Effects of aromatic groups in polymer chains on plasma surface modification

Three polyester films with different repeating units—poly(lactic acid) (PLA), poly(ethylene terephthalate) (PET), and poly(oxybenzoate‐co‐oxynaphthoate) (PBN)—were modified by plasma, and the way in which the chemical compositions of the polymer chains influenced the plasma modification was investigated with contact‐angle measurements and X‐ray photoelectron spectroscopy (XPS). There were large differences in the compensated rates of weight loss among the three polyester films when they were exposed to Ar and O₂ plasmas. The PLA film showed the highest rate for weight loss of the three films, and the PBN film showed the lowest rate. The PET and PBN film surfaces were modified to become more hydrophilic by either argon or oxygen plasma. However, the PLA film surface was not made more hydrophilic by the plasmas. XPS spectra showed that the PLA film surface was not modified in its chemical composition, but the PBN film surface was modified in its chemical composition to form C? O groups in the PBN polymer chains. The reason that the PLA film surface was not modified but the PBN film surface was modified was examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 96–103, 2003     

Hydrophilic and hydrophobic poly(l‐lactic acid) films by building porous topological surfaces

Surface wettability of thin films is significant for their functional properties. Poly(l ‐lactic acid) (PLLA) is proposed as film matrix for building porous topological surfaces. By controlling the dope composition and ambient conditions, the films with ordered pores at micrometer scale are obtained. The results demonstrate that the hydrophilic or hydrophobic surface can be realized by building the porous topological surfaces. Increasing polymer concentration can lead to decreased pore size. The transition behavior of surface pores from discrete bowl‐like to interconnected honeycomb‐like structure with the increasing humidity is observed. The contact angle of top surface of film is higher than that of bottom surface, which verified the different roughness performance. The morphology and scale of topological structure are markedly related with the template effect of water droplets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44572.     

In situ fibre‐reinforced composite films of poly(lactic acid)/low‐density polyethylene blends: effects of composition on morphology,transport and mechanical properties

This study aimed to investigate the effects of blend composition on packaging‐related properties of poly(lactic acid) (PLA) and low density polyethylene (LDPE) blown films. Blend films with PLA contents of 5–20 wt% were produced and compared. Scanning electron micrographs of cross‐sectional cryofractured surfaces of the blend films revealed that in situ fibre‐reinforced composites were obtained. Viscosity ratio of the polymer components of ca 1 confirmed that fibre formation was favourable for this blend system. PLA microdomains were dispersed throughout the film in forms of long fibres (length‐to‐diameter ratio > 100) and ribbons. The number of fibres and ribbons increased with an increase of PLA content. Critical content of PLA was found to be 20 wt% for effective improvement of both moduli and gas barrier properties. Incorporation of poly[ethylene‐co‐(methyl acrylate)] compatibilizer showed minimal effect on PLA structure. However, it did improve moduli and O₂ barrier properties when sufficient amount (1.5 pph) was used in 10 wt% PLA/LDPE. In short, flow behaviour, ratio of polymer components and degree of compatibility together played intricate roles in the morphology and hence mechanical and transport properties of PLA/LDPE immiscible blends. © 2017 Society of Chemical Industry     

Water vapor permeability of poly(lactide)s: Effects of molecular characteristics and crystallinity

Amorphous‐made poly(L ‐lactide) [i.e., poly(L ‐lactic acid) (PLLA)], poly(L ‐lactide‐co‐D ‐lactide)[P(LLA‐DLA)](77/23), and P(LLA‐DLA)(50/50) films and PLLA films with different crystallinity (X_c) values were prepared, and the effects of molecular weight, D ‐lactide unit content (tacticity and optical purity), and crystallinity of poly(lactide) [i.e., poly(lactic acid) (PLA)] on the water vapor permeability was investigated. The changes in number‐average molecular weight (M_n) of PLLA films in the range of 9 × 10⁴–5 × 10⁵ g mol^?1 and D ‐lactide unit content of PLA films in the range of 0–50% have insignificant effects on their water vapor transmission rate (WVTR). In contrast, the WVTR of PLLA films decreased monotonically with increasing X_c from 0 to 20%, while leveled off for X_c exceeding 30%. This is probably due to the higher resistance of “restricted” amorphous regions to water vapor permeation compared with that of the “free” amorphous regions. The free and restricted amorphous regions are major amorphous components of PLLA films for X_c ranges of 0–20% and exceeding 30%, respectively, resulting in the aforementioned dependence of WVTR on X_c. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

