Effect of hydrostatic pressure and temperature on the mechanical loss properties of polymers: 2. Halogen polymers

The shear modulus, G′, and loss tangent, tan δ, of a number of halogen polymers have been measured as a function of temperature at various pressures. The polymers studied were various poly(vinyl chloride) (PVC) samples, poly(vinylidene chloride) (PVDC), poly(vinyl fluoride) (PVF), poly(vinylidene fluoride) (PVDF) and a tetrafluoroethylene-hexafluoropropylene copolymer. The glass transition temperatures are shifted upwards by pressure by amounts varying between about 11°C and 25°C/1000 atm. In the case of PVC it has proved possible to compare the results with theory and the observed shift is found to be considerably smaller than the predicted value. In PVDC and PVDF the secondary relaxations are also shifted upwards by the application of pressure.     

Effect of hydrostatic pressure and temperature on the mechanical loss properties of polymers: 1. Polyethylene and polypropylene

A torsion pendulum ( 1 Hz) has been used to investigate the shear modulus and loss tangent of a number of hydrocarbon polymers as a function of temperature at pressures of up to 1200 atmospheres. Low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene (PP), a natural rubber and an ethylene-vinyl acetate copolymer have been studied. The results show that the relaxation temperatures are increased by the application of hydrostatic pressure, by amounts which range between about 5 and 20°C per 1000 atmospheres. However, it has only proved possible to correlate our results with theory in the case of PP because of the lack of other data, in particular the appropriate compressibility and thermal expansion coefficients. The results also show that if the crystallinity of LDPE and PP is reduced the relaxations are resolvable into two distinct processes.     

Synthesis of vinyl phenyl acetate and an evaluation of vinyl chloride/vinyl phenyl acetate copolymers

The synthesis of vinyl phenyl acetate, by an ester interchange reaction between phenyl acetic acid and vinyl acetate and utilizing a catalyst, is described. Copolymerization with vinyl chloride, in a suspension system and using a peroxide catalyst, is described on a laboratory and pilot plant scale. Monomer/copolymer compositions, for an initial charge consisting of vinyl chloride/vinyl phenyl acetate (80/20 by weight) are presented over a range of conversions, as an indication of reactivity ratios. Discs, molded from unstabilized copolymers, show very good clarity and color stability, which improve with increased comonomer loading. Some retention of unpolymerized vinyl phenyl acetate monomer occurred, and some increase in softening points resulted following two reprecipitations from acetone into excess methanol. Compound from a 96/4 vinyl chloride/vinyl phenyl acetate copolymer has better color stability than does an equivalent vinyl chloride/vinylidene chloride copolymer compound. The enhanced color and heat stability of the copolymers is attributed to the aromatic character of the comonomer vinyl phenyl acetate.     

Polyblends of poly(vinyl chloride) with ethylene/vinyl acetate copolymers: Practical properties and morphology

Five to 15 percent of ethylene/vinyl acetate copolymers was compounded into rigid polyvinyl chloride, with the copolymers dispersed as discrete micro-domains, produced very efficient synergistic improvement of impact strength; as the vinyl acetate content of the copolymer increased from 28 to 60 percent, the synergistic peak moved to higher copolymer content and became higher and broader. Copolymer content correlated directly with melt flow and thermal stability, and inversely to modulus, strength, and heat-deflection temperature. The vinyl acetate content of the copolymer correlated directly with elongation, impact strength, and thermal stability, but inversely to modulus, heat-deflection temperature, low-temperature flexibility, and melt flow. When the copolymer content reached 25 percent, it formed a second continuous-phase, interpenetrating the polymer network structure and acting as a polymeric plasticizer, producing thermoplastic elastoplastics.     

Effect of irradiation on mechanical and structural properties of ethylene vinyl acetate copolymers hollow fibers

Effect of irradiation on mechanical and structural properties of ethylene vinyl acetate copolymers (EVA) hollow fibers was studied by the tests such as determination of gel content, density, tensile, FTIR, SEM, and DMA. These effects were discussed based on dose and irradiation environment. The results of gel content depicted that irradiated EVA in ambient conditions had tendency to chain scission while the crosslinking overcame in irradiated samples under nitrogen. Density insignificantly enhanced with irradiation dose. In tensile test, irradiation induced increase in tensile strength and decrease in elongation at break (especially in samples irradiated in nitrogen). Also, changing in layer orientation could be observed by SEM images. In addition, irradiation caused altering peak intensity in FTIR spectrum. DMA results demonstrated that irradiation broaden the elastic zone. Totally, irradiation enhances features especially in irradiated EVA18 in nitrogen. Since, according to stabilization of induced deformation and improvement of mechanical properties (that created by radiation), the irradiated samples can be used in different applications. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of vinyl acetate content on the mechanical and thermal properties of ethylene vinyl acetate/MgAl layered double hydroxide nanocomposites

