Thermal degradation of polycarbonate, poly(vinyl acetate) and their blends

We have recently developed a novel approach for intimately mixing thermodynamically incompatible polymers, which utilizes the formation of inclusion compounds (ICs) formed with host cyclodextrins (CDs), followed by removal of CD and coalescence of the common guest polymers into a blend. In this paper direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of polycarbonate (PC), poly(vinyl acetate) (PVAc) and PC/PVAc blends, obtained by coalescence from their inclusion compounds formed with host γ-CD (coalesced blend) and by co-precipitation (physical blend), have been performed. Variations in the thermal stabilities of the coalesced polymers were recorded both by TGA and DIP-MS and compared to the corresponding as-received polymers. It has been determined that for both coalesced and physical blends of PC/PVAc, CH₃COOH formed by deacetylation of PVAc above 300 °C, reacts with PC chains decreasing their thermal stability. This process was more effective for the physical blend, most likely due to enhanced diffusion of CH₃COOH, produced by deacetylation of PVAc, into the PC domains, where it can further react producing low molecular weight PC fragments bearing methyl carbonate chain ends.     

An intimate polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blend via coalescence from their common inclusion compound with γ‐cyclodextrin

In this study, we successfully report an intimate ternary blend system of polycarbonate (PC)/poly(methyl methacrylate) (PMMA)/poly(vinyl acetate) (PVAc) obtained by the simultaneous coalescence of the three guest polymers from their common γ‐cyclodextrin (γ‐CD) inclusion compound (IC). The thermal transitions and the homogeneity of the coalesced ternary blend were studied by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The observation of a single, common glass transition strongly suggests the presence of a homogeneous amorphous phase in the coalesced ternary polymer blend. This was further substantiated by solid‐state ¹³C NMR observation of the T_1ρ(¹H)s for each of the blend components. For comparison, ternary blends of PC/PMMA/PVAc were also prepared by traditional coprecipitation and solution casting methods. TGA data showed a thermal stability for the coalesced ternary blend that was improved over the coprecipitated blend, which was phase‐segregated. The presence of possible interactions between the three polymer components was investigated by infrared spectroscopy (FTIR). The analysis indicates that the ternary blend of these polymers achieved by coalescence from their common γ‐CD–IC results in a homogeneous polymer blend, possibly with improved properties, whereas coprecipitation and solution cast methods produced phase separated polymer blends. It was also found that control of the component polymer molar ratios plays a key role in the miscibility of their coalesced ternary blends. Coalescence of two or more normally immiscible polymers from their common CD–ICs appears to be a general method for obtaining well‐mixed, intimate blends. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4182–4194, 2004     

Interactions and prediction of phase diagrams in ternary blends comprising poly(vinyl acetate), poly(vinyl p‐phenol), and poly(methyl methacrylate)

This study investigated and discovered a new miscible ternary blend system comprising three amorphous polymers: poly(vinyl acetate) (PVAc), poly(vinyl p‐phenol) (PVPh), and poly(methyl methacrylate) (PMMA) using thermal analysis and optical and scanning electron microscopies. The ternary compositions are largely miscible except for a small region of borderline ternary miscibility near the side, where the binary blends of PVAc/PMMA are originally of a borderline miscibility with broad T_g. In addition to the discovering miscibility in a new ternary blend, another objective of this study was to investigate whether the introduction of a third polymer component (PVPh) with hydrogen bonding capacity might disrupt or enhance the metastable miscibility between PVAc and PMMA. The PVPh component does not seem to exert any “bridging effect” to bring the mixture of PVAc and PMMA to a better state of miscibility; neither does the Δχ effect seem to disrupt the borderline miscible PVAc/PMMA blend into a phase‐separated system by introducing PVPh. Apparently, the ternary is able to remain in as a miscible state as the binary systems owing to the fact that PVPh is capable of maintaining roughly equal H‐bonding interactions with either PVAc or PMMA in the ternary mixtures to maintain balanced interactions among the ternary mixtures. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1147–1160, 2006     

Thermal and photochemical stability of poly(methyl methacrylate) and its blends with poly(vinyl acetate)

An investigation of the thermal stability of poly(methyl methacrylate) (PMMA) blends with poly(vinyl acetate) (PVAc) revealed that PVAc acts as a stabilizer as concerns thermal and photochemical degradation when the processes take place in air. The temperatures of decomposition of these blends are higher than that of pure PMMA. The efficiency of photodegradation and photooxidation in the blends is lower than that of pure PMMA.     

