Poly(L-lactide)(PLLA)is one of the best candidates as a bio-based plastic material for circular economy because of its biodegradability sustainability,recyclability,and good thermal and mechanical properties.The indus...Poly(L-lactide)(PLLA)is one of the best candidates as a bio-based plastic material for circular economy because of its biodegradability sustainability,recyclability,and good thermal and mechanical properties.The industrial production of PLLA is mainly from tin(II)_(2)-ethylhexanoate[Sn(Oct)_(2)]-catalyzed ring-opening polymerization(ROP)of L-LA in melt and bulk conditions at high temperatures(150-200℃).Despite the huge efforts devoted to the development of organometallics with low toxicity and many highly active catalysts under mild laboratory conditions,very few candidates can compete with Sn(Oct)_(2) under industrially relevant conditions.Herein,we report novel zinc complexes bearing phenylimino-pyridine-phenolate ligands as efficient catalysts for L-LA polymerization under both mild and industrially relevant conditions,with a turnover frequency as high as 6200 h^(-1).The best performing catalyst competed well with Sn(Oct)_(2) under industrial conditions and afforded colorless and semicrystalline PLLA.In addition,preliminary depolymerization experiments suggested that the new catalysts can also be used for the chemical recycling of commercial PLLA directly to L-LA with high selectivity under bulk and melt conditions.展开更多
Herein,the effect of in situ formation of the stereocomplex polylactide(sc-PLA)on the crystallization behaviors of poly(L-lactide)/poly(D-lactide)(PLLA/PDLA)blends was assessed.When the melt-blending temperature of th...Herein,the effect of in situ formation of the stereocomplex polylactide(sc-PLA)on the crystallization behaviors of poly(L-lactide)/poly(D-lactide)(PLLA/PDLA)blends was assessed.When the melt-blending temperature of the PLLA/PDLA blend approached the melting temperature of sc-PLA(approximately 220℃),a higher relative content of sc-PLA was achieved.Additionally,the relative content of sc-PLA in the PLLA/PDLA blend increased progressively with the increase in PDLA content.Differential scanning calorimetry analysis revealed that the overall crystallization rate of the homocrystal polylactide were enhanced by the presence of sc-PLA.After crystallization at the same temperature(115 and 120℃),the PLLA/PDLA blends exhibited a shorter half-crystallization time compared to PLLA alone.The size of the microcrystals of PLLA decreased as the sc-PLA content increased.Furthermore,the storage modulus and complex viscosity of the PLLA/PDLA blend increased with higher sc-PLA content.Dynamic mechanical analysis indicated that the glass transition temperature of PLLA in the PLLA/PDLA blends increased with increasing sc-PLA content.Additionally,the Vicat softening temperature increased from 67.8℃ for PLLA alone to 164.7℃ for the PLLA/25PDLA blend,enhancing the heat resistance of the PLLA/PDLA blends.Compared to PLLA alone,the hydrolytic resistance of the PLLA/PDLA blends showed marked improvement.展开更多
Various sectors of the industry are searching for new materials with specific requirements,providing improved properties.The study presents novel composite materials based on polylactide that have been modified with t...Various sectors of the industry are searching for new materials with specific requirements,providing improved properties.The study presents novel composite materials based on polylactide that have been modified with the organosilicon compound,(3-thiopropyl)polysilsesquioxane(SSQ-SH).The SSQ-SH compound is a mixture of cage structures and not fully condensed random structures.The composite materials were obtained through injection moulding.The study includes a comprehensive characterization of the new materials that analyze their functional properties,such as rheology(MFR),mechanical strength(tensile strength,Charpy impact strength),and thermal properties.SEM microscopic photos were also taken to analyze the microstructure of the samples.The addition of a 5%by-weight organosilicon compound to polylactide resulted in a significant increase in MFR by 73.8%compared to the neat polymer.The greatest improvement in impact strength was achieved for the 5%SSQ-SH/PLA composite,increasing it by 32.0 kJ/m^(2)compared to PLA,which represents an increase of up to 187%.The conducted research confirms the possibility of modifying the properties of the polymer by employing organosilicon compounds.展开更多
Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film tech...Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.展开更多
Polylactide(PLA)films blended with poly(butylene adipate-co-terephthalate)(PBAT)were hot melted using a twin screw extruder with the addition of triethyl citrate(TEC)as a plasticizer and toluene diisocyanate(TDI)as a ...Polylactide(PLA)films blended with poly(butylene adipate-co-terephthalate)(PBAT)were hot melted using a twin screw extruder with the addition of triethyl citrate(TEC)as a plasticizer and toluene diisocyanate(TDI)as a compatibilizer.The synergistic effects of the two additives on the mechanical,thermal,and morphological properties of the PLA/PBAT blend films were investigated.The influence of TEC content on the plasticized PLA films and the effect of TDI’s presence on the PLA/PBAT blend films were also studied by comparing them with neat PLA.The results showed a pronounced increase in elongation at break of the plasticized PLA films with increasing TEC levels,but a slight reduction in thermal stability.Also,the addition of TEC and TDI to the blend system not only synergistically enhanced the tensile properties and tensile-impact strength of the PLA/PBAT blends,but also affected their crystallinity and cold crystallization rate,a result of the improvement of interfacial interaction between PLA and PBAT,including the enhancement of their chain mobility.The synergy of the plasticization and compatibilization processes led to the improvement of tensile properties,tensile-impact strength,and compatibility of the blends,accelerating cold crystallization without affecting crystallization.展开更多
