Miscibility and hydrolytic degradation in alkaline solution of poly(l-lactide) and poly(methyl methacrylate) blends

Poly(l-lactide) (PLLA) was melt blended with poly(methyl methacrylate) (PMMA) using a two-roll mill. The miscibility and hydrolytic degradation of the blend films were characterized. It was found that PLLA/PMMA blend has high miscibility in the amorphous state because only single T_g was observed in the DSC and DMA measurements. In alkaline solution, the hydrolytic degradation rate of the blends whose PMMA content is higher than 30 wt% was decelerated while the rate of the blends whose PMMA content is lower than 30 wt% was accelerated. That is, the hydrolytic degradation rate of the blends could be widely controlled by PMMA content in the blend. It was also found that only PLLA was hydrolyzed and eluted into alkaline solution, while PMMA remained during alkaline hydrolysis.     

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     

Influence of PLA stereocomplex crystals and thermal treatment temperature on the rheology and crystallization behavior of asymmetric poly(L-Lactide)/poly(D-lactide) blends

Asymmetric poly(L-lactide)/poly(D-Lactide) (PLLA/PDLA) blends were prepared by adding small amounts of PDLA into the PLLA matrix with the formation of stereocomplex crystallites (sc-crystallites). Rheological results indicated that the PLLA/PDLA melt at lower temperatures (<T_m,sc, the melting temperature of the formed stereocomplex crystallites) underwent the transition from liquid-like to solid-like viscoelastic behaviors with increasing of the PDLA concentration, which was related to the sc-crystallites reserved in the melt of asymmetric PLLA/PDLA blends. Dissolution experiment indicated the presence of sc-crystallites network structure in the PLLA/PDLA blends, and the size of the sc-crystallite junction particles network increased with increasing of the PDLA concentration. DSC and POM studies indicated that the PDLA concentration and the thermal treatment temperature had a significant influence on the PLLA crystallizability behavior. At low thermal treatment temperature (<T _m,sc ), reserved sc-crystallites showed an obvious promoting effect for PLLA crystallization. With increasing of the thermal treatment temperature, its promoting effect decreased due to melting of the sc-crystallites. This result suggests the sc-crystallites played two roles: nucleation sites and cross-linking points, and the two roles had a competitive relationship with change of the thermal treatment temperature and the PDLA concentration.     

Miscibility of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) and poly(vinyl chloride) blends

The miscibility behaviour of biodegradable poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHB-HV) blended with poly(vinyl chloride) (PVC) was investigated by using differential scanning calorimetry, dynamic mechanical thermal analysis, Fourier-transform infra-red spectroscopy and a mechanical testing system. A blend of PHB-HV containing 8% HV (PHB-8HV) with PVC was immiscible, showing two separate T_g values in all compositions: whereas a blend of PHB-HV containing 18% HV (PHB-18HV) with PVC was miscible, showing a melting-point depression and a single T_g in the whole range of compositions. For the PHB-18HV/PVC system, the C-O-C stretching vibration at 1183 cm⁻¹ of PHB-18HV and the CHCl deformation at 1254cm⁻¹ of PVC were shifted, indicating that there exists a specific intermolecular interaction between the two components. In addition, as the PVC component was increased, tensile strength and Young's modulus were increased, while the inverse behaviour was observed in elongation at break.     

Relationship between the crystallization behavior of poly(ethylene glycol) and stereocomplex crystallization of poly(L‐lactic acid)/poly(D‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a good biomedical polymer material with wide applications. The addition of poly(ethylene glycol) (PEG) as a plasticizer and the formation of stereocomplex crystals (SCs) have been proved to be effective methods for improving the crystallization of PLLA, which will promote its heat resistance. In this work, the crystallization behavior of PEG and PLLA/poly(d ‐lactic acid) (PDLA) in PLLA/PDLA/PEG and PEG‐b‐PLLA/PEG‐b‐PDLA blends has been investigated using differential scanning calorimetry, polarized optical microscopy and X‐ray diffraction. Both SCs and homocrystals (HCs) were observed in blends with asymmetric mass ratio of PLLA/PDLA, while exclusively SCs were observed in blends with approximately equal mass ratio of PLLA/PDLA. The crystallization of PEG was only observed for the symmetric blends of PLLA_39k/PDLA_35k/PEG_2k, PLLA_39k/PDLA_35k/PEG_5k, PLLA_69k/PDLA_96k/PEG_5k and PEG‐b‐PLLA_31k/PEG‐b‐PDLA_27k, where the mass ratio of PLLA/PDLA was approximately 1/1. The results demonstrated that the formation of exclusively SCs would facilitate the crystallization of PEG, while the existence of both HCs and SCs could restrict the crystallization of PEG. The crystallization of PEG is related to the crystallinity of PLLA and PDLA, which will be promoted by the formation of SCs. © 2017 Society of Chemical Industry     