Investigation at the chain segmental level of the miscibility of poly(vinyl chloride)/atactic poly(methyl methacrylate) blends

We employed high‐resolution ¹³C cross‐polarization/magic‐angle‐spinning/dipolar‐decoupling NMR spectroscopy to investigate the miscibility and phase behavior of poly(vinyl chloride) (PVC)/poly(methyl methacrylate) (PMMA) blends. The spin–lattice relaxation times of protons in both the laboratory and rotating frames [T₁(H) and T_1ρ(H), respectively] were indirectly measured through ¹³C resonances. The T₁(H) results indicate that the blends are homogeneous, at least on a scale of 200–300 Å, confirming the miscibility of the system from a differential scanning calorimetry study in terms of the replacement of the glass‐transition‐temperature feature. The single decay and composition‐dependent T_1ρ(H) values for each blend further demonstrate that the spin diffusion among all protons in the blends averages out the whole relaxation process; therefore, the blends are homogeneous on a scale of 18–20 Å. The microcrystallinity of PVC disappears upon blending with PMMA, indicating intimate mixing of the two polymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2390–2396, 2001     

Fire retardant poly(ethylene terephthalate)/polycarbonate/triphenyl phosphite blends

Flame retardant recycled PET blends containing PC and triphenyl phosphite (TPP) have been designed using the following sequential processing strategy: PET and PC are first melt blended with a transesterification catalyst, allowing the compatibilisation of the blend, before adding TPP. The presence of this last component was shown to stop the transesterification reaction between PET and PC, avoiding chain breaking. In addition, TPP acts as a chain extender of PET, allowing the average chain length to be increased. The optimized blends obtained present “V-0” UL94 rating due to a better thermal stability leading to low flammability and to the development of an important, stable and covering char layer, resulting in self-extinguishability and very low Heat Release Rates during combustion.     

聚甲基丙烯酸甲酯与聚醋酸乙烯酯共混的红外光谱研究

用红外光谱(FTIR)研究了聚甲基丙烯酸甲酯(PMMA)与聚醋酸乙烯酯(PVAc)共混体系相容性,在160℃以上共混体系发生相分离;分相体系与非分相体系的FTIR谱明显不同;共混体系的FTIR谱不能从两统组分红外光谱简单加和得到;结果表明大分子构象发生了变化,PMMA/PVAc体系相容可能是大分子构象熵变所致。     

Effect of poly(vinyl acetate) (PVAc) on thermal behavior and mechanical properties of poly(3-hydroxybutyrate)/poly(propylene carbonate) (PHB/PPC) blends

To assess the compatibility of blends of synthetic poly(propylene carbonate) (PPC), with a natural bacterial poly(3-hydroxybutyrate) (PHB), a simple casting procedure of blend was used. poly(3-hydroxybutyrate)/poly(propylene carbonate) blends are found to be incompatible according to DSC and DMA analysis. In order to improve the compatibility and mechanical properties of PHB/PPC blends, poly(vinyl acetate) (PVAc) was added as a compatibilizer. The effects of PVAc on the thermal behavior, morphology, and mechanical properties of 70PHB/30PPC blend were investigated. The results show that the melting point and the crystallization temperature of PHB in blends decrease with the increase of PVAc content in blends, the loss factor changes from two separate peaks of 70PHB/30PPC blend to one peak of 70PHB/30PPC/12PVAc blend. It is also found that adding PVAc into 70PHB/30PPC blend can decrease the size of dispersed phase from morphology analysis. The result of tensile properties shows that PVAc can increase the tensile strength and Young’s modulus of 70PHB/30PPC blend, and both the elongation at break and the tensile toughness increase significantly with PVAc added into 70PHB/30PPC.     