Sustainable blends of poly(propylene carbonate)(PPC)and stereocomplex polylactide(sc-PLA)were prepared by melt blending equimolar poly(L-lactic acid)(PLLA)and poly(D-lactide acid)(PDLA)with PPC to form sc-PLA crystals...Sustainable blends of poly(propylene carbonate)(PPC)and stereocomplex polylactide(sc-PLA)were prepared by melt blending equimolar poly(L-lactic acid)(PLLA)and poly(D-lactide acid)(PDLA)with PPC to form sc-PLA crystals in situ in the melt blending process.Differential seanning calorimetry analysis revealed that only sc-PLA,no homo-crystallization of PLLA or PDLA,formed in the PPC matrix as the sc-PLA con tent was more than 10 wt%.Very in triguingly,scan ning electronic microscopy observati on showed that sc-PLA was evenly dispersed in the PPC phase as spherical particles and the sizes of sc-PLA particles did not obviously increase with in creasing sc-PLA con tent.As a con seque nee,the rheological properties of PPC were greatly improved by incorporation of sc-PLA.When the sc-PLA con tent was 20 wt%,a percolati on n etwork structure was formed,and the blends showed solid-like behavior.The sc-PLA particles could reinforce the PPC matrix,especially at a temperature above the glass transition temperature of PPC.Moreover,the Vicat softening temperature of PPC/sc-PLA blends could be increased compared with that of neat PPC.展开更多
Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The misc...Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.展开更多
Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,an...Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.展开更多
A series of host-vip interaction-adjusted polylactide stereocomplex micelles was prepared via the self-assembly of 4-armed poly（ethylene glycol）-block-poly（L-lactide/D-lactide）-cholesterol （4-armed PEG-b-PLLA/P...A series of host-vip interaction-adjusted polylactide stereocomplex micelles was prepared via the self-assembly of 4-armed poly（ethylene glycol）-block-poly（L-lactide/D-lactide）-cholesterol （4-armed PEG-b-PLLA/PDLA-CHOL） and poly（β-cyclodextrin） （PCD） with the molar ratios of CHOL/β-CD at 1：0.5, 1 ：l, and 1：2 in an aqueous environment. The hydrodynamic diameters of the micelles ranged from 84.1 nm to 107 nm depending on the molar ratio of CHOL/β-CD. It was shown that the micelle with the largest proportion of PCD possessed excellent abilities in drug release, cell internalization as well as proliferation inhibitory effect toward human A549 lung cancer cells. The results demonstrated that the stereocomplex and host-vip interactions-mediated PLA micelles exhibited great potential in sustained drug delivery.展开更多
Polactide(PLA),poly(3-hydroxybutyrate-co-4-hydroxybutyrate)(P(3HB-CO-4HB)),and poly(butylene adipate co-terephthalate)(PBAT)ternary blends were prepared by extrusion blending.The biodegradable PLA/P(3HB-co 4HB)/PBAT f...Polactide(PLA),poly(3-hydroxybutyrate-co-4-hydroxybutyrate)(P(3HB-CO-4HB)),and poly(butylene adipate co-terephthalate)(PBAT)ternary blends were prepared by extrusion blending.The biodegradable PLA/P(3HB-co 4HB)/PBAT films were successfully obtained by using blown films technique.Excellnt siffness-toughness balance was achieved for 55/10/35 PLA/P(3HB-co 4HB)/PBAT film.The tensile strength reached 33.0 MPa(MD)and 23.5 MPa(TD).the elongation at break exceeded 1309%,and tear strength exceeded 110 kN/m.The Young's modulus as low as about 1800 MPa also met packaging applications.SEM observations revealed rough and long ligaments,indicating that the tear specimens were broken yieldingly.The addition of PBAT elastomers was the main reason for the improved toughness of the film.From DMA and SEM analysis,it was demonstrated that PLA P(3HB co 4HB),and PBAT were prilly compatible.With increasing P(3HB CO-4HB)content,the melt and cold crstallization of PLA was promoted.The enzymatic degradation experiments indicated that the films had good biodegradability.These findings gave important implications for designing and manufacturing biodegradation package of high biological carbon content.展开更多
The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homoge...The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.展开更多
Renewable and biodegradable polylactide (PLA) has excellent mechanical strength but is highly flammable which restricts its practical applications. Many phosphorus/nitrogen (P/N)-based flame retardants are ef- fective...Renewable and biodegradable polylactide (PLA) has excellent mechanical strength but is highly flammable which restricts its practical applications. Many phosphorus/nitrogen (P/N)-based flame retardants are ef- fective in PLA, but their high addition loading usually decreases the mechanical strength of the PLA bulk. For polyphosphoramides, despite high fire-retardant efficiency, their chemical synthesis often generates chemical wastes as byproducts. Herein, we report an atom-economic and highly efficient oligomeric P/N fire retardant (APN) prepared using a mild Michael addition polymerization with no byproducts. Using only 3 wt% APN, the resulting PLA exhibits desired fire retardancy including a UL-94 V-0 rating and a limiting oxygen index of 37.6%. Furthermore, the toughness of the fire-retardant PLA increases by 85% compared to pure PLA, with both tensile strength and thermal stability preserved. This work offers an atom-economic strategy for synthesizing highly efficient P/N fire retardants for use in the creation of fire-resistant PLA with robust mechanical properties.展开更多
Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited ...Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited excellent dyeing properties on polylactide compared with the commercial disperse dyes.展开更多
Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distri...Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distribution of SiO_(2) plays a decisive role in the mechanical properties of plastic/elastomer/SiO_(2)nanocomposites,especially for the impact toughness.In this work,we aim to illuminate the role of specific surface area in controlling their selective distribution of fumed SiO_(2) and consequent mechanical properties of plastic/elastomer binary blends.Three types of SiO_(2) with different specific surface areas were incorporated into polylactide/ethylene-co-vinyl-acetate(PLA/EVA)model blends by melt blending directly.It was found that the selective distribution of SiO_(2) is largely determined by their specific surface areas,i.e.SiO_(2) nanoparticles with low specific surface area has a stronger tendency to be located at the interface between PLA matrix and EVA dispersed phase as compared to those with high specific surface area.The specific surface area-dependent interfacial selective distribution of SiO_(2) is mainly attributed to the extent of increased viscosity of EVA dispersed phase in which SiO_(2)nanoparticles are initially dispersed and resultant migration rate of SiO_(2) nanoparticles.The interfacial localized SiO_(2) nanoparticles induce an obvious enhancement in the impact toughness with strength and modulus well maintained.More importantly,in the case of the same interfacial distribution,toughening efficiency is increased with the specific surface area of SiO_(2).Therefore,this is an optimum specific surface area of SiO_(2) for the toughening.This work not only provides a novel way to manipulate the selective distribution of SiO_(2) in elastomer-toughened plastic blends toward high-performance,but also gives a deep insight into the role of interfacial localized nanoparticles in the toughening mechanism.展开更多
Stereocomplex-type polylactide(SC-PLA)consisting of alternatively arranged poly(L-lactide)(PLLA)and poly(D-lactide)(PDLA)chains has gained a good reputation as a sustainable engineering plastic with outstanding heat r...Stereocomplex-type polylactide(SC-PLA)consisting of alternatively arranged poly(L-lactide)(PLLA)and poly(D-lactide)(PDLA)chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide)(PDLLA)into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability(i.e.,the stability of PLLA/PDLA chain assemblies upon melting)could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt%PDLLA having weight-average molecular weight of above 1×10^(5)g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.展开更多
The dyeability of polylactide fabric has been investigated with the substituted aminoanthraquinone hydophobic dyes. Their application to the polylactide fabric led to good exhaustion values and good wash fastness betw...The dyeability of polylactide fabric has been investigated with the substituted aminoanthraquinone hydophobic dyes. Their application to the polylactide fabric led to good exhaustion values and good wash fastness between 4 and 3. MIcroscopic assessment ot cross-sections ot the dyed polylactlde fibres confirmed that these dyes could penetrate into the fibres. The nature of the substituted amino groups showed little influence on the wash fastness, but clearly influenced.the exhauslion and light fastness.展开更多
In the present work, poly（propylene glycol） （PPG） was block copolymerized to form polylactide-poly（propylene glycol）-polylactide （PL-PPG-PL） triblock copolymers for preparing flexible stereocomplex PL （scPL）...In the present work, poly（propylene glycol） （PPG） was block copolymerized to form polylactide-poly（propylene glycol）-polylactide （PL-PPG-PL） triblock copolymers for preparing flexible stereocomplex PL （scPL） blend films. The scPL blend films were prepared by solution blending of poly（L-lactide）-PPG-poly（L-lactide） （PLL-PPG-PLL） and poly（D-lactide）- PPG-poly（D-lactide） （PDL-PPG-PDL） triblock copolymers before film casting. The influences of PL end-block lengths （2 ×10^4 and 4×10^4 g/tool） and blend ratios （75/25, 50/50 and 25/75 W/W） on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the scPL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the scPL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the scPL films were improved by PPG block copolymerization.展开更多
In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PL...In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PLA/BA-EA-GMA blends were partially miscible. The degree of crystallinity of PLA increased while the cold crystallization temperature shifted to higher temperatures with increasing BA-EA-GMA content. The SEM micrographs showed that PLA/BA-EA-GMA blends had a good dispersion and this phenomenon was in good agreement with their higher impact strength. The result showed that the adding of BA-EA-GMA has enhanced the flexibility of PLA/BA-EA-GMA blends as compared with pure PLA. The impact strength was changed from 3.4 kJ/m2 for pure PLA to 29.6 kJ/m2 for 80/20 PLA/BA-EA-GMA blend.展开更多
This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/ hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the pro...This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/ hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the properties of the composite is investigated by electron microscopy, differential scanning calorimetry and tensile tests. Furthermore, the antimicrobial activities of the systems are examined. The degradation behaviour of the composites is studied in both abiotic and biotic （composting） environments at an elevated temperature of 58 ℃. The results reveal good dispersion of the additive in the PLA matrix, a stabilizing effect exerted by the same on the polylactide matrix during processing, and slight reduction in glass transition temperature. The zinc stearate-silver component also reduces brittleness and extends elongation of the composite. Abiotic hydrolysis is not significantly affected, which is in contrast with pure PLA, although mineralization during the early stage of biodegradation increases noticeably. The composite exhibits antimicrobial activity, even at the lowest dosage of the zinc stearate/silver component （1 wt%）. Moreover, Ag and Zn contents were found to be present in the composite during abiotic hydrolysis, which was demonstrated by minimal diffusion of Ag ions from the matrix and very extensive washing of compounds that contained Zn.展开更多
