyesters were examined with various spectroscopic methods such as Fourier transform IR, ¹H NMR and ¹³C NMR. The alkyl chain length at the branch was found to affect the thermal stability of the polyesters, which decreased with longer alkyl chain. These polyesters possessed an aggregation‐induced emission enhancement characteristic evidenced by the transformation of the clear solutions in tetrahydrofuran with weak greenish blue emission to cloudy solutions with enhanced blue emission when water was added to promote aggregation. Furthermore, enhancement in the photoluminescence intensity was observed when the polyesters underwent photocrosslinking upon UV irradiation and appeared as self‐assembled aggregates. The formation of aggregates in the water ? tetrahydrofuran solutions and after photocrosslinking was confirmed via TEM analysis. The SEM images showed that the photocrosslinked polyesters were highly porous which may enhance the π ? π stacking interaction that improved the photoluminescence intensity. © 2015 Society of Chemical Industry     

Eumelanin for nature‐inspired UV‐absorption enhancement of plastics

In the human body, the black‐brown biopigment eumelanin blocks harmful ultraviolet (UV) radiation. In the plastics industry, additives are often added to polymers to increase their UV‐absorption properties. We herein report an assessment of the biopigment eumelanin as a nature‐inspired additive for plastics to enhance their UV absorption. Since eumelanin is produced by natural sources and is nontoxic, it is an interesting candidate in the field of sustainable plastic additives. In this work, the eumelanin‐containing films of commercial ethylene–vinyl acetate copolymer, a plastic used for packaging applications, were obtained by melt compounding and compression molding. The biopigment dispersion in the films was improved by means of the melanin free acid treatment. It was observed that eumelanin amounts as low as 0.8 wt% caused an increase of the UV absorption, up to one order of magnitude in the UVA range. We also evaluated the effect of eumelanin on the thermal stability and photostability of the films: the biopigment proved to be double‐edged, working both as UV‐absorption enhancer and photo‐prooxidant, as thermogravimetric analysis and infrared spectroscopy revealed. © 2019 Society of Chemical Industry     

Photoluminescent enhancement of polyesters via photocrosslinking

A homologous series of soluble photoluminescent polyesters, namely poly{bis(4‐hydroxybenzylidene)acetone‐5‐(m‐alkyloxyisophthalate)}, PAI1‐PAI5 were designed and synthesized via polycondensation reaction. The branches of these polyesters consisted of flexible alkyloxy chains with different chain lengths in order to investigate their influence toward thermal stability as well as the photocrosslinking property. It was found that increasing length of the flexible chain would reduce the thermal stability of the polyesters. Irradiation of these polyesters under UV light induced photocrosslinking and showed fascinate enhancement in their photoluminescence property with greater emission intensity. This was evidenced visually from the transformation of a weak greenish blue emission to highly intense cloudy blue emission. The photocrosslinking system was further confirmed using spectroscopic methods. Morphology analysis using SEM showed that the photocrosslinked polyesters have a fiber‐like or thread‐like texture with more voids as compared to the virgin polyesters. This was because of the formation of cyclobutanes through photodimerization involving 2π + 2π cycloaddition. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41504.     

Synthesis and characterization of high‐molecular weight aliphatic polyesters from monomers derived from renewable resources

A series of high‐molecular weight aliphatic polyesters have been synthesized, at temperatures of < 200°C, through a polycondensation reaction between 1,4‐butanediol and three diacids of different chain length (succinic acid, azelaic acid, and sebacic acid). All the polyesters obtained have a bio‐based content of 100% and number average molecular weight in the range of 28,000–116,000 Da. These average molecular weights are about 5–10 times higher than those of most reported aliphatic polyesters synthesized through similar reaction routes but at temperatures > 230°C. The over‐heating phenomenon, i.e., the observation of thermal degradation behavior of these polyesters at 230°C is reported. The crystallization behavior, mechanical properties, and enzymatic hydrolysis rate of the polyesters obtained are characterized. Poly(butylene succinate) (PBSu) shows the highest crystallinity and melting temperature, but the lowest thermal stability and slowest potential rate of enzymatic biodegradation rate compared with poly(butylene azelate) and poly(butylene sebacate). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40579.     