Viscometric study of poly(vinyl chloride)/poly(vinyl acetate) blends in various solvents

The intermolecular interactions between poly(vinyl chloride) (PVC) and poly(vinyl acetate) (PVAc) in tetrahydrofuran (THF), methyl ethyl ketone (MEK) and N,N^′-dimethylformamide (DMF) were thoroughly investigated by the viscosity measurement. It has been found that the solvent selected has a great influence upon the polymer-polymer interactions in solution. If using PVAc and THF, or PVAc and DMF to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+THF) or (PVAc+DMF) is less than in corresponding pure solvent of THF or DMF. On the contrary, if using PVAc and MEK to form polymer solvent, the intrinsic viscosity of PVC in polymer solvent of (PVAc+MEK) is larger than in pure solvent of MEK. The influence of solvent upon the polymer-polymer interactions also comes from the interaction parameter term Δb, developed from modified Krigbaum and Wall theory. If PVC/PVAc blends with the weight ratio of 1/1 was dissolved in THF or DMF, Δb<0. On the contrary, if PVC/PVAc blends with the same weight ratio was dissolved in MEK, Δb>0. These experimental results show that the compatibility of PVC/PVAc blends is greatly associated with the solvent from which polymer mixtures were cast. The agreement of these results with differential scanning calorimetry measurements of PVC/PVAc blends casting from different solvents is good.     

Poly(vinyl alcohol)/poly(methyl methacrylate) blend membranes for pervaporation separation of water + isopropanol and water + 1,4-dioxane mixtures

Pervaporation (PV) separation of water + isopropanol and water + 1,4-dioxane mixtures has been attempted using the blend membranes of poly(vinyl alcohol) (PVA) with 5 wt.% of poly(methyl methacrylate) (PMMA). These results have been compared with the plain PVA membrane. Both plain PVA and PVA/PMMA blend membranes have been crosslinked with glutaraldehyde in an acidic medium. The membranes were characterized by differential scanning calorimetry and universal testing machine. Pervaporation separation experiments have been performed at 30 °C for 10, 15, 20, 30 and 40 wt.% of feed water mixtures containing isopropanol as well as 1,4-dioxane. PVA/PMMA blend membrane has shown a selectivity of 400 for 10 wt.% of water in water + isopropanol feed, while for water + 1,4-dioxane feed mixture, membrane selectivity to water was 104 at 30 °C. For both the feed mixtures, selectivity for the blend membrane was higher than that observed for plain PVA membrane, but flux of the blend membrane was lower than that observed for the plain PVA membrane. Membranes of this study are able to remove as much as 98 wt.% of water from the feed mixtures of water + isopropanol, while 92 wt.% of water was removed from water + 1,4-dioxane feed mixtures at 30 °C. Flux of water increased for both the feed mixtures, while the selectivity decreased at higher feed water concentrations. The same trends were observed at 40 and 50 °C for 10, 15 and 20 wt.% of water mixtures containing isopropanol as well as 1,4-dioxane feed mixtures, which also covered their azeotropic composition ranges. Membrane performance was studied by calculating flux (J_p), selectivity (), pervaporation separation index (PSI) and enrichment factor (β). Permeation flux followed the Arrhenius trend over the range of temperatures investigated. It was found that by introducing a hydrophobic PMMA polymer into a hydrophilic PVA, the selectivity increased dramatically, while flux decreased compared to plain PVA, due to a loss in PVA chain relaxation.     

Structural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) copolymer by nuclear magnetic resonance and mass spectrometry

Mass spectrometry (MS) and nuclear magnetic resonance (NMR) have been combined to achieve the complete microstructural characterization of a poly(methacrylic acid)-poly(methyl methacrylate) (PMAA-PMMA) copolymer synthesized by nitroxide-mediated polymerization. Various PMAA-PMMA species could be identified which mainly differ in terms of terminaisons. ¹H and ¹³C NMR experiments revealed the structure of the end-groups as well as the proportion of each co-monomer in the copolymers. These end-group masses were further confirmed from m/z values of doubly charged copolymer anions detected in the single stage mass spectrum. In contrast, copolymer composition derived from MS data was not consistent with NMR results, obviously due to strong mass bias well known to occur during electrospray ionization of these polymeric species. Tandem mass spectrometry could reveal the random nature of the copolymer based on typical dissociation reactions, i.e., water elimination occurred from any two contiguous MAA units while MAA-MMA pairs gave rise to the loss of a methanol molecule. Polymer backbone cleavages were also observed to occur and gave low abundance fragment ions which allowed the structure of the initiating end-group to be confirmed.     