The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blend...The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blends. Tricresyl phosphate（TCP） and montmorillonite（MMT） were the additives used to improve the mechanical characteristics and fire resistance of PLA. Differential scanning calorimetry（DSC） thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors. The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior. The impact strength and limiting oxygen index（LOI） value of PLA significantly increased with the presence of PBS. The failure mode of the blends as evidenced by scanning electron microscopy（SEM） changed from brittle to ductile. The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends, achieving V-0 rating. For the PLA/PBS blends, the synergistic combination of PBS and additives led to an acceleration of cold crystallization, a significant increment of flexibility and impact toughness, and an improvement of flame retardancy.展开更多
基金supported by the National Natural Science Foundation of China(No.52222302)。
文摘Poly(L-lactide)(PLLA)is one of the best candidates as a bio-based plastic material for circular economy because of its biodegradability sustainability,recyclability,and good thermal and mechanical properties.The industrial production of PLLA is mainly from tin(II)_(2)-ethylhexanoate[Sn(Oct)_(2)]-catalyzed ring-opening polymerization(ROP)of L-LA in melt and bulk conditions at high temperatures(150-200℃).Despite the huge efforts devoted to the development of organometallics with low toxicity and many highly active catalysts under mild laboratory conditions,very few candidates can compete with Sn(Oct)_(2) under industrially relevant conditions.Herein,we report novel zinc complexes bearing phenylimino-pyridine-phenolate ligands as efficient catalysts for L-LA polymerization under both mild and industrially relevant conditions,with a turnover frequency as high as 6200 h^(-1).The best performing catalyst competed well with Sn(Oct)_(2) under industrial conditions and afforded colorless and semicrystalline PLLA.In addition,preliminary depolymerization experiments suggested that the new catalysts can also be used for the chemical recycling of commercial PLLA directly to L-LA with high selectivity under bulk and melt conditions.
基金supported by the Science and Technology Development Plan Project of Jilin Province of China(No.20250203127SF)Chinese Academy of Sciences(Changchun Branch)(No.2025SYHZ0045)+1 种基金Science and Technology Bureau of Jilin Province of China(No.20240302126GX)Science and Technology Bureau of Changchun City of China(No.23SH08).
文摘Herein,the effect of in situ formation of the stereocomplex polylactide(sc-PLA)on the crystallization behaviors of poly(L-lactide)/poly(D-lactide)(PLLA/PDLA)blends was assessed.When the melt-blending temperature of the PLLA/PDLA blend approached the melting temperature of sc-PLA(approximately 220℃),a higher relative content of sc-PLA was achieved.Additionally,the relative content of sc-PLA in the PLLA/PDLA blend increased progressively with the increase in PDLA content.Differential scanning calorimetry analysis revealed that the overall crystallization rate of the homocrystal polylactide were enhanced by the presence of sc-PLA.After crystallization at the same temperature(115 and 120℃),the PLLA/PDLA blends exhibited a shorter half-crystallization time compared to PLLA alone.The size of the microcrystals of PLLA decreased as the sc-PLA content increased.Furthermore,the storage modulus and complex viscosity of the PLLA/PDLA blend increased with higher sc-PLA content.Dynamic mechanical analysis indicated that the glass transition temperature of PLLA in the PLLA/PDLA blends increased with increasing sc-PLA content.Additionally,the Vicat softening temperature increased from 67.8℃ for PLLA alone to 164.7℃ for the PLLA/25PDLA blend,enhancing the heat resistance of the PLLA/PDLA blends.Compared to PLLA alone,the hydrolytic resistance of the PLLA/PDLA blends showed marked improvement.
基金supported by the Smart Growth Operational Programme(No.POIR.04.02.00-00-D003/20-00)European Funds(No.RPWP.01.01.00-30-0004/18)Ministry of Science and Higher Education(No.21/529535/SPUB/SP/2022).
文摘Various sectors of the industry are searching for new materials with specific requirements,providing improved properties.The study presents novel composite materials based on polylactide that have been modified with the organosilicon compound,(3-thiopropyl)polysilsesquioxane(SSQ-SH).The SSQ-SH compound is a mixture of cage structures and not fully condensed random structures.The composite materials were obtained through injection moulding.The study includes a comprehensive characterization of the new materials that analyze their functional properties,such as rheology(MFR),mechanical strength(tensile strength,Charpy impact strength),and thermal properties.SEM microscopic photos were also taken to analyze the microstructure of the samples.The addition of a 5%by-weight organosilicon compound to polylactide resulted in a significant increase in MFR by 73.8%compared to the neat polymer.The greatest improvement in impact strength was achieved for the 5%SSQ-SH/PLA composite,increasing it by 32.0 kJ/m^(2)compared to PLA,which represents an increase of up to 187%.The conducted research confirms the possibility of modifying the properties of the polymer by employing organosilicon compounds.
