Recycling of thermoplastic waste: Phase equilibrium in polystyrene-PVC-polyolefin solvent systems

The contribution of plastics to the total amount of waste produced is increasing significantly. Not only do plastics present disposal difficulties, but traditional disposal techniques constitute a waste of valuable resources. A process to recycle plastic waste economically would provide an attractive solution to both problems. Approximately 70 percent of the U.S. plastics production is comprised of only three families of plastics; polyethylene, PVC and polystyrene. Mixtures of these three polymers invariably have poor properties because of their thermodynamic incompatibility, so a recycle scheme will have to achieve separation into nearly pure components. A process is proposed which takes advantage of the thermodynamic incompatibility of polymers in solution to effect such a separation. The equilibration of a simulated waste mix containing 4 parts polyolefin (polyethylene and polypropylene), 1 part polystyrene and I part PVC was investigated in a variety of solvents at total polymer concentrations of up to 15 percent, in the temperature range 115 to 125°C, using differential refractometry. In an 85 percent xylene, 15 percent cyclohexanone solvent, the polyolefins (polypropylene and the various densities of polyethylene) coexisted in a single phase, but the three phases obtained—polyolefin, polystyrene and PVC—routinely contained 99 + percent pure polymer, indicating that excellent separations of the major thermoplastic components of a waste mix can indeed be obtained.     

Experimental study of the spontaneous thermal homopolymerization of methyl and n‐butyl acrylate

This article presents an experimental study of the spontaneous thermal homopolymerization of methyl acrylate (MA) and n‐butyl acrylate (nBA) in the absence of any known added initiators at 120 and 140°C in a batch reactor. The effects of the solvent type, oxygen level, and reaction temperature on the monomer conversion and polymer average molecular weights were investigated. Three solvents, dimethyl sulfoxide (DMSO; polar, aprotic), cyclohexanone (polar, aprotic), and xylene (nonpolar) were used. The spontaneous thermal polymerization of MA and nBA in DMSO resulted in a lower conversion and higher average molecular weights in comparison to polymerization in cyclohexanone and xylene under the same conditions. The highest final conversion of both monomers was obtained in cyclohexanone. The high polymerization rate in cyclohexanone was most likely due to an additional initiation mechanism where cyclohexanone complexed with the monomer to generate free radicals. Bubbling air through the mixture led to a higher monomer conversion during the early stage of the polymerization and a lower polymer average molecular weight in xylene and cyclohexanone; this indicated the existence of a distinct behavior between the air‐ and nitrogen‐purged systems. Matrix‐assisted laser desorption/ionization time‐of‐flight analysis of the polymer samples taken from nitrogen‐bubbled batches did not reveal fragments from initiating impurities. On the basis of the identified families of peaks, monomer self‐initiation is suggested as the principal mode of initiation in the spontaneous thermal polymerization of MA and nBA at temperatures above 100°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of thermodynamic models on the predictions of free volume diffusion theory for concentrated polymer solutions

Three thermodynamic models were used to demonstrate the effects of model choice on solvent–polymer binary diffusion coefficients predicted by free volume theory. Poly(vinyl acetate) and four solvents were used as typical solutions for these calculations. Thermodynamic models affect the predictions the most at high solvent weight fractions and for solutions which exhibit positive enthalpic interactions. For solutions dilute in solvent where Henry's law might describe phase equilibria, diffusion coefficients can be estimated without reference to thermodynamic data.     

Effect of solvent balance on the surface properties of poly(vinyl chloride)

Films of poly(vinyl chloride) have been cast from solutions of varying thermodynamic quality and the film properties studied by inverse phase gas chromatography. The solvents included tetrahydrofuran, cyclohexanone, and mixtures of toluene with both tetrahydrofuran and cyclohexanone. The solvent composition was followed during evaporation and film formation for the mixed solvents, and it was shown that the slower evaporating solvent component has the greatest effect on the surface properties of the films. The porosity of the polymer film surfaces is interpreted in terms of the mobility of the polymer chains during film formation. At high concentrations, polymer chain–polymer chain interactions become stronger when thermodynamically less powerful solvents are used or are last to leave during film formation; therefore, the solvent balance has a critical influence on the film surface properties. Annealing the poly(vinyl chloride) above the glass transition temperature reduces the surface porosity of the cast polymer.     