High molecular weight poly (L‐lactic acid) clay nanocomposites via solid‐state polymerization

We propose here, a novel technique to synthesize high molecular weight (MW) poly (L ‐lactic acid)‐clay nanocomposite (PLACN), via solid state polymerization (SSP). We synthesize prepolymer of PLACN (pre‐PLACN) from both, L ‐lactic acid and L ‐lactide, as starting materials. Synthesis of pre‐PLACN from L ‐lactic acid is carried out via in situ melt polycondensation (MP) of L ‐lactic acid oligomer, followed by SSP, to achieve high MW PLACN (M_w ∼ 138,000 Da). In case of L ‐lactide as the starting material, we prepare L ‐lactide–clay intercalated mixture which yields moderate MW pre‐PLACN during subsequent ring opening polymerization (ROP). Interestingly, ROP is performed by using hydroxyl functionalized ternary catalyst system (L ‐lactide–Sn(II) octoate–oligo (L‐lactic acid) complex), which provides the terminal hydroxyl end‐groups, required for step‐growth SSP. Pre‐PLACN MW is now increased to M_w ∼ 127,000 Da, by the subsequent SSP process. ¹H NMR analyses confirm that these end‐groups, are indeed consumed during SSP. During SSP, the PLACN also achieves up to 90% crystallinity, which may be due to the synchronization of the slow step‐growth SSP of poly(L ‐lactic acid) (PLA) with the crystallization kinetics. Optical purity of PLACNs is similar to that of neat PLA, whereas the thermal stability of PLACNs is significantly superior. As evidenced by wide‐angle X‐ray scattering/small‐angle X‐ray scattering analyses and in line with the literature, both, intercalated and exfoliated PLACN morphologies, have been synthesized, by suitable selection of clays. We also verify the correlation between the PLA semicrystalline morphology and the PLACN morphology, which is consistent with those of PLACN synthesized by other techniques. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Blends of poly(ε‐caprolactone‐b‐lactic acid) and poly(lactic acid) for hot‐melt applications

The condensation reaction product of poly(lactic acid) (PLA) and a hydroxyl‐terminated four‐armed poly(ε‐caprolactone) (PCL) was studied by size‐exclusion chromatography, DSC, and NMR. The use of both L ‐lactic acid (LLA) and rac‐lactic acid (rac‐LA) was studied and the use of two different catalysts, stannous 2‐ethylhexanoate [Sn(Oct)₂] and ferrous acetate [Fe(OAc)₂], was also investigated. The thermal stability and adhesive properties were also measured for the different formulations. The characterization results suggested the formation of a blend of PLA and a block‐copolyester of PLA and PCL. The results further indicated partial miscibility in the amorphous phase of the blend showing only one glass‐transition temperature in most cases, although no randomized structures could be detected in the block‐copolymers. The polymerization in the Fe(OAc)₂‐catalyzed experiments proceeded slower than in the Sn(Oct)₂‐catalyzed experiments. The discoloring of the polymer was minor when Fe(OAc)₂ was used as catalyst, but significant when Sn(Oct)₂ was used. The ferrous catalyst also caused a slower thermal degradation. Differences in the morphology and in the adhesive properties could be related to the stereochemistry of the poly(lactic acid). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 196–204, 2004     

Fabrication of starch‐g‐poly(l‐lactic acid) biocomposite films: Effects of the shear‐mixing and reactive‐extrusion conditions

In this study, we developed a new approach for the fabrication of a green poly(l ‐lactic acid)‐grafted starch (St‐g‐PLA) copolymer and nanocomposite (St‐g‐PLA/organoclay)‐based films via shear‐mixing and reactive‐extrusion systems. The chemical and physical structures, thermal behavior, and morphology of the synthesized blends and some other parameters were examined by Fourier transform infrared spectroscopy and ¹³C cross‐polarization/magic angle spinning NMR spectroscopy, X‐ray diffraction, thermogravimetric analysis–derivative thermogravimetry, and scanning electron microscopy, respectively. Significant increases in the mechanical and permeability properties were evident in the high value of grafted poly(lactic acid) molar percentages and high exfoliation of organoclay. The biodegradability of films were investigated under aerobic composting conditions through the measurement of the temperature, moisture, pH, consumed O₂ value, and carbon dioxide produced. This new strategy mainly improved the good adhesion between both phases, and it was an interesting method for the production of environmentally friendly biocomposites that could easily be scaled up for commercial production with the potential for replacing petroleum‐based plastics. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44490.     

