Compatibility of binary systems of poly(methyl methacrylate), poly(vinyl chloride) and poly(vinyl acetate)

The influence of the thermal treatment on the stability in time of the dispersion degree of films containing binary polymer mixtures, poly(vinyl chloride)/poly(methyl methacrylate), poly(vinyl chloride)/poly(vinyl acetate) and poly(vinyl acetate)/poly(methyl methacrylate), was studied by thermogravimetry and optical microscopy with phase contrast. The dispersion degree depends particularly on the composition of the polymer mixture and can be improved by thermal treatment at temperatures above the glass temperatures of both homopolymers. It seems that this thermal treatment yields exclusively metastable structures with a general tendency to phase separation in a short time after thermal treatment, the heterogeneity mixtures (as film) being more pronounced.     

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 degradation of poly(vinyl bromide), vinyl bromide-methyl methacrylate copolymers,and poly(vinyl bromide)-poly(methyl methacrylate) blends

Degradation behavior has been compared for PVB, five VB-MMA copolymers which span the composition range, PMMA, and PVC by using thermogravimetry in dynamic nitrogen and thermal volatilization analysis (TVA) under vacuum for programmed heating at 10°C/min. Volatile products have been separated by subambient TVA and identified. PVB is substantially less stable than PVC but shows inmost respects analogous degradation behavior. The introduction of VB into the PMMA chain leads to intramolecular lactonization with release of methyl bromide at temperatures a little above 100°C; after this reaction is complete, however, the polymer is more stable toward volatilization than PMMA. Copolymers with moderate and high VB contents also lose hydrogen bromide. Carbon dioxide is a significant product at intermediate compositions. The variation of product distribution with copolymer composition is discussed in relation to the several reactions involved and comparisons are made with VC-MMA copolymers. PVB-PMMA blends snow some features of degradation behavior in common with the PVC-PMMA system but also very important differences. The effect of PVB is only to stabilize the PMMA; the mechanism is discussed. The role of PVB as an additive and VB as a comonomer for fire-retardant PMMA compositions is briefly considered in relation to earlier studies.     

Pyrolysis mass spectrometry analysis of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate) ternary blends

Direct insertion probe pyrolysis mass spectrometry (DIP-MS) analyses of polycarbonate/poly(methyl methacrylate)/poly(vinyl acetate), (PC/PMMA/PVAc), ternary blends have been performed. The PC/PMMA/PVAc ternary blends were obtained by coalescing from their common γ-cyclodextrin-inclusion compounds (CD-ICs), through the removal of the γ-CD host (coalesced blend), and by a co-precipitation method (physical blend). The coalesced ternary blend showed different thermal behaviors compared to the co-precipitated physical blend. The stability of PC chains decreased due to the reactions of CH₃COOH formed by deacetylation of PVAc above 300 °C, for both coalesced and physical blends. This process was more effective for the physical blend most likely due to the enhanced diffusion of CH₃COOH into the amorphous PC domains, where it can further react producing low molecular weight PC fragments bearing methyl carbonate chain ends. The decrease in thermal stability of PC chains was less significant for the coalesced ternary blend indicating that the diffusion of CH₃COOH was either somewhat limited or competed with intermolecular reactions between PMMA and PC and between PMMA and PVAc, which were detected and were associated with their close proximity in the intimately mixed coalesced PC/PMMA/PVAc ternary blend.     

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.     

Degradation of polymer mixtures. VIII. Blends of poly(vinyl acetate) with poly(methyl methacrylate)

The degradation of blends of PVA and PMMA in the form of films cast from a common solution of the polymers has been studied by TVA, TG, and EGA (evolved gas analysis) for acetic acid. Volatile degradation products have been characterized by spectroscopic and GLC techniques. Molecular weight, spectral and thermal stability changes in PMMA extracted from partially degraded blends have been examined. These blends behave in a closely analogous manner to PVC-PMMA blends already investigated. The results suggest that the PMMA component of the heterogeneous blends is modified in two ways: (1) in a destabilization reaction series initiated by attack of acetate radicals generated in the PVA phase which migrate into the PMMA phase, and (2) in a stabilization reaction involving conversion of ester side groups to acid and subsequently to anhydride ring structures which act as blocking points for depolymerization. The rate of acetic acid production in the blend is less than in PVA degraded alone. The mechanism of degradation of PVA is reconsidered in the light of these results.     