Synthesis and characterization of biodegradable polyurethanes with unsaturated carbon bonds based on poly(propylene fumarate)

The segmented polyurethanes synthesized from biodegradable polyesters are very promising and widely applicable because of their excellent physiochemical properties. Poly(propylene fumarate) (PPF), a kind of linear aliphatic unsaturated and biodegradable polyesters, has been well recognized in biomedical applications. Herein novel polyurethanes (PPFUs) were synthesized based on the PPF‐diol, diisocyanates such as 1,6‐diisocyanatohexane, l ‐lysine diisocyanate, and dicyclohexylmethane diisocyanate, and chain extenders such as 1,4‐butylene glycol and l ‐lysine methyl ester hydrochloride (Lys‐OMe·2HCl). By varying the types of diisocyanates, and chain extenders, and the proportion of hard segments, the PPFUs with tailored properties such as mechanical strength and degradation rate were easily obtained. The synthesized PPFUs had an amorphous structure and slight phase separation with strong hydrogen bonding between the soft segments and the hard segments. The elongation of PPFU elastomers reached over 400% with a slow deformation‐recovery ability. The PPFUs were more sensitive to alkaline (5 M, NaOH) hydrolysis than acid (2 M, HCl) and oxidative (30 vol.%, H₂O₂) erosion. The tensile strength, deformation‐recovery ability, and glass transition temperature of the PPFUs were improved with the increase of hard segment proportion, while the degradation rate was opposite because of the faster degradation of the soft segments. In vitro culture of smooth muscle cells in the extractant of the PPFUs or on the PPFUs film surface revealed low cytotoxicity and good cytocompatibility in terms of cell viability, adhesion, and proliferation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42065.     

Biodegradable polymers based on renewable resources. V. Synthesis and biodegradation behavior of poly(ester amide)s composed of 1,4:3,6‐dianhydro‐D‐glucitol, α‐amino acid,and aliphatic dicarboxylic acid units

A series of poly(ester amide)s were synthesized by solution polycondensations of various combinations of p‐toluenesulfonic acid salts of O,O′‐bis(α‐aminoacyl)‐1,4:3,6‐dianhydro‐D ‐glucitol and bis(p‐nitrophenyl) esters of aliphatic dicarboxylic acids with the methylene chain lengths of 4–10. The p‐toluenesulfonic acid salts were obtained by the reactions of 1,4:3,6‐dianhydro‐D ‐glucitol with alanine, glycine, and glycylglycine, respectively, in the presence of p‐toluenesulfonic acid. The polycondensations were carried out in N‐methylpyrrolidone at 40°C in the presence of triethylamine, giving poly(ester amide)s having number‐average molecular weights up to 3.8 × 10⁴. Their structures were confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. Most of these poly(ester amide)s are amorphous, except those containing sebacic acid and glycine or glycylglycine units, which are semicrystalline. All these poly(ester amide)s are soluble in a variety of polar solvents such as dimethyl sulfoxide, N,N‐dimethylformamide, 2,2,2‐trifluoroethanol, m‐cresol, pyridine, and trifluoroacetic acid. Soil burial degradation tests, BOD measurements in an activated sludge, and enzymatic degradation tests using Porcine pancreas lipase and papain indicated that these poly(ester amide)s are biodegradable, and that their biodegradability markedly depends on the molecular structure. The poly(ester amide)s were, in general, degraded more slowly than the corresponding polyesters having the same aliphatic dicarboxylic acid units, both in composted soil and in an activated sludge. In the enzymatic degradation, some poly(ester amide)s containing dicarboxylic acid components with shorter methylene chain lengths were degraded more readily than the corresponding polyesters with Porcine pancreas lipase, whereas most of the poly(ester amide)s were degraded more rapidly than the corresponding polyesters with papain. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2721–2734, 2001     