Mechanical,barrier, and thermal properties of poly(lactic acid)/poly(trimethylene carbonate)/talc composite films

Poly(l ‐lactic acid) (PLA) is now a very attractive polymer for food packaging applications. In this study, PLA/poly(trimethylene carbonate) (PTMC)/talc composite films were prepared by solvent casting. The influence of the talc loading (0, 1, 2, and 3 wt %) on the phase morphology of the PLA/PTMC/talc composites and the improvement in the resulting properties are reported in this article. The scanning electron microscopy images of the composite films demonstrated good compatibility between the PLA and PTMC, whereas talc was not thoroughly distributed in the PLA matrix at talc contents exceeding 3 wt %. The tensile strength and elongation at break of the composite films significantly improved (p < 0.05). On the contrary, the water vapor permeability and oxygen properties of the composite films decreased by 24.7 and 39.2%, respectively, at the 2 wt % talc loading. Differential scanning calorimetry showed that the crystallinity of the PLA phase increased with the presence of talc filler in the PLA/PTMC/talc composites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40016.     

Properties of a poly(L‐lactic acid)/poly(D‐lactic acid) stereocomplex and the stereocomplex crosslinked with triallyl isocyanurate by irradiation

A poly(L ‐lactic acid) (PLLA)/poly(D ‐lactic acid) (PDLA) stereocomplex was prepared from an equimolar mixture of commercial‐grade PLLA and PDLA by melt processing for the first time. Crosslinked samples were obtained by the radiation‐induced crosslinking of the poly(lactic acid) (PLA) stereocomplex mixed with triallyl isocyanurate (TAIC). The PLA stereocomplex and its crosslinked samples were characterized by their gel behavior, thermal and mechanical measurements, and enzymatic degradation. The crosslinking density of the crosslinked stereocomplex was described as the gel fraction, which increased with the TAIC content and radiation dose. The maximum crosslinking density was obtained in crosslinked samples of PLA/3% TAIC and PLA/5% TAIC irradiated at doses higher than 30 kGy. The stable crosslinking networks that formed in the irradiated PLA/TAIC substantially suppressed the segmental mobility for the crystallization of single crystals as well as stereocomplex crystals. The crosslinking network also significantly improved the mechanical properties and inhibited the enzymatic degradation of crosslinked PLA/3% TAIC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Surface modification and degradation of poly(lactic acid) films by Ar-plasma

Surface modification of poly(lactic acid) (PLA) film surface by Ar-plasma was investigated by contact angle measurements and XPS in order to answer the following two questions. (1) Could the Ar-plasma modify the PLA film surfaces? (2) What chemical reactions occurred on the film surfaces during the Ar-plasma treatment? The Ar-plasma treatment did not lead to hydrophilic modification of the PLA film surface, but to degradation reactions of the PLA film. Poor modification may be due to instability of the carbon radicals formed from C—O bond scission in the PLA chains by the Ar-plasma.     

Effect of mixing poly(lactic acid) with glycidyl methacrylate grafted poly(ethylene octene) on optical and mechanical properties of the blown films

Poly(lactic acid) (PLA) was plasticized with acetyl tributyl citrate (ATBC). The plasticized PLA was further blended with poly(ethylene octene) grafted with glycidyl methacrylate (POE‐g‐GMA denoted as GPOE) using a twin‐screw extruder and the extruded samples were blown using the blown thin film technique. Both ATBC and GPOE significantly influenced the physical properties of the films. Compared to neat PLA, the elongation at break and tear strength of the films were significantly improved. The cavitation and large plastic deformation observed in films subjected to the tear test were the important energy‐dissipation process, which led to a torn PLA film. Moreover, the PLA/ATBC/GPOE blown films had better transparency and water tolerance than that of neat PLA. GPOE could act as a tear resistance modifier for PLA blown films. These findings contributed new knowledge to the additives area and gave important implications for designing and manufacturing polymer packaging materials. POLYM. ENG. SCI., 55:2801–2813, 2015. © 2015 Society of Plastics Engineers     