Thermal degradation processes of poly(carbonate) and poly(methyl methacrylate) in blends coalesced either from their common inclusion compound formed with γ-cyclodextrin or precipitated from their common solution

Direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of a PC/PMMA blend, coalesced from their common inclusion compound (ICs) formed with host γ-cyclodextrin (γ-CD) through removal of the γ-CD host, and a physical PC/PMMA blend, precipitated from their common solution, have been performed and compared with those of the coalesced and as-received homopolymers. A slight increase in the thermal stability of the PMMA component in the presence of PC was recorded both by TGA and DIP-MS compared to the corresponding homopolymers. The DIP-MS observations pointed out that the thermal stability and degradation products of these polymers are affected once they are included inside the IC channels created by the stacked host CDs. DIP-MS observations suggested that for both coalesced and physical PC/PMMA blends, an exchange reaction occurs between carbonates of PC and MMA, formed by depolymerization of PMMA above 300 °C, most likely due to diffusion of MMA monomer at the interface or even into the PC domains, where it can react producing low molecular weight PC bearing methyl carbonate and methacrylate chain ends. The results also indicated an ester-ester interchange reaction between PC and PMMA yielding a graft copolymer and low molecular weight PC chains bearing methyl carbonate end groups in the case of the coalesced blend. This can be atttributed to the presence of specific molecular interactions between the intimately mixed PMMA and PC chains in the coalesced PC/PMMA blend.     

Poly(ethylene-co-vinyl alcohol) and poly(methyl methacrylate) blends: Phase behavior and morphology

In this work blends of poly(ethylene-co-vinyl alcohol) (EVOH) with different ethylene contents (27, 32, 38 and 44 mol%) and poly(methyl methacrylate) (PMMA) were prepared by mechanical mixing in the melted state. The miscibility and melting behavior as a function of blend composition and the ethylene content in EVOH copolymers were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The morphology of the cryofractured surfaces was examined by scanning electron microscopy (SEM). DSC and DMTA data show that EVOH/PMMA blends are immiscible, independent of EVOH and blend composition. The SEM analysis in agreement with DMTA analysis indicates that the morphology of phases depends on the blend composition, with phase inversion occurring as the concentration of one or other polymer component increases. However, the copolymer composition apparently does not affect the domain size distribution for blends containing 20 wt% of EVOH or 20 wt% of PMMA. A better phase adhesion is observed mainly for blends with 50 wt% of each polymer component.     

Crystallization and melting behavior of poly(ethylene oxide)/poly(n-butyl methacrylate) blends

The phase diagram, crystallization and melting behavior of poly(ethylene oxide) (PEO)/poly(n-butyl methacrylate) (PnBMA) blends have been investigated using differential scanning calorimetry and optical microscopy. The results show that the blends are miscible up to 85 °C and show an lower critical solution temperature-type demixing at a higher temperature. The isothermal crystallization studies of the blends indicate a reduction in the overall rate of crystallization. Analysis of isothermal crystallization data by means of Avrami equation leads to average values of the Avrami index of 2.5 for pure PEO and 3.0 for the different blend compositions. The melting behavior of the blends reveals double endotherms, which is ascribed to both secondary crystallization and recrystallization. The melting point depression study yielded χ₁₂=0, indicating a relatively low interaction strength.     

Compatibilization of blends of polybutadiene and poly(methyl methacrylate) with poly(butadiene-block-methyl methacrylate)

Compatibilization of blends of polybutadiene and poly(methyl methacrylate) with butadiene-methyl methacrylate diblock copolymers has been investigated by transmission electron microscopy. When the diblock copolymers are added to the blends, the size of PB particles decreases and their size distribution gets narrower. In PB/PMMA7.6K blends with P(B-b-MMA)25.2K as a compatibilizer, most of micelles exist in the PMMA phase. However, using P(B-b-MMA)38K as a compatibilizer, the micellar aggregation exists in PB particles besides that existing in the PMMA phase. The core of a micelle in the PMMA phase is about 10 nm. In this article the influences of temperature and homo-PMMA molecular weight on compatibilization were also examined. At a high temperature PB particles in blends tend to agglomerate into bigger particles. When the molecular weight of PMMA is close to that of the corresponding block of the copolymer, the best compatibilization result would be achieved. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 85–93, 1998     

Preparation of poly (methyl methacrylate)/LDH nanocomposite by exfoliation-adsorption process

Exfoliated nanocomposite based on Mg, Al layered double hydroxide (Mg,Al-LDH) and poly(methyl methacrylate) (PMMA) has been prepared by exfoliation/adsorption process with acetone as co-solvent. The product was characterized by X-ray diffraction (XRD), thermal analysis and High Resolution Transmission Electronic Microscope (HREM). The results suggest that the brucite-like sheets of LDH disperse individually in the polymer matrix, and the thermal stability of the nanocomposite increases highly.     