Ethylene vinyl acetate (EVA)/Mg‐Al layered double hydroxide (LDH) nanocomposites using EVA of different vinyl acetate contents (EVA‐18 and EVA‐45) have been prepared by solution blending method. X‐ray diffraction and transmission electron microscopic studies of nanocomposites clearly indicate the formation of exfoliated/intercalated structure for EVA‐18 and completely delaminated structure for EVA‐45. Though EVA‐18 nanocomposites do not show significant improvement in mechanical properties, EVA‐45 nanocomposites with 5 wt % DS‐LDH content results in tensile strength and elongation at break to be 25% and 7.5% higher compared to neat EVA‐45. The data from thermogravimetric analysis show that the nanocomposites of EVA‐18 and EVA‐45 have ≈10°C higher thermal decomposition temperature compared to neat EVA. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of the molecular weight of ethylene vinyl acetate copolymers on the flow and mechanical properties of uncompatibilized polystyrene/ethylene–vinyl acetate copolymer blends

Rubber‐toughened polystyrene (PS) has been extensively studied and is a well‐established material. However, the use of thermoplastic elastomers to toughen PS is new and not well understood. In this study, three types of ethylene vinyl acetate (EVA) copolymers with the same vinyl acetate (VA) content (27.2–28.8 wt %) but with different melt flow indexes (MFI; g (10 min)⁻¹) of 365–440 (Elvax 210), 38.0–48.0 (Elvax 240) and 2.6–3.4 (Elvax 265) were used as impact modifiers for PS. The uncompatibilized blend systems at different compositions were prepared using a twin‐screw extruder and injection moulding to produce the required test pieces. The viscosity of the dispersed phase (EVA) has a significant effect on the mechanical properties of the blends. Rheological studies show that uncompatibilized PS/EVA265 blends exhibit some degree of compatibility when the amount of EVA265 added is below 30 wt %. These results indicate that EVA265 with the lowest melt flow index or highest molecular weight is the most effective impact modifier for PS. The mechanism for such behaviour is still unclear. © 2001 Society of Chemical Industry     

Strain-induced crystallization kinetics of vinylidene chloride/vinyl chloride (VDC/VC) copolymers. Part II. Effect of temperature

The strain-induced crystallization (SIC) behavior of vinylidene chloride/vinyl chloride (VDC/VC) copolymer is reported as a function of the uniaxial extension ratio and the temperature of the rubbery amorphous specimen. The copolymer studied was an 88/12 wt/wt VDC/VC copolymer with a weight average molecular weight of 100,000 containing liquid additives that function as processing aids. It was found that SIC is initiated at an extension ratio of approximately 3.5, independent of the stress and stretching temperature. The growth rate of the crystalline phase increases sharply with extension ratio above 3.5. The crystalline phase growth rate at a given extension ratio also increases sharply with temperature between 15°C and 35°C. The implications of film temperature control during bubble expansion on the blown film process are discussed.     

Effect of polymerization conditions on the melt rheological properties of vinyl chloride–vinyl acetate copolymers

Mathematical models have been developed which predict the composition, molecular weight, and melt rheological properties for vinyl chloride/vinyl acetate copolymers of inherent viscosity range 0.4–0.7 dL/g and bound vinyl acetate levels of 3.8–17.4%. The effect of polymer long chain branching on the viscous/elastic moduli ratio is discussed as well as the comparison of Tinius–Olsen melt index measurements vs. mechanical spectrometer results. The reactivity ratio for vinyl chloride/vinyl acetate comonomer pairs was remeasured and found to be significantly different from literature values.     

Radical terpolymerization of ethylene,methyl acrylate and vinyl acetate under high pressure. Physical properties of the polymers

Polymerization tests were carried out in a stirred autoclave designed for continuous operation in order to determine the influence of the reaction pressure and temperature and of the acrylic acid methyl ester and vinyl acetate comonomers on the ethylene-acrylic acid methyl ester-vinyl acetate terpolymer formed. Pressures between 1100 and 1900 bar and temperatures of 180 and 230°C were used. The average residence time was 40 seconds. Tertiary butyl perpivalate and tertiary butyl perethyl hexanoate in concentrations of 50 to 180 mol-ppm in the ethylene feed were used as initiators. The characteristic properties of the polymers obtained were assessed by determining their composition, density, crystallinity, melting point, glass transition temperature, melt index, the average molecular weight, tensile strength and elongation at break.     