Evidences of solvent‐induced miscibility in polychloroprene‐co‐ethylene‐propene diene terpolymer blends

Solvent dependent changes in the compatibility behavior of Polychloroprene/Ethylene–propylene–diene terpolymer blends (CR/EPDM) have been investigated using dilute solution viscometry and solvent permeability analysis. To predict the compatibility of rubber blends of different compositions in solvents of different cohesive energy densities, Huggins interaction parameter (ΔB), hydrodynamic interaction (Δη) and Sun's parameter (α) were evaluated from the analysis of the specific and reduced viscosity data of two and three‐component polymer solutions. Miscibility criteria were not satisfied for CR/EPDM blends over the entire composition range in toluene, xylene, and carbon tetrachloride (CCl₄), however, a narrow miscibility domain was observed in chloroform (CHCl₃) for CR/EPDM/CHCl₃ system. These results were further corroborated with the analysis of heat of mixing (ΔH_m) and polymer–polymer interaction parameter (χ₁₂), for all rubber blend compositions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Miscibility study of cellulose acetate/carboxylated poly(vinyl chloride) blend in cyclohexanone by viscosity,ultrasonic velocity,refractive index,and polarizing microscopic methods

The viscosity, ultrasonic velocity, refractive index, and density of cellulose acetate/carboxylated poly(vinyl chloride) (CA/C‐PVC) blends in cyclohexanone, a common solvent, were measured at 30°C. After casting films of the blend for a 50:50 composition, polarizing micrographs were taken. Using the viscosity data, the interaction parameters were computed by employing two different equations. These values indicated that the CA/C‐PVC blend is miscible. This was confirmed by ultrasonic, refractive index, density, and polarizing microscopic methods. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 557–561, 2001     

Inverse gas chromatography study of polyvinylacetate–solvent and polyethylene–solvent systems

In this article, the thermodynamic behavior of polyvinylacetate (PVAc)–solvent, and polyethylene (PE)–solvent mixtures have been studied by determining the thermodynamic sorption parameters (enthalpy, entropy, and free energy), the mass‐based solvent activity coefficients (Ω) and the Flory Huggins parameters (χ), by means of inverse gas chromatography (IGC) measurements. According to the Flory Huggins parameters of the PE–solvent mixtures, determined between 40 and 60°C the compatibility (the ability to interact with each other) of this polymer with the different types of solvents follows this order: dispersion solvents > polar solvents > association solvents. In the case of PVAc mixtures, the thermodynamic parameters were determined between 60 and 80°C, only for polar‐type and association‐type solvents due to, in the studied temperature range, the retention diagrams of dispersion solvents show that there are not bulk interactions. The Hildebrand solubility parameters of both polymers were also determined, according to Guillet procedure. The higher values of PVAc material (14.1 MPa^0.5 for PE and 19.8 MPa^0.5 for PVAc, at 60°C) are related to the strong interactions of vinyl acetate monomer. POLYM. ENG. SCI., 56:36–43, 2016. © 2015 Society of Plastics Engineers     

Solubilities and diffusivities of N2O and CO2 in aqueous sulfolane solutions

The solubilities of N₂O and CO₂ in aqueous sulfolane solutions and pure sulfolane solvent, and the diffusivities of N₂O in aqueous sulfolane solutions were measured and correlated over the temperature range from 20° to 85°C; also, the data for density and viscosity that were needed in this experimental work were measured. This experiment revealed that the parameter of N₂O analogy method depends not only on the temperature, but also on the character of the solvent. Therefore, different solvents possess different analogy parameters. Only for dilute aqueous solutions can the parameter be replaced by the analogy parameter of water. The results also proved that the sum of volume fractions contribution is a simple method to estimate the solubility in aqueous sulfolane solutions over the whole range of the concentrations and experimental temperatures, with an average deviation of less than 4·0%.     

