Miscibility of poly(vinyl chloride) with styrene/acrylonitrile copolymers

Poly(vinyl chloride) (PVC) is shown to be miscible with styrene/acrylonitrile copolymers (SAN) having AN compositions from 11.5 to 26%. Blend samples were prepared using several methods, including solution casting, melt mixing, and precipitation of solutions by a nonsolvent. It is shown that the blend phase behavior is affected by preparation method due to the solvent effect, or Δ_χ effect, and lower critical solution temperature (LCST) behavior. The intramolecular repulsion between styrene and acrylonitrile units in SAN is shown to be the cause of miscibility using heats of mixing obtained from low-molecular-weight analog compounds. An FTIR analysis supplements the above results.     

The fusion of highly crystalline poly(vinyl chloride)

Low molecular weight PVC polymers of known degree of crystallinity (44% by x-ray diffraction), prepared in the presence of the chain-transfer agents n-butyraldehyde and n-butyl mercaptan, are examined by differential scanning calorimetry in order to ascertain temperatures and heats of fusion. Initial thermal scans are accompanied by large endotherms and appreciable weight losses due to the lability of the terminal groups originating from the chain-transfer agents. However, further successive scans result in approximately invariant endotherms attributable to crystalline fusion. The maximum melting point, about 265°C, exceeds the value for commercial PVC, about 210°C, but is lower than a value deduced for a hypothetical completely syndiotactic polymer, about 400°C. The average heat of fusion ΔH_u is 1180 ± 90 cal/mole, and the resultant entropy of fusion is 1.1 cal/deg/bond. The present ΔH_u value differs significantly from previously reported values of 660–785 and 2700 cal/mole, based on melting point depression theory, but appears to be concordant with known heats for a series of vinyl polymers.     

Miscibility of poly(vinyl chloride) with ethyl acrylate 4-vinyl pyridine copolymers

Blends (50:50, w:w) of poly(vinyl chloride) (PVC) and poly(ethyl acrylate-co-4-vinyl pyridine) (PEA–4-VP) of different 4-VP contents (2–14 mol %) were prepared. These were found to be partially miscible as evidenced by the presence of a single, through broad, tangent δ peak obtained from torsion pendulum experiments. Several possible types of interactions which might exist between PVC and PEA-4-VP, such as ion-dipole, crosslinking, charge transfer, hydrogen bonding, and dipole–dipole interactions, were explored. From ultraviolet, conductance, infrared, and solubility studies, it was shown that hydrogen bonding or dipole–dipole (or possibly a combination of the two) interactions were the most likely in this system. These interactions have been suggested previously for other systems by various investigators.     

Miscibility of bisphenol-A polycarbonate with poly(methyl methacrylate)

The miscibility of bisphenol-A polycarbonate (PC) with poly(methyl methacrylate) (PMMA) has been reexamined using differential scanning calorimetry (DSC) and optical indications for phase separation on heating, i.e., lower critical solution temperature (LCST) behavior. Various methods have been used to prepare the blends including methylene chloride (CH₂Cl₂) and tetrahydrofuran (THF) solution casting, melt mixing, and precipitation of PC and PMMA simultaneously from THF solution by using the nonsolvents methanol and heptane. It is shown that the resulting phase behavior for PC/PMMA blends is strongly affected by the blend preparation method. However, these blends are miscible over the whole blend composition range (unambiguous single composition-dependent T_g's and LCST behavior) when prepared by precipitation from solution using heptane as the nonsolvent. To the contrary, solution-cast and melt-mixed PC/PMMA blends were all phase separated, which may be attributed to the “solvent” effect and LCST behavior, respectively, not discovered in previous reports. Methanol precipitation does not lead to fully mixed blends, which demonstrates the importance of the choice of nonsolvent when using the precipitation method.     