基金financially supported by the fund of Science&Technology Bureau of Jilin Province of China(No.20130305028NY)Chinese Science Academy(Changchun Branch)(No.2014SYHZ0019)+1 种基金the National High Technology Research and Development Program of China(863 Program)(No.2012AA062904)the National Natural Science Foundation of China(No.51021003)
文摘Poly（propylene carbonate） （PPC） was blended with polylactide （PLA） and poly（1,2-propylene glycol adipate） （PPA） using a twin screw extruder. Then the PPC/PLA/PPA films were prepared using the blown film technique. DMA results showed that PPA could act as a plasticizer and improve the miscibility between PPC and PLA. Crystal morphology displayed that blending PLA with the amorphous PPC led to a decrease of the spherulite size of PLA. The results of mechanical tests indicated that PPC-rich films showed high elongation at break and PLA-rich films showed high tear strength and good optical properties. The content of PPC and PLA significantly affected the physical properties of the films. With increasing PPC content, the melt strengths of the PPC/PLA/PPA films were enhanced. These findings contributed to the biodegradable materials application for designing and manufacturing polymer packaging.
基金financially supported by Development and Promotion of Science and Technology Talents (DPST) (No. 013/2559)
文摘Polylactide(PLA)films blended with poly(butylene adipate-co-terephthalate)(PBAT)were hot melted using a twin screw extruder with the addition of triethyl citrate(TEC)as a plasticizer and toluene diisocyanate(TDI)as a compatibilizer.The synergistic effects of the two additives on the mechanical,thermal,and morphological properties of the PLA/PBAT blend films were investigated.The influence of TEC content on the plasticized PLA films and the effect of TDI’s presence on the PLA/PBAT blend films were also studied by comparing them with neat PLA.The results showed a pronounced increase in elongation at break of the plasticized PLA films with increasing TEC levels,but a slight reduction in thermal stability.Also,the addition of TEC and TDI to the blend system not only synergistically enhanced the tensile properties and tensile-impact strength of the PLA/PBAT blends,but also affected their crystallinity and cold crystallization rate,a result of the improvement of interfacial interaction between PLA and PBAT,including the enhancement of their chain mobility.The synergy of the plasticization and compatibilization processes led to the improvement of tensile properties,tensile-impact strength,and compatibility of the blends,accelerating cold crystallization without affecting crystallization.
基金the Chinese Academy of scienee and technology service network planning(No.KFJSTS-QYZD-140)a program of Cooperation of Hubei Province and Chinese Academy of Sciences,Innovation team project of Beijing Institute of Science and Technology(No.IG201703N)"13^th five-year"Science and Technology Research Program of the Education Department of Jilin Provinee(No.JJKH20190862KJ).
文摘Sustainable blends of poly(propylene carbonate)(PPC)and stereocomplex polylactide(sc-PLA)were prepared by melt blending equimolar poly(L-lactic acid)(PLLA)and poly(D-lactide acid)(PDLA)with PPC to form sc-PLA crystals in situ in the melt blending process.Differential seanning calorimetry analysis revealed that only sc-PLA,no homo-crystallization of PLLA or PDLA,formed in the PPC matrix as the sc-PLA con tent was more than 10 wt%.Very in triguingly,scan ning electronic microscopy observati on showed that sc-PLA was evenly dispersed in the PPC phase as spherical particles and the sizes of sc-PLA particles did not obviously increase with in creasing sc-PLA con tent.As a con seque nee,the rheological properties of PPC were greatly improved by incorporation of sc-PLA.When the sc-PLA con tent was 20 wt%,a percolati on n etwork structure was formed,and the blends showed solid-like behavior.The sc-PLA particles could reinforce the PPC matrix,especially at a temperature above the glass transition temperature of PPC.Moreover,the Vicat softening temperature of PPC/sc-PLA blends could be increased compared with that of neat PPC.
文摘Polylactide （PLA） was successfully toughened by blending with bio-based poly（ester）urethane （TPU） elastomers which contained bio-based polyester soft segments synthesized from biomass diols and diacids. The miscibility, mechanical properties, phase morphology and toughening mechanism of the blend were investigated. Both DSC and DMTA results manifested that the addition of TPU elastomer not only accelerated the crystallization rate, but also increased the final degree of crystallinity, which proved that TPU has limited miscibility with PLA and has functioned as a plasticizer. All the blend samples showed distinct phase separation phenomenon with sea-island structure under SEM observation and the rubber particle size in the PLA matrix increased with the increased contents of TPU. The mechanical property variation of PLA/TPU blends could be quantitatively explained by Wu＇s model. With the variation of TPU, a brittle-ductile transition has been observed for the TPU/PLA blends. When these blends were under tensile stress conditions, the TPU particles could be debonded from the PLA matrix and the blends showed a high ability to induce large area plastic deformation before break, which was important for the dissipation of the breaking energy. Such mechanism was demonstrated by tensile tests and scanning electron microcopy （SEM） observations.