Casting solvent effect on crystallization behavior and morphology of poly(ethylene oxide)/poly(methyl methacrylate)

Poly(ethylene oxide) (PEO)/poly(methyl methacrylate) (PMMA) blends were prepared by casting from either chloroform or benzene solvents. After casting from solvents, all samples used in this study were preheated to 100°C and held for 10 min. Then, the solvent effect on the crystallization behavior and thermodynamic properties were studied by differential scanning calorimeter (DSC). Also, the morphology of spherulite of casting film was studied by polarized optical microscope. From the DSC and polarizing optical microscopy (POM) results, it was found that PEO/PMMA was miscible in the molten state no matter which casting solvent was used. However, the crystallization of PEO in the chloroform‐cast blend was more easily suppressed than it was in the benzene‐cast blend. Relatively, the chloroform‐cast blend showed the greater melting‐point depressing of PEO crystals. Also, the spherulite of chloroform‐cast film showed a coarser birefringence. It was supposed that the chloroform‐cast blend had more homogeneous morphology. It is fair to say that polymer blends, cast from solvent, are not necessarily in equilibrium. However, the benzene‐cast blends still were not in equilibrium even after preheating at 100°C for 10 min. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1627–1636, 2000     

Miscibility studies of polymer blends by viscometry methods

The intrinsic viscosities of blends of poly(vinyl chloride)/poly(ethylene-co-vinyl acetate) (PVC/EVA), poly(vinyl chloride)/poly(styrene-co-acrylonitrile) (PVC/SAN), and poly(ethylene-co-vinyl acetate)/poly(styrene-co-acrylonitrile) (EVA/SAN) have been studied in cyclohexanone as a function of blend composition. In order to predict the compatibility of polymer pairs in solution, the interaction parameter term, Δb, obtained from the modified Krigbaum and Wall theory, and the difference in the intrinsic viscosities of the polymer mixtures and the weight average intrinsic viscosities of the two polymer solutions taken separately are used. © 1994 John Wiley & Sons, Inc.     

Study of the solvent effect on miscibility between poly(vinyl chloride) and poly(methyl methacrylate) in the solution state – viscometric measurements

In this work, the solvent effect on the miscibility between poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) in ternary polymer solutions was examined by the viscometric method. In these systems, we could understand that the used solvents, tetrahydrofuran (THF) or N,N‐dimethylformamide (DMF), mainly affect the interaction between PVC and PMMA, while prompting various miscible properties. In PVC/PMMA/THF solution, THF is a near θ‐solvent and a poor solvent for PVC and PMMA, respectively. The mixing of the tighter PMMA coils and more extended PVC coils in THF may cause the sea–island heterogeneous structure below the weight fraction of PMMA in the polymer mixture w_PMMA = 0.7, resulting in immiscible PVC/PMMA mixtures. At w_PMMA ≥ 0.7, the PVC/PMMA mixtures are relatively miscible, giving homogeneous polymer solutions. It means that the miscibility between PVC and PMMA depends on the composition of polymer mixture. However, due to the similar affinity of DMF to PVC and PMMA, PVC/PMMA/DMF solutions exhibit high miscibility between PVC and PMMA at about w_PMMA = 0.5. © 2000 Society of Chemical Industry     