Miscibility of poly(vinyl chloride) with poly(methyl-co-hexyl acrylate) and poly(methyl-co-2 ethyl hexyl acrylate)

The miscibility and phase behavior in blends of PVC with poly(methyl-co-hexyl acrylate)[MHA] and poly(methyl-co-2 ethyl hexyl acrylate)[MEH] were studied. It was found that PVC is miscible with MHA copolymers having a HA volume fraction from 0.30 to 0.92 and MEH copolymers having an EH volume fraction from 0.30 to 0.83 at 100°C. By applying the mean field theory to the phase diagrams of these blend systems, segmental interaction parameters which represent the binary interaction between different monomer units were estimated. The calculated values reflect the fact that the miscibility window observed for PVC/MHA and PVC/MEH blend systems was attributed to the effect of repulsion between different monomer units within the copolymer. To investigate the effect of specific interaction on the miscibility for these blend systems, an attempt was also made to describe the blend interaction parameter as a function of polar group concentration in the acrylate copolymer. The blend interaction parameter values exhibit a u-shaped curve as a function of the weight fraction of C?O group in the copolymer, and the lowest blend interaction parameter value appears at about 0.24 C?O weight fraction.     

Miscibility of poly(vinyl chloride) with chitin derivatives having poly(2-methyl-2-oxazoline) side chains

Binary blends of poly(vinyl chloride) (PVC) and chitin-graft-poly(2-methyl-2-oxazoline) showed miscibility in the blend fraction range of the latter lower than ca. 10 wt.-%. The glass transition temperature of PVC, which was determined by differential scanning calorimetry, changed to lower temperatures with increasing modified chitin contents up to 10 wt.-%. Segmental interaction between PVC and the graft copolymer was confirmed by the carbonyl stretching band shift in the FT-IR analysis.     

Synthesis and characterization of thermotropic liquid crystalline poly(ester imide)s

Two closely series of poly(ester imide)s had been synthesized by solution polycondensation of p‐phenylenebis(trimellitate) dianhydride with aliphatic diamines. The differential scanning calorimetry (DSC) traces of the most poly(ester imide)s exhibited two endotherms representing the solid state to anisotropic phase transition (T_m1) and the anisotropic to isotropic melt transition (T_m2), respectively. Observation under polarizing microscope and wide‐angle X‐ray diffraction (WAXD) measurements suggested that the anisotropic phase formed above the melting points (T_m1) had a smectic character. The thermogravimetric analyses (TGA) revealed that the thermal stabilities of the poly(ester imide)s were up to 350°C. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 211–218, 1999     

Synthesis and characterization of random semi-flexible thermotropic liquid crystalline poly(ester-imide)s

A series of novel poly(ester-imide)s were prepared by the reaction of meta- and para-substituted trimellitimide dicarboxylic diacid chlorides with various diols containing four, five, six, seven, eight, nine, 10, and 12 methylene groups by a solution polymerization technique utilizing refluxing 1,2,4-trichlorobenzene as a solvent. The poly(ester-imide)s were characterized by dilute solution viscosity, infrared spectroscopy, differential scanning calorimetry, and polarized light microscopy. The inherent viscosities of the meta-substituted poly(ester-imide)s ranged from 0.06 to 0.25 dL/g while those of the para-substituted poly(ester-imide)s ranged from 0.10 to 0.65 dL/g and were obviously of higher molecular weight. The meta series were amorphous and showed no mesophase formation. All para-substituted poly(ester-imide)s exhibited monotropic mesophase identified as smectic A order. © 1994 John Wiley & Sons, Inc.     

Miscibility and orientation behavior of poly(vinyl alcohol) / poly(vinyl pyrrolidone) blends