基金financially supported by the National Science Foundation of Zhejiang Province of China (No. LQY19B040001)the fund of Science and Technology Bureau of Jilin Province of China (No. 20170204012SF)+1 种基金the Program of Changchun Science and Technology Bureau (No. 16CX23)National Key Research and Development Program of China (No. 2016YFC0501402-5)
文摘Polylactide(PLA),methyl methacrylate-butadiene-styrene copolymer(MBS),and poly(propylene carbonate)polyurethane(PPCU)were blended and subjected to blown film process.The rheological,mechanical,morphological,thermal,and crystalline properties of the PLA/MBS/PPCU ternary blends and the mechanical properties of the resulting films were studied.Results of mechanical test showed that PPCU and MBS could synergistically toughen PLA.The impact strength of 50/10/40 PLA/MBS/PPCU blend(74.7 k J/m^2)was about 7.5 times higher than that of the neat PLA(10.8 k J/m^2),and the elongation at break of 50/10/40 PLA/MBS/PPCU blend(276.5%)was higher by about 45 times that of PLA(6.2%).The tear strength of PLA/MBS/PPCU films was 20 k N/m higher than that of PLA,and the elongation at break(MD/TD)of 50/10/40 PLA/MBS/PPCU films was 271.1%/222.3%,whereas that of PLA was only 2.7%/3.0%.POM observations displayed that the density of spherulite nucleation increased and the size of crystalline particles decreased with the addition of MBS.With increasing PPCU content from 5%to 20%,the density of spherulite nucleation increased and the size of crystalline particles decreased continuously,but the nucleation density of spherulites was slightly lowered with increasing PPCU content from 30%to 40%.The PLA/MBS/PPCU films exhibited excellent mechanical properties,which expanded the application range of these biodegradable films.
基金financially supported by the National Natural Science Foundation of China(Nos.51673190,51303174,51603204 and 51390484)
文摘A series of host-vip interaction-adjusted polylactide stereocomplex micelles was prepared via the self-assembly of 4-armed poly（ethylene glycol）-block-poly（L-lactide/D-lactide）-cholesterol （4-armed PEG-b-PLLA/PDLA-CHOL） and poly（β-cyclodextrin） （PCD） with the molar ratios of CHOL/β-CD at 1：0.5, 1 ：l, and 1：2 in an aqueous environment. The hydrodynamic diameters of the micelles ranged from 84.1 nm to 107 nm depending on the molar ratio of CHOL/β-CD. It was shown that the micelle with the largest proportion of PCD possessed excellent abilities in drug release, cell internalization as well as proliferation inhibitory effect toward human A549 lung cancer cells. The results demonstrated that the stereocomplex and host-vip interactions-mediated PLA micelles exhibited great potential in sustained drug delivery.
基金This work was financially supported by the fund of Science and Technology Bureau of Jilin Province of China(No.201702040125F)Chinese Academy of Sciences(Changchun Branch)(No.2020SYHZ0002)+1 种基金Science and Technology Services Network Program of Chinese Academy of Sciences(STS Project)(No.KFJ-STS-ZDTP-082)the National Science Foundation of Zhejiang Province of China(No.LQY19B040001).
文摘Polactide(PLA),poly(3-hydroxybutyrate-co-4-hydroxybutyrate)(P(3HB-CO-4HB)),and poly(butylene adipate co-terephthalate)(PBAT)ternary blends were prepared by extrusion blending.The biodegradable PLA/P(3HB-co 4HB)/PBAT films were successfully obtained by using blown films technique.Excellnt siffness-toughness balance was achieved for 55/10/35 PLA/P(3HB-co 4HB)/PBAT film.The tensile strength reached 33.0 MPa(MD)and 23.5 MPa(TD).the elongation at break exceeded 1309%,and tear strength exceeded 110 kN/m.The Young's modulus as low as about 1800 MPa also met packaging applications.SEM observations revealed rough and long ligaments,indicating that the tear specimens were broken yieldingly.The addition of PBAT elastomers was the main reason for the improved toughness of the film.From DMA and SEM analysis,it was demonstrated that PLA P(3HB co 4HB),and PBAT were prilly compatible.With increasing P(3HB CO-4HB)content,the melt and cold crstallization of PLA was promoted.The enzymatic degradation experiments indicated that the films had good biodegradability.These findings gave important implications for designing and manufacturing biodegradation package of high biological carbon content.
文摘The montmorillonite, a form of layered silicate, was successfully intercalated into polylactide （PLA） matrix through solvent-casting technique. In addition, PLA/MMT nanocomposite films were produced, in which homogenous distribution of the silicate lamellae plays a key role in the mechanical properties of the films. A small amount（5wt%） of OMMT intercalated into the PLA matrix resulted in their flexibility enhancement, from 3.68%（pure PLA film） to 352.65%. The results of wide-angle X-ray diffraction （WAXD） patterns confirmed that the silicate interlayer distance increased from 3.044 nm （for OMMT） to 3.56nm （for 5wt%, maximum） with increasing OMMT contents, but decreased to 3.319 nm when OMMT content was over 8wt%. FT-IR also verified the molecular-level associations between PLA chains and OMMT lamellae by vibration variances of hydrogen bonding. DSC thermograms demonstrated that thermal stabilities of the nanocomposite films enhanced, due to the silicate lamellae dispersed into PLA matrix.