Miscibility and interactions of polystyrene/polyolefine and polystyrene/poly(n-alkyl methacrylate) mixtures in dilute xylene solutions

The miscibility and intermolecular interactions between polystyrene (PS) and poly(ethylene-co-propylene) (EPC), as well as between PS and long-chain poly(alkyl methacrylates) (PAMA), namely, poly(dodecyl methacrylate) (PDDMA) and poly(octadecyl methacrylate) (PODMA), in dilute xylene solutions at 30 °C were studied. Investigated polymers are widely used as rheology modifiers, i.e. viscosity index improvers and pour point depressants for lubricating mineral oils. The specific and reduced viscosities of two- and three-component polymer solutions as well as intrinsic viscosities and Huggins’ parameter values were determined as functions of the polymer mixture composition and overall polymer concentration. The reduced viscosity was found to be linearly dependent on the overall polymer concentration. The observed viscosities of polymer mixtures were intermediate to those of the mixture constituents; the values decrease in the order: EPC > PS > PAMA. The specific viscosities of all the polymer mixtures obtained as the experimental results and calculated applying the Catsiff-Hewett and Krigbaum-Wall theoretical equations were considered. Since all the polymer/polymer pairs showed the negative viscometric interaction parameter values (Δb₁₂ < 0), the PS/EPC and EPC/PAMA mixtures were found to be immiscible. The observed repulsive molecular interactions originate from the differences in polymer composition and molar masses. This conclusion was supported by calculations employing the group contribution approach of Coleman, Graf and Painter. The calculated values of interaction parameters for (co)polymer blends, Λ₁₂, were 5.47, 6.42 and 13.1 J cm⁻³ for PS/PDDMA, PS/PODMA and PS/EPC, respectively.     

Compatibility studies on solid polyblends of poly(methyl methacrylate) with poly(vinyl acetate) and polystyrene by ultrasonic technique

The behaviours of solid compatible, poly(methyl methacrylate)-poly(vinyl acetate), and incompatible, poly(methyl methacrylate)-polystyrene, blends have been studied by ultrasonic velocity measurements. It has been found that, in the compatible blends, the ultrasonic velocity varies linearly with composition; it deviates from linearity in the incompatible blends. These results are in conformity with the results of sonic velocity measurements for various compatible and incompatible blends reported by Hourston and Hughes. The variation of ultrasonic velocity has been explained in terms of morphology of the blends, with further evidence from scanning electron microscopy.     

Behavior of binary and ternary systems based on poly(vinyl chloride), poly(methyl methacrylate), and their copolymers

Mechanical properties, optical transmission, surface topography, and dielectric loss are studied for films formed by blends of polymers of vinyl chloride and methyl methacrylate with their copolymers.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1360–1365.Original Russian Text Copyright © 2004 by Bichuch, Izvozchikova, Zaitsev, Kronman, Semchikov.     

Study of the miscibility of poly(vinyl pyridines) with poly(vinyl acetate), poly(vinyl alcohol) and their copolymers

Miscibility of poly(4-vinyl pyridine) (P4VP) and poly(2-vinyl pyridine) (P2VP) with poly(viny acetate) (PVAc), poly(vinyl alcohol) PVA and poly(vinyl acetate-co-alcohol) (ACA copolymers) has been investigated over a wide composition range. Differentiaal scanning calorimetry (DSC) results indicate that P2VP is immiscible with PVAC, PVA, and their copolymers over the whole composition range. In turn, P4VP appears to be immiscible with PVAC and PVA, but miscible with some ACA copolymers in certain range of composition. The P4VP-ACA phase diagram for different copolymer compositions has been determined. The variation of the glass transition temperature with composition for miscible mixtures was found to follow the Gordon-Taylor equation, with the parameter κ dependent upon copolymer composition. FTIR analysis of blends reveal the existence of specific interactions via hydrogen bonding between hydroxyl groups and the nitrogen of the pyridinic ring, which appear to be decisive for miscibility. © 1994 John Wiley & Sons, Inc.     

Edge-excitation red shift of the fluorescence of flexible solute molecules in a poly(methyl methacrylate) polymer matrix

An excitation wavelength dependence of the fluorescence of tert-butyl and methyl esters of 9-anthroic acid and of tetraphenylbutadiene and tetraphenylmethylbutadiene in a poly(methyl methacrylate) (PMMA) polymer matrix is explained in terms of the presence of conformers that experience different free volumes at 77 K relative to room temperature.     