The miscibility of poly(viny1 alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) blends is investigated by differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD). The molecular orientation induced by uniaxial stretching of the blends is also examined by WAXD and birefringence measurements. It is shown by the DSC thermal analysis that the polymer pair is miscible, since a single glass transition temperature (T_g) is situated between the T_gs of the two homopolymers at every composition. The T_g versus composition curve does not follow a monotonic function but exhibits a cusp point at a PVP volume fraction of a little under 0.7, as in a case predicted by Kovacs' theory. The presence of a specific intermolecular interaction between the two polymers is suggested by an observed systematic depression in the melting point of the PVA component. A negative value of the polymer-polymer interaction parameter, χ₁₂ = 0.35 (at 513 K), is estimated from a thermodynamic approach via a control experiment using samples crystallized isothermally at various temperatures. The extent of optical birefringence (Δn) of the drawn blends decreases drastically with increasing PVP content up to 80 wt %, when compared at a given draw ratio, and ultimately Δn is found to change from positive to negative at a critical PVP concentration of a little over 80 wt %. Discussion of the molecular orientation behavior takes into consideration a birefringence compensation effect in the miscible amorphous phase due to positive and negative contributions of oriented PVA and PVP, respectively.     

Retardation of discoloration of poly(vinyl chloride) and decolorization of discolored poly(vinyl chloride) with diimide

Retardation of discoloration of poly(vinyl chloride) with diimide was studied in dimethylformamide at 130°C. with the use of p-toluenesulfonylhydrazide (PSH) as a source of diimide. A process was proposed that involved prolonging the induction periods of discoloration by inhibiting the development of conjugated polyene structure. The optimum proportion of PSH was one fourth of the poly(vinyl chloride), the best results. Furthermore, poly(vinyl chloride) discolored by thermal degradation in o-dichlorobenzene or gamma-ray irradiation under vacuum was decolorized in solution at 130°C. by addition of PSH. The decolorized poly(vinyl chloride) thus obtained was thermally stable compared with that obtained by oxidative methods.     

Miscibility and crystallization kinetics in blends of poly(ethylene terephtalate) and thermotropic liquid crystal polyesters

Binary blends of poly(ethylene terephtalate) (PET) and thermotropic liquid crystal polyester (TLCP) have been prepared by both solution and melt blending methods. The TLCPs utilized were Vectra (Hoechst Celanese), TR-4, a TLCP synthesized in our laboratory, and a block copolymer consisting of three TR-4 units followed by three PET units. The phase behavior of the blends was studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA) and optical microscopy. The results show that none of the blends is miscible, but significant interactions exist between the PET phase and the TLCP phase in the case of TR-4 and TR-4 block copolymer blends. These interactions lead to a different nucleation mechanism in these blends compared to that in PET/Vectra.     

Study on the thermotropic liquid crystalline polycarbonates. IV. Synthesis and properties of liquid crystalline poly(imide-carbonate)s

Two series of novel thermotropic liquid crystalline poly(imide-carbonate)s were prepared by melt polycondensation from various arylene or alkylene bis(phenylcarbonate)s by using N,N′-bis(hydroxyethyl)pyromellitimide and N,N′-bis(hydroxypropyl)pyromellitimide as monomers. Thermotropic liquid crystalline properties were characterized by a polarizing microscope with a heating stage and a differential scanning calorimeter (DSC). Nematic melts were found for the synthesized aromatic poly(imide-carbonate)s. In order to investigate whether the pyromellitimide unit could be used as a mesogenic unit for preparing LC polymers, a series of aliphatic poly(imide-carbonate)s was prepared in this study. However, no significant LC textures were found under the observation by polarizing microscope. It was suggested that the aspect ratio of the pyromellitimide unit was too short to form liquid crystalline poly(imide-carbonate)s. In addition, it was interesting that the aliphatic poly(imide-carbonate)s with a longer spacer (n = 3) in the pyromellitimide unit showed better crystallinity. Thermostabilities of all synthesized poly(imide-carbonate)s were measured by thermogravimetric analysis (TGA). © 1994 John Wiley & Sons, Inc.     

Reaction of n-butyllithium with poly(vinyl chloride)

The reactions of poly(vinyl chloride) and butyllithium in tetrahydrofuran were investigated. A deep purple color developed at first with addition of butyllithium to the THF–PVC solution, and a spontaneous color change of the misture occurred successively to blue, green, and finally pale vellow. In these reaction stages, the PVC might be butylated, dehydrochlorinated, and partially lithiated by BuLi. These facts were substantiated by the results of successive reactions with various substances such as Michler's ketone, carbon dioxide, and styrene.     