Immiscibility–miscibility phase transitions in blends of poly(L‐lactide) with poly(methyl methacrylate)

BACKGROUND: The nature of phase transitions and apparently irreversible phase homogenization upon heating in blends of biodegradable poly(L ‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were proven using differential scanning calorimetry, polarized optical microscopy, scanning electron microscopy and ¹H NMR spectroscopy. The complex phase behaviour in this blend system is puzzling and is a matter of debate; this study attempts to clarify the true nature of the phase behaviour. RESULTS: A PMMA/PLLA blend is immiscible at ambient temperature but can become miscible upon heating to higher temperatures with an upper critical solution temperature (UCST) at 230 °C. The blends, upon rapid quenching from the UCST, can be frozen into a quasi‐miscible state. In this state, the interaction strength was determined to be χ₁₂ = ? 0.15 to ? 0.19, indicating relatively weak interactions between the PLLA ester and PMMA acrylic carbonyl groups. CONCLUSION: The absence of chemical exchange reactions above the UCST and phase reversibility back to the original phase separation morphology, assisted by solvent re‐dissolution, in the heat‐homogenized PLLA/PMMA blend was shown. Verification of UCST behaviour, phase diagrams and solvent‐assisted phase reversibility were experimentally demonstrated in PMMA/PLLA blends. Copyright © 2008 Society of Chemical Industry     

Nanocomposites based on vermiculite clay and ternary blend of poly(L‐lactic acid), poly(methyl methacrylate), and poly(ethylene oxide)

Vermiculite (VMT) as clay was introduced into a ternary polymer blend composed of poly(L ‐lactic acid) (PLLA), poly(methyl methacrylate) (PMMA), and poly(ethylene oxide) (PEO), whose ternary miscibility was proven within low certain contents of PMMA and PEO in PLLA. VMT was incorporated to the ternary polymer blend as matrix after proper organic modification on the clay. The organically modified vermiculite (OVMT) shows good interaction and acceptable dispersion in the ternary polymer matrix without altering the crystal structures of PLLA/PEO constituents. The effect of OVMT addition was then analyzed in isothermal crystallization by using the Avrami kinetic analysis, and the addition of OVMT is evident in altering nucleation process of the polymer blend as well as the crystal perfection. The activation energy is much lowered by the addition of OVMT, as evident from the analysis; the overall crystallization kinetic rates are increased with the incorporation of OVMT. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

不同构型聚乳酸共混体系的立构复合结晶研究进展

左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)在共混体系中可形成立构复合(sc)结晶,与聚乳酸(PLA)同质结晶材料相比,sc 结晶材料具有良好的耐热性和耐化学稳定性。因此,sc 结晶是改善PLA 综合性能的一种有效手段。但在PLLA/PDLA 共混体系中,存在各自的同质结晶与两者之间sc 结晶的竞争,所以制备高耐热sc 型PLA 材料的关键之一是理解其sc 结晶的形成条件与机理,进而调控和促进其sc 结晶程度。在PLLA/PDLA 共混物中,sc 结晶受聚合物化学结构、结晶与加工条件等诸多因素影响,其影响规律和机理较复杂。根据PLLA/PDLA共混物sc 结晶行为影响因素的不同,从聚合物分子量、立构规整性、共混比例、分子链拓扑结构、结晶方式与条件、加工助剂和其他组分加入6 个方面出发,详细综述了PLLA/PDLA 共混物sc 结晶及其sc 材料制备的研究进展,以期为高耐热生物基PLA 材料的加工制备提供指导。     

Thermomechanical properties of stereoblock poly(lactic acid)s with different PLLA/PDLA block compositions

Stereoblock poly(lactic acids) (sb-PLAs), having abundant enantiomeric compositions of poly(l-lactic acid) (PLLA), were successfully synthesized by solid-state polycondensation (SSP) of the melt blends of medium molecular weight prepolymers: both PLLA and poly(d-lactic acid) (PDLA) that had primarily been prepared by melt-polycondensation. The molecular weight of the resultant PLLA-rich sb-PLA was effectively enhanced by the dehydrative coupling of abundant PLLA molecules followed by the increase in homo-chiral crystallinity. These sb-PLA were successfully fabricated into polymer films by solution casting to analyze their crystalline morphology and properties. Both DSC and WAXS revealed preferential stereocomplexation in spite of concomitant homo-chiral crystallization for these sb-PLA. Particularly, exclusive sc crystallization was observed with melt-quenched sb-PLA represented whose PDLA ratio was above 15%. Therefore, the stereoblock structure can suppress the homo-chiral crystallization and increase the sc crystallinity even with the non-equivalent PLLA/PDLA compositions. Their thermal resistivity up to 200 °C was supported by the dynamic mechanical analysis of the sb-PLA films.     