Miscibility and thermal behavior of poly(vinyl chloride)/feather keratin blends

Various poly(vinyl chloride) (PVC)/feather keratin (FK) blends were prepared via a solution blending method in the presence of N,N‐dimethylformamide as a solvent. The miscibility of the blends was studied with different analytical methods, such as dilute solution viscometry, differential scanning calorimetry, refractometry, and atomic force microscopy. According to the results obtained from these techniques, it was concluded that the PVC/FK blend was miscible in all the studied compositions. Specific interactions between carbonyl groups of the FK structure and hydrogen from the chlorine‐containing carbon of the PVC were found to be responsible for the observed miscibility on the basis of Fourier transform infrared spectroscopy. Furthermore, increasing the FK content in the blends resulted in their miscibility enhancement. The thermal stability of the samples, as an important characteristic of biobased polymer blends, was finally examined in terms of their FK weight percentage and application temperature. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The influence of the solvent upon the low shear viscosity of styrene–acrylonitrile copolymer solutions

This paper describes the results of an experimental investigation concerning the effect of polymer–solvent thermodynamics on low-shear viscosity of copolymer soltions. Thermodynamic parameters and low-shear solution viscosities were measured for solutions of polystyrene homopolymer and styrene–acrylonitrile copolymers in four solvents: benzene, dioxane, methyl ethyl ketone, and dimethylformamide. The thermodynamic quality of a solvent for a polymer is characterized by free-energy-of-mixing parameters. These quantities are: the Flory-Huggins thermodynamic interaction parameter χ, the second virial coefficient (from light scattering), the intrinsic viscosity, and the polymer expansion factor. The thermodynamic interaction between a solvent and a polymer in solution influences the rheological behavior of the system. At low concentrations of polymer in solvent, the low-shear solution viscosity is larger in a good solvent than in a poor solvent. In solutions of higher concentration, the reverse may be true and the viscosity is often significantly larger in a poor solvent than in a good one. These results are not predicted quantitatively by existing theory. The parameters in existing viscosity correlation techniques are found to be solvent dependent. The so-called entanglement concentrations for polymer solutions are not unique for a particular polymer but are related to the free energy of mixing polymer with solvent.     

Properties of dilute solutions of polymer mixtures intended for preparation of nanofibrous materials of increased hydrophobicity by capillaryless electroforming

The viscosity characteristics of dilute DMSO solutions of pure polymers fluoroplast-42V and chlorinated polyvinylchloride (CPVC) and their mixtures in various ratios were determined in order to facilitate further processing of such polymer mixtures by capillaryless electroforming. The more viscous F-containing component had a decisive influence on the properties of the dilute solutions. The additive intrinsic viscosity of the mixtures was always less than that of the pure fluoroplast but greater than that of pure CPVC. The solubility parameters of the used solvents and polymers were calculated a priori by the Small—van Krevelen method with subsequent calculation of the heat of mixing equation constant for the polymer and solvent.     

Solubilities,viscosities and unperturbed dimensions of poly (2,6-diisopropylphenyl methacrylate)

The dilute solution properties of poly(2,6-diisopropylphenyl methacrylate) (PDPP) in various solvents were studied by viscosity, exclusion chromatography and osmotic pressure measurements. The Mark-Houwink-Kuhn-Sakurada relationships were established. The unperturbed dimensions, the rigidity factor σ, the characteristic ratio C∞ and the thermodynamic parameters were determined using the Stockmayer-Fixman equation and from data in theta solvent (binary mixture). The rigidity factor of PDPP is abnormally high. The conformational behaviour of this polymer is analysed in terms of the effect of the side chain structure. The results are compared with other polymers of the same series.     

Enzymatic degradation of poly(D,L‐lactide) and its blends with poly(vinyl acetate)

The enzymatic degradation of poly(D ,L ‐lactide) (PLA) was investigated using two different lipases, Novozym 435 and Lipolase. The optimum temperature was 50°C for the enzymatic degradation of PLA. The effect of various solvents on the degradation of PLA was investigated at 50°C using Novozym 435, and toluene was found to be the best solvent among the solvents investigated. The enzymatic degradation of the blends of PLA and PVAc was investigated at 50°C in toluene. The enzymatic degradation of the blends of PLA and PVAc showed that there is an interaction between the polymers during degradation, which results in the reduction of degradation rate of both polymers in the blend. A continuous distribution model was used to determine the rate coefficients for polymer degradation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 657–680 2006     