Self-stratified films obtained from poly(methyl methacrylate/n-butyl acrylate) colloidal dispersions containing poly(vinyl alcohol): a spectroscopic study

These studies focus on the role of poly(vinyl alcohol) (pVOH) during colloidal synthesis of poly(methyl methacrylate/n-butyl acrylate) (pMMA/nBA) and its effect on particle coalescence. Using 2D photoacoustic FT-IR spectroscopy and internal reflection IR imaging, we showed that the presence of pVOH creates competing environments between the copolymer particle surfaces, aqueous phases, and dispersing agents which results in migration and self-induced stratification occurring during coalescence. pMMA/nBA/pVOH films stratify to form sodium dodecyl sulfate rich film-air interfaces, and the -SO3- moieties exhibit preferential parallel orientation with respect to the surface. At the same time, the bulk of the film is dominated by intramolecular hydrogen bonding between the pVOH phase and the copolymer matrix. This behavior is attributed to significant interactions between pVOH and pMMA/nBA, resulting in limited mobility of pVOH.     

Interaction of water in polymers: Poly(ethylene‐co‐vinyl acetate) and poly(vinyl acetate)

We studied the interaction of water in poly(ethylene‐co‐vinyl acetate) of various vinyl acetate compositions and poly(vinyl acetate), on the basis of the infrared spectrum of the water dissolved therein. The spectrum shows a very sharp and distinct band at about 3690 cm^?1 (named as A), and less‐sharp two bands around 3640 (B) and 3550 cm^?1 (C), the A band being outstanding especially at a low vinyl acetate composition. As the vinyl acetate composition increases, the A band decreases in intensity relative to the C band, whereas the B band increases contrarily. Analysis of the spectral change has elucidated that one‐bonded water (of which one OH is hydrogen‐bonded to the C?O of an ester group and the other OH is free) and two‐bonded water (each OH of which is hydrogen‐bonded to one C?O) coexist in the copolymer and that two‐bonded water increases in relative population with increasing vinyl acetate composition. Dissolved water is entirely two‐bonded in poly(vinyl acetate), in which C?O groups are densely distributed in the matrix. We proved that dissolved water in polymers is hydrogen‐bonded through one or two OH groups to the possessed functional groups but does not cluster. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 777–785, 2005     

Reactions of organolithium compounds with poly(vinyl chloride), poly(methyl methacrylate) and poly(styrene-co-acrylonitrile) as labelling pathways with fluorescent chromophores

This paper reports pathways to attach anthracene and naphthalene to preformed poly(vinyl chloride) (PVC), poly(methyl methacrylate) (PMMA) and styrene-acrylonitrile random copolymer (SAN). The addition of 9-methylanthryl Li(1) or α-methyl-naphthyl Li(2) on the carbonyl of ester groups is an efficient means of labelling PMMA. The SN₂ nucleophilic substitution of the secondary chlorine atoms by (1) and (2) works well when Li is the counter-anion. The alkylation of SAN by 9-methylanthryl chloride in the presence of NLi diisopropylamide is another appropriate labelling pathway.     

Effects of poly(methyl methacrylate)-block-poly(vinyl acetate) copolymer on the spinodal decomposition of corresponding homopolymer blends

Effects of adding a small amount of poly(methyl methacrylate)-block-poly(vinyl acetate) (PMMA-b-PVAc) to poly(methyl methacrylate)/poly(vinyl acetate) (PMMA/PVAc) blends with a lower critical solution temperature (LCST) phase diagram on the kinetics of late-stage spinodal decomposition (SD) were investigated by time-resolved light scattering at 160°C. It is found that the coarsening process of the structure was slowed down or accelerated upon addition of PMMA-b-PVAc depending on the composition of the block copolymer and the blend. The effect of the block copolymer on the domain size were interpreted as compatibilizing and incompatibilizing effects of the block copolymer on PMMA/PVAc blends based on the evaluation of changes in the stability limits of PMMA/PVAc with the addition of block copolymer using random phase approximation (RPA).     

Thermal degradation of mixtures of poly(methyl methacrylate) and silver acetate

The degradation behavior of silver acetate—PMMA blends at salt/polymer ratios of 1:1, 1:5, and 1:10 has been studied by using thermal volatilization analysis (TVA) as the principal technique. Degradation of the salt has also been examined; it gives a variety of products best explained by a series of reactions resulting from an initial cleavage of CH₃COO. radicals and silver atoms. Silver acetate, when present with PMMA during degradation, results in a severe destabilization of the polymer, which breaks down to monomer at a high rate at temperatures as low as 200°C. This effect is explained by diffusion of radicals from silver acetate decomposition into the polymer phase, in which they initiate chain scission and depolymerization.     

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