Hydrolytic degradation of poly(l‐lactic acid)/poly(methyl methacrylate) blends

The hydrolytic degradation of poly(l ‐lactic acid)/poly(methyl methacrylate) (PLLA/PMMA) blends was carried out by the immersion of thin films in buffer solutions (pH = 7.24) in a shaking water bath at 60 °C for 38 days. The PLA/PMMA blends (0/100; 30/70; 50/50; 70/30; 100/0) were obtained by melt blending using a Brabender internal mixer and shaped into thin films of about 150 µm in thickness. Considering that PMMA does not undergo hydrolytic degradation, that of PLLA was followed via evolution of PLA molecular weight (recorded by size exclusion chromatography), thermal parameters (differential scanning calorimetry (DSC)) and morphology of the films (scanning transmission electron microscopy). The results reveal a completely different degradation pathway of the blends depending on the polymethacrylate/polyester weight ratio. DSC data suggest that, during hydrolysis at higher PMMA content, the polyester amorphous chains, more sensitive to water, are degraded before being able to crystallize, while at higher PLLA content, the crystallization is favoured leading to a sample more resistant to hydrolysis. In other words, and quite unexpectedly, increasing the content of water‐sensitive PLLA in the PLLA/PMMA blends does not mean de facto faster hydrolytic degradation of the resulting materials. © 2018 Society of Chemical Industry     

New insight into the mechanism of enhanced crystallization of PLA in PLLA/PDLA mixture

Poly(lactic acid) (PLA) is a bio‐based and compostable polymer that has quickly developed into a competitive material, but the control of crystallinity is a bottleneck in extended utilization. The crystallization of PLA has been a rich topic because of the existence of two enantiomeric forms of poly(L‐lactic acid) (PLLA) and poly(d ‐lactic acid) (PDLA) can form stereocomplex (SC) crystal with high melting point that can be used to control the crystallization behaviors. The SC crystal was regarded as an effective nucleating agent for promoting the crystallization rate and crystallinity of PLA. We investigated cold crystallization of PLLA/PDLA (1:1) mixture with in situ WAXS measurements and found that the homo‐crystal of PLA formed earlier than the SC‐crystal in the mixture within the measured temperature range, which is different from the melting crystallization. The final crystalline structures are in correspondence with the melting and cold crystallization temperature, and the transition of homo‐PLA (δ to α) is not altered by the crystallization procedure. The SC‐crystal can be detected in both cold and melting crystallization of the mixture at the temperatures lower than 150 °C, which is conflict with the reported results. A new crystallization mechanism of the mixture was proposed to understand the crystallization behaviors in PLLA/PDLA mixtures. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45663.     

Surface functionalization of poly(lactic acid) film by UV‐photografting of N‐vinylpyrrolidone

The photoinitiated grafting of N‐vinylpyrrolidone (NVP) onto poly(lactic acid) (PLA) film with the use of benzophenone (BP) as the initiator, modified the natural hydrophobic PLA behavior to an hydrophilic film with desirable wettability. The surface photografting parameters‐percent conversion of monomer to overall photopolymerization (Cp), percent conversion of monomer to the photograft polymerization (Cg), and grafting efficiency (Eg) were calculated. The resulting film surface was analyzed using ATR‐FTIR and UV spectroscopy, derivative spectroscopy and water contact angle. Besides, we demonstrated that the grafted polyvinylpyrrolidone chains could easily react with iodine to form a complex as the homopolymer does with antibacterial activity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Transfer of a low-molecular-weight compound between two immiscible polymers

We investigated plasticizer transfer between poly(ethylene-co-vinyl acetate) (EVA) and poly(lactic acid) (PLA) and its temperature dependence using laminated films comprising EVA and PLA, each containing equal amounts of a plasticizer [i.e., diethyl phthalate (DEP) or dibutyl phthalate (DBP)]. Because the miscibility between PLA and DEP is better than that between EVA and DEP, a large amount of DEP was detected in the PLA film after annealing the laminated films at 80 °C; that is, some DEP moved from the EVA film to the PLA film. Furthermore, more DEP migrated to the PLA film at 130 °C, suggesting that the difference in the interaction parameter with DEP between PLA and EVA is more pronounced at higher temperatures. In laminated films containing DBP, the DBP content in each film was almost equal after annealing at 80 °C, although DBP migrated from the PLA film to the EVA film at 130 °C. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47386.     

Surface hydrophilicity and enzymatic hydrolyzability of biodegradable polyesters: 1. effects of alkaline treatment