一次性塑料制品污染防治的法律法规及检测标准研究进展

综述了国内外治理一次性塑料制品污染出台的法律法规及进展,重点介绍了含有部分可生物可降解组分或非生物降解方式的一次性塑料制品相关标准、传统不可降解塑料废弃物的回收塑料鉴别检测标准、全生物降解塑料制品评价标准及禁塑快速检测技术与标准,并对未来检验检测技术发展做出了展望。     

Polyesters with small structural variations improve the mechanical properties of polylactide

Improving the properties of biodegradable polymeric materials is needed to obtain materials competitive with current bulk plastics. Low‐molecular weight polyesters with small differences in their backbone were synthesized using a straight‐forward method and were subsequently blended with polylactide (PLA). The materials showed an improved ductility of up to 100% points and otherwise retained material properties. The changes in mechanical properties were shown to match the miscibility range of the materials and can be predicted by the solubility parameters of the materials up to a polyester content of roughly 10% w/w. The thermal stability of all the low‐molecular weight polyesters was higher than that of PLA, and most 25% w/w blends showed a thermal degradation behavior similar to that of neat PLA. Low‐molecular weight polyesters were demonstrated as being potential enhancers of the properties of PLA, while the materials degradability was maintained. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Biodegradation process of a blend of thermoplastic unripe banana flour—polyethylene under composting: Identification of the biodegrading agent

Starch‐based biodegradable polymers are obtained by incorporating plant‐derived polymers into plastics. This blending allows for a reduction in the polymer's resistance to microbial degradation. Assessing biodegradability is a key step in the characterization of newly designed polymers. Composting has been taken into consideration in waste management strategies as an alternative technology for plastic disposal. This study analyzed the biodegradability of an injection‐molded plastic material in which thermoplastic unripe banana flour (TPF) acts as a matrix (70%) and metallocene catalyzed polyethylene acts as a reinforcing filler (30%). This plastic was termed 70 TPF, and the structural, physical, and mechanical changes associated with its degradation were analyzed. The characterization of the microorganism that contributes to 70 TPF biodegradation was also performed. After composting, 70 TPF decreased in tensile strength and the TPF moiety in the blend was lost, greatly affecting the microstructure of the sample. Based on these indicators of degradation, this study identified the fungus Mortierella elongata as the microorganism responsible for the degradation of the plastic, a finding that supports the role of fungal communities in the biodegradation of designed materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42258.     

Hydrolytic degradation of biobased poly(butylene succinate‐co‐furandicarboxylate) and poly(butylene adipate‐co‐furandicarboxylate) copolyesters under mild conditions

It is indispensable to investigate hydrolytic degradation behavior to develop novel (bio)degradable polyesters. Biobased and biodegradable copolyesters poly(butylene adipate‐co ‐butylene furandicarboxylate) (PBAF) and poly(butylene succinate‐co ‐butylene furandicarboxylate) (PBSF) with BF molar fraction (?_BF) between 40 and 60% were synthesized in this study. The hydrolytic degradation of film samples was conducted in a pH 7.0 PBS buffer solution at 25 °C. Slight mass loss (1–2%) but significant decrease in intrinsic viscosity (35–44%) was observed after 22 weeks. The apparent hydrolytic degradation rate decreased with increasing ?_BF and initial crystallinity. Meanwhile, PBAFs degraded slightly faster than PBSFs with the same composition. The ?_BF and crystallinity increased slowly with degradation time, suggesting the aliphatic moiety and the amorphous region are more susceptible to hydrolysis. And high enough tensile properties were retained after hydrolysis degradation, indicating PBAF and PBSF copolyesters are hydrolytically degradable, with tunable hydrolytic degradation rate and good balance between hydrolytic degradability and durability. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44674.     