Absorption and photoluminescence of Buriti oil/polystyrene and Buriti oil/poly(methyl methacrylate) blends

This work reports the preparation and characterization of Buriti (Mauritia flexuosa L.) oil/polystyrene (PS) and Buriti oil/poly(methyl methacrylate) blends. The Buriti is an abundant palm tree of the Amazon region. This oil was used because of its chemical composition (high concentrations of oleic acid, tocopherols and carotenoids, especially β-carotene) and interesting optical properties, such as absorption and photoluminescence. The incorporation of the vegetable oil in the PS and PMMA matrices renders orange-colored blends, which were verified to absorb UV-Vis radiation and emit light in the green region. The intensity of these properties is proportional to the oil content in the samples. Micrographs of the blends showed that the oil is located in cavities distributed in the polymeric matrices. This work shows that it is possible to employ the Buriti oil, a cheaper and abundant natural resource, to improve absorption and light emission properties of PS and PMMA polymers.     

Effect of transesterification products on the miscibility and phase behavior of poly(trimethylene terephthalate)/bisphenol A polycarbonate blends

Blends of poly(trimethylene terephthalate)/bisphenol A polycarbonate (PTT/PC) with different compositions were prepared by melt blending. The effect of transesterification on the miscibility and phase behavior of the blends was studied using DSC, DMA, and ¹H NMR. The DMA results revealed a two-phase system with partial miscibility. DSC thermograms of the first heating scan showed a crystallizable system in which addition of PC-phase reduces the degree of crystallinity. However, the cooling and also the second heating scans revealed the complete miscibility of all the blends. It was concluded that annealing at 300 °C (to remove thermal history of the blends) caused the constituents to undergo the transesterification reaction, which changes the blend to a miscible system. The miscibility is due to formation of block copolymers with different block lengths which also suppress the crystallization of the system. The degree of randomness and sequence lengths of the copolymers were determined to analyze the extent of transesterification reaction and structure of the system. It was observed that as the reaction progresses, the degree of randomness increases and the sequence length of the copolymers decreases. Moreover, both increase of reaction time and temperature increased the extent of reaction. The results of DSC and ¹H NMR showed that a small amount of reaction is needed to change this system to a miscible blend.     

Effects of ceramic filler in poly(vinyl chloride)/poly(ethyl methacrylate) based polymer blend electrolytes

Effects of nano-ceramic filler titanium oxide (TiO₂) have been investigated on the ionic conductance of polymeric complexes consisting of poly(vinyl chloride) (PVC)/poly(ethyl methacrylate) (PEMA), and lithium perchlorate (LiClO₄). The composite polymer blend electrolytes were prepared by solvent casting technique. The TiO₂ nanofillers were homogeneously dispersed in the polymer electrolyte matrix and exhibited excellent interconnection with PVC/PEMA/PC/LiClO₄ polymer electrolyte. The addition of TiO₂ nanofillers improved the ionic conductivity of the polymer electrolyte to some extent when the content of TiO₂ is 15 wt%. The addition of TiO₂ also enhanced the thermal stability of the electrolyte. The changes in the structural and complex formation properties of the materials are studied by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) techniques. The scanning electronmicroscope image of nano-composite polymer electrolyte membrane confirms that the TiO₂ nanoparticles were distributed uniformly in the polymer matrix.     

Emulsion terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate: Experimental results

A systematic study of the terpolymerization of butyl acrylate/methyl methacrylate/vinyl acetate (BA/MMA/VAc) was conducted. In this stage of the study, batch emulsion terpolymerizations were performed in a 5 L stainless steel pilot plant reactor. The experiments were designed using a Bayesian (optimal) technique. The polymers produced were characterized for conversion, composition, molecular weight, and particle size. Conversion, terpolymer composition, number- and weight-average molecular weight, and average particle size results are discussed in light of the influence of seven factors and the interaction of these factors. The factors studied include monomer feed composition, initiator concentration, chain transfer agent concentration, impurity concentration, initiator type, emulsifier concentration, and temperature. A “two-stage rate” phenomenon, similar to that occurring in bulk co- and terpolymerization and emulsion copolymerization of acrylic/vinyl acetate systems was observed in the conversion, composition and molecular weight data. Furthermore, an interesting yet often ignored effect of impurities on emulsion polymerization kinetics was explained. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 1659–1672, 1997