基金the National Natural Science Foundation of China(No.21801097)the Australian Re-search Council(Nos.DP190102992 and FT190100188).
文摘Renewable and biodegradable polylactide (PLA) has excellent mechanical strength but is highly flammable which restricts its practical applications. Many phosphorus/nitrogen (P/N)-based flame retardants are ef- fective in PLA, but their high addition loading usually decreases the mechanical strength of the PLA bulk. For polyphosphoramides, despite high fire-retardant efficiency, their chemical synthesis often generates chemical wastes as byproducts. Herein, we report an atom-economic and highly efficient oligomeric P/N fire retardant (APN) prepared using a mild Michael addition polymerization with no byproducts. Using only 3 wt% APN, the resulting PLA exhibits desired fire retardancy including a UL-94 V-0 rating and a limiting oxygen index of 37.6%. Furthermore, the toughness of the fire-retardant PLA increases by 85% compared to pure PLA, with both tensile strength and thermal stability preserved. This work offers an atom-economic strategy for synthesizing highly efficient P/N fire retardants for use in the creation of fire-resistant PLA with robust mechanical properties.
文摘Attempts were made to develop dyes with high affinity for polylactide as an alternative to the existent commercial disperse dyes. The dyes synthesized according to the affinity concept of dye to polylactide exhibited excellent dyeing properties on polylactide compared with the commercial disperse dyes.
基金the National Natural Science Foundation of China(No.51803130)China Postdoctoral Science Foundation(No.2018M640915)+1 种基金Sichuan Science and Technology Program(No.2019JDRC010)Fundamental Research Funds for Central Universities.
文摘Adding fumed silica(Si0_(2))has been considered as an effective method for tailoring the phase morphology and performance of elastomer-toughened plastic binary blends.It has been demonstrated that the selective distribution of SiO_(2) plays a decisive role in the mechanical properties of plastic/elastomer/SiO_(2)nanocomposites,especially for the impact toughness.In this work,we aim to illuminate the role of specific surface area in controlling their selective distribution of fumed SiO_(2) and consequent mechanical properties of plastic/elastomer binary blends.Three types of SiO_(2) with different specific surface areas were incorporated into polylactide/ethylene-co-vinyl-acetate(PLA/EVA)model blends by melt blending directly.It was found that the selective distribution of SiO_(2) is largely determined by their specific surface areas,i.e.SiO_(2) nanoparticles with low specific surface area has a stronger tendency to be located at the interface between PLA matrix and EVA dispersed phase as compared to those with high specific surface area.The specific surface area-dependent interfacial selective distribution of SiO_(2) is mainly attributed to the extent of increased viscosity of EVA dispersed phase in which SiO_(2)nanoparticles are initially dispersed and resultant migration rate of SiO_(2) nanoparticles.The interfacial localized SiO_(2) nanoparticles induce an obvious enhancement in the impact toughness with strength and modulus well maintained.More importantly,in the case of the same interfacial distribution,toughening efficiency is increased with the specific surface area of SiO_(2).Therefore,this is an optimum specific surface area of SiO_(2) for the toughening.This work not only provides a novel way to manipulate the selective distribution of SiO_(2) in elastomer-toughened plastic blends toward high-performance,but also gives a deep insight into the role of interfacial localized nanoparticles in the toughening mechanism.
基金financially supported by the National Natural Science Foundation of China(No.51873129)。
文摘Stereocomplex-type polylactide(SC-PLA)consisting of alternatively arranged poly(L-lactide)(PLLA)and poly(D-lactide)(PDLA)chains has gained a good reputation as a sustainable engineering plastic with outstanding heat resistance and durability,however its practical applications have been considerably hindered by the weak SC crystallizability.Current methods used to enhance the SC crystallizability are generally achieved at the expense of the precious bio-renewability and/or bio-degradability of PLAs.Herein,we demonstrate a feasible method to address these challenges by incorporating small amounts of poly(D,L-lactide)(PDLLA)into linear high-molecular-weight PLLA/PDLA blends.The results show that the incorporation of the atactic PDLLA leads to a significant enhancement in the SC crystallizability because its good miscibility with the isotactic PLAs makes it possible to greatly improve the chain mixing between PLLA and PDLA as an effective compatibilizer.Meanwhile,the melt stability(i.e.,the stability of PLLA/PDLA chain assemblies upon melting)could also be improved substantially.Very intriguingly,SC crystallites are predominantly formed with increasing content and molecular weight of PDLLA.More notably,exclusive SC crystallization can be obtained in the racemic blends with 20 wt%PDLLA having weight-average molecular weight of above 1×10^(5)g/mol,where the chain mixing level and intermolecular interactions between the PLA enantiomers could be strikingly enhanced.Overall,our work could not only open a promising horizon for the development of all SC-PLA-based engineering plastic with exceptional SC crystallizability but also give a fundamental insight into the crucial role of PDLLA in improving the SC crystallizability of PLLA/PDLA blends.
基金Supported by the National Science Foundation for Distinguished Young Scholars of China （20525620） and Dalian University of Technology Youth Teacher Foundation （893227）.