Enhanced crystallization rate and mechanical properties of poly(l‐lactic acid) by stereocomplexation with four‐armed poly(ϵ‐caprolactone)‐block‐poly(d‐lactic acid) diblock copolymer

Poly(l ‐lactic acid) (PLLA) was blended with a series of four‐armed poly(? ‐caprolactone)‐block ‐poly(d ‐lactic acid) (4a‐PCL‐b ‐PDLA) copolymers in order to improve its crystallization rate and mechanical properties. It is found that a higher content of 4a‐PCL‐b ‐PDLA copolymer or longer PDLA block in the copolymer lead to faster crystallization of the blend, which is attributed to the formation of stereocomplex crystallites between PLLA matrix and PDLA blocks of the 4a‐PCL‐b ‐PDLA copolymers. Meanwhile, the PDLA block can improve the miscibility between flexible PCL phase and PLLA phase, which is beneficial for improving mechanical properties. The tensile results indicate that the 10% 4a‐PCL_5k‐b ‐PDLA_5k/PLLA blend has the largest elongation at break of about 72% because of the synergistic effects of stereocomplexation between enantiomeric PLAs, multi‐arm structure and plasticization of PCL blocks. It is concluded that well‐controlled composition and content of 4a‐PCL‐b ‐PDLA copolymer in PLLA blends can significantly improve the crystallization rate and mechanical properties of the PLLA matrix. © 2017 Society of Chemical Industry     

Synchronous and separate homo-crystallization of enantiomeric poly(l-lactic acid)/poly(d-lactic acid) blends

High-molecular-weight poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) are blended at different ratios and their crystallization behavior was investigated. Solely homo-crystallites mixtures of PLLA and PDLA were synchronously and separately formed during isothermal crystallization in the temperature (T_c) range of 90–130 °C, irrespective of blending ratio, whereas in addition to homo-crystallites, stereocomplex crystallites were formed in the equimolar blends at T_c above 150 and 160 °C. Interestingly, in isothermal crystallization at T_c = 130 °C, the spherulite morphology of blends became disordered, the periodical extinction (periodical twisting of lamellae) in spherulites disappeared, and the radial growth rate of spherulite (G) of the blends was reduced by the synchronous and separate crystallization of PLLA and PDLA and the coexistence of PLLA and PDLA homo-crystallites. However, the interplane distance (d), the crystallinity (X_c), the transition crystallization temperature (T_c) from α′-form to α-form, the alternately stacked structure of the crystalline and amorphous layers, and the nucleation mechanism were not altered by the synchronous and separate crystallization of PLLA and PDLA and the coexistence of PLLA and PDLA homo-crystallites. The unchanged d, X_c, transition T_c, long period of stacked lamellae, and nucleation mechanism strongly suggest that the chiral selection of PLLA or PDLA segments on the growth sites of PLLA or PDLA homo-crystallites to some extent was performed during solvent evaporation and this effect remained even after melting.     

Investigation of poly(lactide) stereocomplexation between linear poly(L‐lactide) and PDLA‐PEG‐PDLA tri‐block copolymer

In this study, stereocomplexed poly(lactide) (PLA) was investigated by blending linear poly(l ‐lactide) (PLLA) and tri‐block copolymer poly(d ‐lactide) ? (polyethylene glycol) ? poly(d ‐lactide) (PDLA‐PEG‐PDLA). Synthesized PDLA‐PEG‐PDLA tri‐block copolymers with different PEG and PDLA segment lengths were studied and their influences on the degree of sterecomplexation and non‐isothermal crystallization behaviour of the PLLA/PDLA‐PEG‐PDLA blend were examined in detail by DSC, XRD and polarized optical microscopy. A full stereocomplexation between PLLA and PDLA‐PEG_4k‐PDLA200 could be formed when the L/D ratio ranged from 7/3 to 5/5 without the presence of PLA homocrystals. The segmental mobility and length of both PEG and PDLA are the dominating factors in the critical D/L ratio to achieve full stereocomplexation and also for nucleation and spherulite growth during the non‐isothermal crystallization process. For fixed PEG segmental length, the stereocomplexed PLA formed showed first an increasing and then a decreasing melting temperature with increasing PDLA segments due to their intrinsic stiff mobility. Furthermore, the effect of PEG segmental mobility on PLA stereocomplexation was investigated. The results clearly showed that the crystallization temperature and melting temperature of stereocomplexed‐PLA kept increasing with increasing PEG segmental length, which was due to PEG soft mobility in the tri‐block copolymers. However, PEG was not favourable for nucleation but could facilitate the spherulite growth rate. Both the PDLA and PEG segmental lengths in the tri‐block copolymers affect the crystallinity of stereocomplexed‐PLA and the stereocomplexation formation process; they have a different influence on blends prepared by solution casting or the melting method. © 2015 Society of Chemical Industry     