Surface treatment using alkaline solutions was attempted to enhance the surface hydrophilicity and enzymatic hydrolyzability of hydrophobic poly(L ‐lactide) [ie poly(L ‐lactic acid) (PLLA) and poly(ε‐caprolactone) (PCL). The alkaline treatment was performed by immersing the PLLA and PCL films in 0.01 and 4 N NaOH solutions, respectively, for various periods of time. The effects of the alkaline treatment on the hydrophilicity of the films were monitored by dynamic contact angle measurements, while the enzymatic hydrolyzability of the PLLA and PCL films after the alkaline treatment were evaluated by weight losses in the presence of proteinase K and Rhizopus arrhizus lipase, respectively. With the alkaline treatment the hydrophilicity of the PLLA and PCL films was controllable in the advancing contact angle (θ_a) ranges of 84–108° and of 69–93°, respectively, by varying the alkaline treatment time. The enzymatic hydrolysis rates of the PLLA films became higher with decrease of the θ_a, irrespective of the crystallinity, strongly suggesting that the surface hydrophilicity or the surface molecular weight is crucial to determine their enzymatic hydrolyzability. In contrast, the enzymatic hydrolyzability of the PCL films remained unchanged even when the θ_a decreased from 93° to 73° by alkaline treatment for 4 h. However, prolonged alkaline treatment for periods of time exceeding 4 h, which insignificantly altered the θ_a but caused the formation of pores and cracks on the PCL film surface, accelerated the enzymatic hydrolysis of the PCL films. This indicates that the enzymatic hydrolyzability of the PCL film depends on the surface area per unit weight rather than the surface hydrophilicity. Copyright © 2003 Society of Chemical Industry     

Toughening of poly(lactic acid) with the renewable bioplastic poly(trimethylene malonate)

The aim of this work was to enhance poly(lactic acid)'s (PLA) flexibility and ductility by blending it with another bioplastic. Poly(trimethylene malonate) (PTM), developed as part of this study, was synthesized from 1,3‐propane diol and malonic acid via melt polycondensation. Blend films of PLA and PTM were prepared by solvent casting from chloroform. Differential scanning calorimetry and thermogravimetric analysis were used to show shifted phase transitions and a single glass‐transition temperature, indicating miscibility of PTM in the blend films. Morphology and mechanical characterizations of the PLA/PTM blend films were performed by atomic force microscopy using a quantitative nanomechanical property mapping mode, tensile testing, and scanning electron microscopy. Miscible blends exhibited Young's modulus and elongation at break values that can significantly extend the usefulness of PLA in commercial applications. The blending of PTM with PLA resulted in films with a 27‐fold increase in toughness compared with neat PLA film. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40888.     

Influence of casting substrate on the surface free energy of various polyesters

The surface free energies of various polyester surfaces have been determined from contact angle measurements using several liquid types. The geometric mean, the harmonic mean, and Fowkes' methods for obtaining the components of surface free energy have been compared for poly(L ‐lactic acid) (PLLA), poly(DL ‐lactic acid) (PDLLA), poly(hydroxybutyrate) (PHB), and poly(hydroxybutyrate‐hydroxyvalerate) (PHB–HV) copolymers. Polymer films were obtained by solution casting onto a number of smooth substrates, ranging from high‐energy surfaces (aluminum, mercury, glass, and freshly cleaved mica) to low‐energy surfaces [poly(ethyleneterephthalate) (PET), polytetrafluoroethylene (PTFE), and air]. Results show that the dispersion and polar surface free energy components of polyester surfaces cast against high surface energy (hydrophilic) substrates decrease with aging time toward a stable value. However, when cast against low surface energy substrates, the surface free energy of the resulting polymer/substrate‐contacting surface was independent of aging time. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 997–1008, 2002     

Permeability of ethanol solution through poly(lactic acid) film

The permeation properties of ethanol solution through poly(lactic acid) (PLA) films were investigated. The total flux of ethanol solution through PLA films was strongly depended on the flux of water. In addition, the diffusion coefficient of water was 1000 times higher than that of ethanol, and decreased with increasing feed concentration. After the permeation measurement, crystallization (X_C‐DSC = 1–2%) was observed. However, the crystallinity was not dependent on the feed concentration. On the other hand, the mole ratio of ethanol and water molecules in the PLA film strongly depended on the feed concentration. Based on the results, we concluded that the interaction with ethanol molecules caused the decrease in diffusion coefficient of water in PLA film. Thus, the permeation mechanism of the ethanol solution to the PLA film was investigated in detail. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42031.     

金属离子对脂肪族聚酯降解性能的影响

在土壤培养液中添加不同种类的金属离子,研究了它们对可生物降解聚酯聚乳酸（PLA）、聚丁二酸丁二酯（PBS）膜降解性能的影响。采用傅里叶变换红外光谱仪表征了PLA和PBS膜降解前后的化学结构。结果表明：所有降解后的膜表面均有明显被侵蚀的痕迹;在土壤培养液中的Mg^2＋,Zn^2＋,Ca^2＋对PLA的降解性能有促进作用,对PBS的降解性能则影响不大;降解后PLA膜的玻璃化转变温度有所升高,但PBS膜变化不大。