文摘The dyeability of polylactide fabric has been investigated with the substituted aminoanthraquinone hydophobic dyes. Their application to the polylactide fabric led to good exhaustion values and good wash fastness between 4 and 3. MIcroscopic assessment ot cross-sections ot the dyed polylactlde fibres confirmed that these dyes could penetrate into the fibres. The nature of the substituted amino groups showed little influence on the wash fastness, but clearly influenced.the exhauslion and light fastness.
基金financially supported by the Academic Development Fund of Rajabhat Maha Sarakham University(PhD scholarship for D.Pholharn)the Division of Research Facilitation and Dissemination,Mahasarakham University(2017)
文摘In the present work, poly（propylene glycol） （PPG） was block copolymerized to form polylactide-poly（propylene glycol）-polylactide （PL-PPG-PL） triblock copolymers for preparing flexible stereocomplex PL （scPL） blend films. The scPL blend films were prepared by solution blending of poly（L-lactide）-PPG-poly（L-lactide） （PLL-PPG-PLL） and poly（D-lactide）- PPG-poly（D-lactide） （PDL-PPG-PDL） triblock copolymers before film casting. The influences of PL end-block lengths （2 ×10^4 and 4×10^4 g/tool） and blend ratios （75/25, 50/50 and 25/75 W/W） on the stereocomplexation and mechanical properties of the blend films were evaluated. From DSC and WAXD results, the 50/50 blend films had complete stereocomplexation. Phase separation between the scPL and PPG phases was not observed from their SEM images. The tensile stress and elongation at break increased with the sterecomplex crystallinities and PL end-block lengths. The PPG middle-blocks enhanced elongation at break of the scPL films. The results showed that the PL-PPG-PL triblock structures did not affect stereocomplexation of the PLL/PDL block blending. In conclusion, the phase compatibility and flexibility of the scPL films were improved by PPG block copolymerization.
基金financially supported by the Science&Technology Bureau of Jilin Province of China(No.20126023)
文摘In this work, a specific polylactide （PLA） 4032D was melt-mixed with a new toughener： butyl acrylate （BA）, ethyl acrylate （EA） and glycidyl methacrylate （GMA） copolymer （BA-EA-GMA）. DMA tests showed that PLA/BA-EA-GMA blends were partially miscible. The degree of crystallinity of PLA increased while the cold crystallization temperature shifted to higher temperatures with increasing BA-EA-GMA content. The SEM micrographs showed that PLA/BA-EA-GMA blends had a good dispersion and this phenomenon was in good agreement with their higher impact strength. The result showed that the adding of BA-EA-GMA has enhanced the flexibility of PLA/BA-EA-GMA blends as compared with pure PLA. The impact strength was changed from 3.4 kJ/m2 for pure PLA to 29.6 kJ/m2 for 80/20 PLA/BA-EA-GMA blend.
基金financially supported by the Czech Science Foundation (No.17-16928Y)the Ministry of Education,Youth and Sports of the Czech Republic within the NPU I programme (No.LO1504)
文摘This work investigates the degradation and properties of a thermoplastically prepared composite comprising a polylactide/ hybrid zinc stearate-silver system. The influence of the zinc stearate-silver system on the properties of the composite is investigated by electron microscopy, differential scanning calorimetry and tensile tests. Furthermore, the antimicrobial activities of the systems are examined. The degradation behaviour of the composites is studied in both abiotic and biotic （composting） environments at an elevated temperature of 58 ℃. The results reveal good dispersion of the additive in the PLA matrix, a stabilizing effect exerted by the same on the polylactide matrix during processing, and slight reduction in glass transition temperature. The zinc stearate-silver component also reduces brittleness and extends elongation of the composite. Abiotic hydrolysis is not significantly affected, which is in contrast with pure PLA, although mineralization during the early stage of biodegradation increases noticeably. The composite exhibits antimicrobial activity, even at the lowest dosage of the zinc stearate/silver component （1 wt%）. Moreover, Ag and Zn contents were found to be present in the composite during abiotic hydrolysis, which was demonstrated by minimal diffusion of Ag ions from the matrix and very extensive washing of compounds that contained Zn.
基金financially supported by Prince of Songkla University (No.SCI600593S)the Faculty of Science Research Fund,Prince of Songkla University (No.1-2558-02-006)Development and Promotion of Science and Technology Talents Project (DPST)
文摘The main aim of this research was to investigate the synergistic influence of additives and poly（butylene succinate）（PBS） in improving both the mechanical and flame retardant properties of polylactide（PLA） blends. Tricresyl phosphate（TCP） and montmorillonite（MMT） were the additives used to improve the mechanical characteristics and fire resistance of PLA. Differential scanning calorimetry（DSC） thermograms revealed that the addition of TCP and MMT significantly affected their thermal behaviors. The results of the mechanical and morphological characterizations were in agreement with the changes in thermal behavior. The impact strength and limiting oxygen index（LOI） value of PLA significantly increased with the presence of PBS. The failure mode of the blends as evidenced by scanning electron microscopy（SEM） changed from brittle to ductile. The addition of TCP and MMT produced excellent anti-dripping and self-extinguishing behaviors of the blends, achieving V-0 rating. For the PLA/PBS blends, the synergistic combination of PBS and additives led to an acceleration of cold crystallization, a significant increment of flexibility and impact toughness, and an improvement of flame retardancy.