Degrees of order from X-ray diffraction in highly crystalline poly(vinyl chloride)

Convenient x-ray diffraction instrumentation for assessing PVC order is described. A reflectance diffractometer, copper radiation, a monochromator, and a proportional detector are used to make measurements on low molecular weight, highly crystalline PVC prepared using chain-transfer agents. Interpretation includes a correction for air scattering, employment of a trimodal noncrystalline pattern, and the calculation of crystallinity from the ratio of the crystalline to the total integrated intensity. The results are reasonably insensitive to the assumptions made. The noncrystalline pattern used is taken to indicate a single, partially ordered mesomorphous phase. A whole polymer prepared in the presence of butyraldehyde, a fraction therefrom prepared by precipitation, and a similar fraction terminated by butyl mercaptan have similar molecular weights (M?_n ca. 1600) and crystallinities of 30, 44, and 44%, respectively. Fractionation apparently effects a separation with respect to syndiotactic content, and the resultant crystallinity appears to be the highest valid x-ray value reported to date for a PVC polymer, irrespective of polymerization variables, fractionation procedure, or molecular weight. The order in these polymers is due in part to their greater syndiotacticity (about 64% for the fractions by ¹³C NMR spectroscopy), although a more favorable tactic placement distribution may be involved in addition to a possible effect of molecular weight itself.     

Photo-oxidation of poly(vinyl chloride)

Hydrogen chloride is evolved at an increasing rate in the light-induced oxidation of poly(vinyl chloride) films. These accelerated kinetics were shown to result from an increased absorption of light by the polyenes formed, since the quantum yield of dehydrochlorination (Φ_HCl = 0·015) is independent of the extent of the reaction in the dose range investigated. Determination of the quantum yields of the different processes involved indicate that, for each scission of the polymer backbone, 11 molecules of hydrogen chloride are evolved while three carbonyl groups, two hydroperoxides and 0·4 intermolecular crosslinks appear on the polymer chain. A mechanism that involves β-scissions of the tertiary alkoxy radicals, resulting from non-terminating interactions of α-chloro-peroxy radicals, is suggested to explain the observed increase of the polymer degradation in the presence of oxygen.     

Radiolysis of poly(vinyl chloride)

Allyl free-radical intermediates are detected by ultraviolet absorption at 255 mu in poly(vinyl chloride) irradiated at ?196°C and stored at 25°C. In vacuum at 25°C, allyl radicals are converted into polyenyl free radicals and polyenes. From the nature of allyl radical decay in vacuum, radical chain transfer between polyenyl radicals and poly(vinyl chloride) is inferred. Allyl and polyenyl free radicals are scavenged by oxygen on post-irradiation storage in air.     

Reaction of sulfur with poly(vinyl chloride)

The reaction of elemental sulfur with poly(vinyl chloride) is studied in 1,2,4-trichlorobenzene and without any solvent under various conditions. Black polymers containing 3.77–57.64% chemically bonded sulfur and, according to IR spectroscopy, including >C=C< and >C=S groups in macromolecules are obtained. It is shown that the diffraction curves of poly(vinyl chloride) and of the reaction product containing 7.82% almost coincide but that the thermal stability of the latter is considerably higher than that of the initial polymer. The prospects of the practical use of the products of the reaction of poly(vinyl chloride) with elemental sulfur are demonstrated.     

Pyrolysis of poly(vinyl chloride)

A pyrolysis–gas chromatography–mass spectrometric technique has been developed to study the thermal degradation of poly(vinyl chlorides) polymerized at different temperatures. Hydrogen chloride and benzene evolution during successive stages of pyrolysis have been quantitatively determined and correlated to the tacticity and molecular weight of the polymer. It was found that lowering the temperature of polymerization and molecular weight depresses benzene evolution and increases char weight but does not affect the HCl yield. It is suggested that the syndiotactic trans microstructure favored at low temperature of polymerization yields polyenes which cannot cyclize to form benzene. As the molecular weight decreases, the increase in number of vinyl chain ends facilitates pyrolytic crosslinking and char formation.