A nonradiative energy transfer fluorescence spectroscopy study of poly(vinyl chloride)/poly(methyl methacrylate) blends

The miscibility of poly(vinyl chloride)/atactic poly(methyl methacrylate (PVC/a-PMMA) blends was investigated by nonradiative energy transfer fluorescence spectroscopy using naphthalene-labeled PVC (PVC-N) with anthracene-labeled PMMA (PMMA-A), or anthracene-labeled PVC (PVC-A) with carbazole-labeled PMMA (PMMA-C). The two sets of results indicate an increase in energy transfer efficiency, corresponding to an increase in blend miscibility, as the PVC concentration increases and, more importantly, demonstrate that the same information about blend miscibility can be obtained using different donor-acceptor chromophore pairs and by changing the polymer to which the donor or the acceptor is attached. The effect of the tacticity of PMMA on its miscibility with PVC was also investigated using PMMA-C and PVC-A labeled polymers. The results confirm that PVC/a-PMMA blends are more miscible than PVC/i-PMMA blends over a large range of compositions.     

Photocurrent in and miscibility of poly(N-vinylcarbazole)/poly(methyl methacrylate) blends

Summary Steady-state photocurrent in poly(N-vinylcarbazole)(PVCz) (26,48 wt%)/poly(methyl methacrylate)(PMMA) blends is for the first time measured. The PVCz(26,48 wt%)/PMMA blends showed almost the same carrier-generation efficiencies at electric fields higher than 1 × 10⁵ V · cm⁻¹. The results are explained by high miscibility of the PVCz(26,48 wt%)/PMMA blends, suggesting the existence of PVCz chains in continous PMMA-rich phase in the phase-separated structure. The miscibility is also evaluated by means of excimer fluorescence of PVCz in these blends and fluorescence microscopy. Received: 26 December 2000/Revised version: 16 January 2001/Accepted: 19 January 2001     

Investigation on the miscibility of the blends of poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile)

The miscibility was investigated in blends of poly(methyl methacrylate) (PMMA) and styrene‐acrylonitrile (SAN) copolymers with different acrylonitrile (AN) contents. The 50/50 wt % blends of PMMA with the SAN copolymers containing 5, 35, and 50 wt % of AN were immiscible, while the blend with copolymer containing 25 wt % of AN was miscible. The morphologies of PMMA/SAN blends were characterized by virtue of scanning electron microscopy and transmission electron microscopy. It was found that the miscibility of PMMA/SAN blends were in consistence with the morphologies observed. Moreover, the different morphologies in blends of PMMA and SAN were also observed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization behavior and hydrophilicity of poly(vinylidene fluoride)/poly(methyl methacrylate)/poly(vinyl pyrrolidone) ternary blends

Ternary blends composed of matrix polymer poly(vinylidene fluoride) (PVDF) with different proportions of poly(methyl methacrylate) (PMMA)/poly(vinyl pyrrolidone) (PVP) blends were prepared by melt mixing. The miscibility, crystallization behavior, mechanical properties and hydrophilicity of the ternary blends have been investigated. The high compatibility of PVDF/PMMA/PVP ternary blends is induced by strong interactions between the carbonyl groups of the PMMA/PVP blend and the CF₂ or CH₂ group of PVDF. According to the Fourier transform infrared and wide‐angle X‐ray difffraction analyses, the introduction of PMMA does not change the crystalline state (i.e. α phase) of PVDF. By contrast, the addition of PVP in the blends favors the transformation of the crystalline state of PVDF from non‐polar α to polar β phase. Moreover, the crystallinity of the PVDF/PMMA/PVP ternary blends also decreases compared with neat PVDF. Through mechanical analysis, the elongation at break of the blends significantly increases to more than six times that of neat PVDF. This confirms that the addition of the PMMA/PVP blend enhances the toughness of PVDF. Besides, the hydrophilicity of PVDF is remarkably improved by blending with PMMA/PVP; in particular when the content of PVP reaches 30 wt%, the water contact angle displays its lowest value which decreased from 91.4° to 51.0°. Copyright © 2011 Society of Chemical Industry     