Nucleation and plasticization with recycled low-molecular-weight poly-3-hydroxybutyrate toughens virgin poly-3-hydroxybutyrate

Poly-3-hydroxybutyrate (PHB) is a widely distributed carbon storage molecule in prokaryotes and can serve as a biodegradable plastic replacement. However, the handling and material properties of virgin PHB are not as robust as some traditional petroleum-based plastics. Additives can be added to PHB to improve its qualities, but these additives are themselves often not biobased. A strategy was developed to utilize lower molecular weight PHB fragments derived from the recycling process as biobased additives. To simulate recycling, PHB was thermolyzed at elevated temperatures, and this degraded PHB (dPHB) was reactively processed with virgin PHB. Incorporation of dPHB nucleated and plasticized the virgin PHB as evidenced by increased crystallization temperature and crystallinity as well as decreased melt viscosity, stiffness, and melting temperature. Additionally, samples containing dPHB had increased toughness. Processing with dPHB decreased M_n, had little effect on M_w, and increased the Z-average molecular weight, indicating branching. These results demonstrate a route for nucleating, plasticizing, and toughening virgin PHB by using recycled PHB. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47432.     

Biodegradable polymers. XI. Spectral,thermal, morphological,and biodegradability properties of environment‐friendly green plastics of soy protein modified with thiosemicarbazide

The demand for biodegradable polymers produced from renewable natural resources continues to grow as environmental concerns increase. Biodegradable plastics derived from agricultural feedstock are a new generation of materials capable of reducing the environmental impact in terms of energy consumption and greenhouse effect in specific applications to perform as traditional/conventional plastics when in use and are completely biodegradable within a composting cycle through the action of living/micro‐organisms. The objective of this study is to examine the potentiality and performance pattern of soy protein isolate (SPI) resin, modified with various concentrations of thiosemicarbazide (TSC), as a thermoplastic to substitute some conventional petroleum‐based plastics. The spectral, thermal, morphological properties and the biodegradability of the modified resin have been investigated. The spectral studies indicate that TSC is not crosslinked with the protein moiety; rather, it acts as a modifier. Thermogravimetric analysis of the modified material has been followed using a computer analysis method (LOTUS package) developed by us for assigning the degradation mechanism. A number of equations have been used to evaluate the kinetic parameters. The degradation mechanism has been ascertained on the basis of the kinetic parameters. It is expected that, this environment‐friendly, fully biodegradable and sustainable TSC‐modified SPI green plastic could be commercially used for making molded products. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3134–3142, 2007     

Production and recovery of poly‐3‐hydroxybutyrate from Methylobacterium sp V49

Bacterial polyesters have shown potential as biodegradable plastics. Microorganisms capable of producing these polyesters from cheaper carbon sources and methods for their efficient recovery are widely studied worldwide. Methylobacterium sp V49, an environmental isolate, was cultivated on a mineral salts medium containing different carbon sources. Maximum accumulation of poly‐3‐hydroxybutyrate (PHB) within the bacterial cell was observed with glucose as the carbon source. Methanol and sugars such as sucrose and lactose also induced PHB accumulation. The effect of C:N ratio on polymer accumulation was studied. Different strategies for the extraction and recovery of the polymer from the cells were compared. A non‐solvent‐based method using a high‐pressure homogenizer in the presence of SDS was found to be the most satisfactory. Maximum recovery of 98% was achieved by homogenizing the cells at 400 kgcm^?2 in 5% SDS solution. © 2002 Society of Chemical Industry     

Synthesis,characterization and biodegradation studies of chain‐coupled polyesters based on tartaric acid

A series of chain‐coupled polyesters based on tartaric acid was synthesized and characterized following a two‐step procedure. In the first step, tartaric acid based hydroxyl terminated polyesters with various alkane diols were prepared and then, in a second step, a chain‐coupling approach using hexamethylene diisocyanate was employed on the synthesized polyesters to prepare a series of chain‐coupled polyesters. The number‐average molecular weights (M_n) of the polyesters were found to vary in the range (4.8 ? 28.1) × 10³ g mol^?1. Thermomechanical studies demonstrate that the storage modulus of the chain‐coupled polyesters decreases with increasing polymethylene chain length which is attributable to enhanced flexibility. The isolation of bacteria on medium containing polymer as the sole source of carbon indicates the ability of the synthesized polyesters to be taken up by microorganisms for growth. © 2013 Society of Chemical Industry     

Biodegradable polymers based on renewable resources. IV. Enzymatic degradation of polyesters composed of 1,4:3.6‐dianhydro‐D‐glucitol and aliphatic dicarboxylic acid moieties