Studies on miscibility of poly(vinyl chloride) with natural rubber-graft-polyacrylonitrile and natural rubber-graft-poly(methyl methacrylate)

The miscibility of poly(vinyl chloride)/natural rubber-graft-polyacrylonitrile (PVC/NRPACN) and PVC/NR-graft-poly(methyl methacrylate) (PMMA) were studied by differential scanning calorimetry (DSC) and viscometry. DSC curves of PVC/NR graft copolymer blends showed a major endotherm at about 265°C that was assigned to the thermal decomposition of PVC. PVC/NRPMMA blends showed a minor endothermic peak at about 124°C and the PVC/NRPACN blends showed a broad peak (which develops into two peaks) at about 160°–180°C, respectively. Absolute viscosity versus weight percent PVC plots of the two sets of blends were nonlinear. X-ray diffraction patterns of the PVC/NRPACN blends showed overlapping spacings due to the constituent polymers. Phase-contrast micrographs of the PVC/NRPACN blends showed gross phase discontinuity. The heats of mixing solutions of PVC blended with NRPMMA were found to be well above the upper limit of miscibility. © 1996 John Wiley & Sons, Inc.     

Binary interactions in dimethyl terephthalate/bis(2-ethylhexyl)adipate/poly(vinyl chloride) blends studied by melting point depression method

A novel approach is developed to estimate the interaction energy density, B, of polymer solutions by the melting point depression method using a crystallizable molecule as the probe. It rests on the classical Flory–Huggins lattice model of polymer solutions, and considers the polymer–solvent interaction parameter to be concentration dependent. The ternary system dimethyl terephthalate (DMT)/bis(2-ethylhexyl)adipate (DOA)/poly(vinyl chloride) (PVC) is chosen for the present study. The data of B for the three possible binary interactions are reported as the functions of composition at elevated temperatures. For a plasticized PVC resin containing 20 vol % DOA, the B is estimated to be 6 MJ m⁻³, which is approximately 2 MJ m⁻³ higher than the B value cited in the literature for the PVC mixed with almost 100% DOA. The thermodynamic stability of the ternary, system is discussed. © 1996 John Wiley & Sons, Inc.     

Evaluation of compatibility of poly(vinyl chloride)/starch acetate blends using simple techniques

Solution blending of poly(vinyl chloride) (PVC) and starch acetate (d.s. 2.5) synthesized in our laboratory was carried out in 1,4‐dioxane. The compatibility of these blends based on the heat of mixing and the free‐energy concept was examined theoretically. Experimental evidence for the compatibility of these blends was derived from viscometric and ultrasonic studies and density measurements. Interaction parameters suggest that polymer–polymer interaction is greater than polymer–solvent interaction in the blends under study. All the experimental and theoretical evidence show that the blends are incompatible at the compositions studied. Morphological studies showed a uniform dispersion of starch acetate in PVC. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1851–1861, 1999     

Estimation of solvent diffusion coefficient in amorphous polymers using the Sanchez-Lacombe equation-of-state

A modified free-volume model was proposed to predict the solvent diffusion coefficient in rubbery polymers without knowledge of any diffusion data. With the introduction of the Sanchez-Lacombe (SL) equation-of-state (EOS) into the Vrentas-Duda model, this model is an attempt to bridge the gap between the thermodynamic and transport properties of polymer solutions. The free volume provided by polymers for solvent diffusion can be estimated solely using the parameters of the SL EOS characteristics and the polymer glass transition temperature; thus the proposed model avoids the need to use polymer viscoelastic data in determination of polymer free-volume parameters. The other parameters in the Vrentas-Duda model remain applicable. Calculated results of solvent self- and mutual-diffusion coefficients of four common solvents in two polymers indicated that the modified model can give reliable predictions. In addition, it can reflect the effect of pressure on solvent diffusivity for concentrated polymer solutions.