Effect of nucleation and plasticization on the stereocomplex formation between enantiomeric poly(lactic acid)s

The effect of nucleation and plasticization on the stereocomplex formation between poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) was investigated in blends where PDLA is added as a minor phase in a major phase of PLLA. The use of small amounts of PDLA is aimed at creating a high melting point stereocomplex phase that in turn can serve as nucleating agent for the major phase of PLLA. Blends containing 5% PDLA with talc or organic phosphonate as nucleants and polyethylene glycol as plasticizer were prepared via melt-blending. Their crystallization behavior was investigated through Differential Scanning Calorimetry (DSC) using various thermal histories. Two peculiar stereocomplex melting endotherms were found. The peak temperature and enthalpy of these two endotherms were correlated to prior isothermal crystallization temperature. The different endotherms were also associated with two different crystalline morphologies observed by optical microscopy and referred to as Network and Spherulitic morphologies. The influence of plasticization and of heterogeneous nucleation on these morphologies was investigated through optical microscopy and calorimetric observations.     

Viscoelastic properties,morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly(methyl methacrylate) blends

Viscoelastic properties, morphology, and thermal stability of rigid and plasticized poly(vinyl chloride)/poly (methyl methacrylate) (PVC/PMMA) blends were studied. For that purpose, blends of variable composition from 0 to 100 wt% were prepared in the presence (15, 30, and 50 wt%) and in the absence of di(2‐ethylhexyl) phthalate as plasticizer. Their miscibility was investigated by using dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The DMTA and SEM results showed that the two polymers are miscible. Thermogravimetric studies on these blends were carried out in a flowing atmosphere of air from ambient temperature to 550°C. The results showed that the thermal degradation of rigid and plasticized PVC/PMMA in this broad range of temperature is a three‐step process and that PMMA exerted a stabilizing effect on the thermal degradation of PVC during the first step by reducing the rate of dehydrochlorination. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Studies on miscibility in homopolymer/ random copolymer blends by equation of state theory

The miscibility of poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymers (SAN) blends was investigated on the basis of the Flory—Orwoll—Vrij equation of state theory. To obtain the equation of state parameters (P*, V*_sp, T*: characteristic parameters), the pressure—volume—temperature (PVT) behaviour was measured for PMMA and a series of SANs with various acrylonitrile contents. The exchange energy parameter X_ij was also calculated by fitting the theory to some phase diagrams of PMMA/SAN blends. The Flory—Huggins interaction parameter χ was separated into two contributions based on the equation of state theory for mixtures: the exchange energy term χ_inter and the free volume term χ_free. Both the temperature and copolymer composition dependences of χ_inter and χ_free were estimated by calculations using the equation of state parameters. There exists a region in which χ_inter is negative, leading to a miscibility window in PMMA/SAN blends. However, the immiscibility at high temperatures in the blends cannot be explained only by χ_inter; it is caused by the free volume contribution, χ_free. The miscibility window behaviour in PMMA/SAN blends may be explained within the framework of the equation of state theory.     

Stereocomplex Crystallization Induced Significant Improvement in Transparency and Stiffness–Toughness Performance of Core-Shell Rubber Nanoparticles Toughened Poly(l-lactide) Blends

Toughening modification of poly(l -lactide) (PLLA) with rubber particles is often realized at the cost of transparency, mechanical strength, and modulus because high rubber loadings are generally required for toughening. In this work, a promising strategy to simultaneously improve the transparency and stiffness–toughness performance of poly(butyl acrylate)-poly(methyl methacrylate) (BAMMA) core-shell rubber nanoparticles toughened PLLA blends by utilizing the stereocomplex (SC) crystallization between PLLA and poly(d -lactide) (PDLA) is devised. The results reveal that the construction of SC crystallites in PLLA matrix via melt-mixing PLLA/BAMMA blends with PDLA can prevent BAMMA nanoparticles from aggregation and promote them to form network-like structure at lower contents. As a result, not only higher toughening efficiency with less rubber contents but also superior transparency is achieved in the PLLA/PDLA/BAMMA blends as compared with the PLLA/BAMMA ones where large aggregated BAMMA clusters are formed. Moreover, the outstanding reinforcement of SC crystallites network for PLLA can impart an enhanced tensile strength and modulus to PLLA/PDLA/BAMMA blends, thus improving the stiffness–toughness performance of PLLA/PDLA/BAMMA blends to a higher degree. This work demonstrates that SC crystallization is a promising solution to solve the contradiction between transparency and mechanical properties and then obtain superior comprehensive performances in rubber toughened PLLA blends.