Enzymatic degradation of a series of polyesters prepared from 1,4:3.6‐dianhydro‐D ‐glucitol (1) and aliphatic dicarboxylic acids of the methylene chain length ranging from 2 to 10 were examined using seven different enzymes. Enzymatic degradability of these polyesters as estimated by water‐soluble total organic carbon (TOC) measurement is dependent on the methylene chain length (m) of the dicarboxylic acid component for most of the enzymes examined. The most remarkable substrate specificity was observed for Rhizopus delemar lipase, which degraded polyester derived from 1 and suberic acid (m = 6) most readily. In contrast, degradation by Porcine liver esterase was nearly independent of the structure of the polyesters. Enzymatic degradability of the polyesters based on three isomeric 1,4:3.6‐dianhydrohexitols and sebacic acid was found to decrease in the order of 1, 1,4:3.6‐dianhydro‐D ‐mannitol (2), and 1,4:3.6‐dianhydro‐L ‐iditol (3). Structural analysis of water‐soluble degradation products formed during the enzymatic hydrolysis of polyester 5g derived from 1 and sebacic acid has shown that the preferential ester cleavage occurs at the O(5) position of 1,4:3.6‐dianhydro‐D ‐glucitol moiety in the polymer chain by enzymes including Porcine pancreas lipase, Rhizopus delemar lipase, and Pseudomonas sp. lipase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 338–346, 2000     

Biomimetic soy protein-based exterior-use films with excellent UV-blocking performance from catechol derivative Acacia mangium tannin

Polymer plastic is the main component of current outdoor packaging film materials that are mostly derived from fossil fuels. Its poor ultraviolet (UV) barrier performance and short service life caused by aging degradation result in increased non-renewable consumption and environmental pollution. The most effective way to solve these problems is the development of a biomass-based and eco-friendly packaging with excellent UV-blocking performance. Herein, inspired by mussels, a facile strategy is reported for the preparation of a biomimetic polymeric material via the incorporation of a biomass-derived catechol derivative Acacia mangium tannin (AMT) into a biodegradable soy protein isolate (SPI) matrix. The morphologies, mechanical, thermal properties, and UV-blocking abilities and mechanisms of the modified films were evaluated. With the increase of the AMT content, the stress of the composite film was found to gradually increase, and the modified SPI composite film exhibited a powerful tensile strength of 7.64 MPa and a high breaking strain of 145.6%. After the introduction of AMT, the films exhibited excellent UV-blocking performance. As both SPI and AMT are biodegradable, this work presents an innovative design strategy for fully-biodegradable and robust polymeric materials with excellent UV-blocking performance that have promising potential applications in packaging.     

Effect of pro-oxidants on the aerobic biodegradation,disintegration, and physio-mechanical properties of compostable polymers

Biodegradable polymers are gaining momentum to resolve the globally acknowledged plastic waste problem. Understanding, characterizing, and developing new generations of biodegradable plastics is crucial to provide industries with alternative green materials that can fully satisfy biodegradation rates and lifetime specifications. This study evaluates the influence of metal pro-oxidant additives on the degradation properties of various biodegradable polymer systems. For this purpose, iron (III) stearate (FeSt₃) and bismuth oxide (Bi₂O₃), as oxidant agents, were incorporated into poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), poly(butylene adipate-co-terephthalate) (PBAT), cellulose acetate (CA), poly(lactic acid) (PLA), and thermoplastic starch (TPS) bioplastics. The material performances and biodegradability properties due to the additives on the resulting bioplastic formulations were investigated. A mechanism was proposed in which both pro-oxidant additives can accelerate the thermo-oxidation processes under composting conditions and cleave the polymer chains into smaller fragments to stimulate the biodegradation rate through microorganisms' activity. The study revealed that both pro-oxidant additives, FeSt₃ and Bi₂O₃, effectively improved the biodegradation process for all tested polymers except TPS, which already had a very high biodegradation rate. The observed change in the barrier and mechanical properties due to the additives were within tolerable limits of corresponding neat polymers.