Studies on the polyblends of poly(vinyl chloride) with various methacrylate copolymers,physical and mechanical properties. I

The effect of blending various methacrylate copolymers on the physical and mechanical properties of poly(vinyl chloride) (PVC) has been investigated. Copolymers of methylmethacrylate with methylacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate in 80:20 and 50:50 wit methylmethacrylate have been prepared and characterized by nuclear magnetic resonance spectroscopy. Polyblends of PVC and such polyacrylates have been prepared in 80:20 ratio by melt blending technique and characterized by thermomechanical analysis to study the glass transition behavior vis-à-vis the compatibility of these blends. Mechanical properties of these blends revealed a substantial increase in impact strength particularly when long chain acrylate polymers like butyl acrylate and 2-ethyl hexyl acrylates are used; however, there is a decrease in the yield stress and initial modulus. A shift from brittle failure to ductility has been observed in blends of PVC on incorporation of these acrylate copolymers. Scanning electron microscopic studies have been carried out to support these observations.     

Terpolymers. II. Mechanical properties and transition temperatures of terpolymers of vinyl stearate,vinyl acetate,and vinyl chloride

Vinyl stearate was studied as a major internal plasticizer in terpolymers containing vinyl acetate and vinyl chloride. The terpolymers were prepared by systematically replacing vinyl acetate by close increments of vinyl stearate starting with combinations of vinyl acetate and vinyl chloride, in increments, over all compositions. For comparison of properties, a complete range of copolymers of vinyl stearate and vinyl chloride, as well as mixtures of poly(vinyl chloride) and di-2-ethylhexyl phthalate (DOP) were also made. The external plasticizer was more efficient in reducing the glass temperature than was vinyl stearate. The decline in T_g with weight fraction of plasticizer was linear for the copolymers and terpolymers but concave downward with the liquid diluent. The linear decline was shown to involve mere additivity of the free volume contributed by each side-chain methylene (or methyl) group in both vinyl esters to reducing T_g. The mechanism of the diluent system was more complex. However, the magnitude of the reduction of tensile modulus at a given weight fraction of DOP could be equaled or exceeded by the same amount of vinyl stearate, by increasing the vinyl acetate content of the base copolymer to 40 mole-% or more. Unfortunately, the ultimate strengths and elongations of internally plasticized systems were reduced more than those of the mixtures at comparable compositions. Vinyl stearate was found to markedly retard photolytic degradation compared to both vinyl acetate and the external plasticizer in unstabilized samples having nearly the same thermal treatment. The effect was greater than could be ascribed to dilution by the long alkyl group. The production of a stearoyl radical more stable than the radicals initiating dehydrochlorination is suggested as a possible mechanism.     

Iodine reaction of vinyl acetate/vinyl propionate copolymers. III. Iodine affinities of the radically polymerized copolymers and the copolymers derived from partially saponified polyvinyl acetate

The minimum sequence lengths (n_c) of vinyl acetate (VAc) units necessary to form a colored iodine complex were determined to be 4 and 17 for radically polymerized VAc/vinyl propionate (VPr) and VAc/isopropenyl acetate (IPAc) copolymers, respectively. The iodine affinities (I/VAc) of VAc/VPr copolymers (SP-series) obtained by propionylation of partially saponified polyvinyl acetate (PVAc) were remarkably affected by the saponification conditions. An increase of the water content in acetone/water mixture as saponification solvent brought about a decrease of the iodine affinities of the SP-series. The dependence of the iodine affinity on the saponification of monomer units in the SP-series was compared with that in the radically polymerized VAc/VPr copolymers by taking the sequence probability as the measure of monomer unit distribution. The results strongly supported an occurence of the slide fastener reaction at high degrees of saponification, which was well-known in the saponification of PVAc. Furthermore, it was found that the saponification mode of PVAc at low degrees of saponification was influenced uniquely by the water content in saponification solvents and the saponification temperature.     

Thermal and photodegradation of vinyl chloride/vinyl bromide copolymers

Vinyl chloride/vinyl bromide (VC/VBr) copolymers have been synthesized by radical copolymerization in bulk. Conversion increases and molecular weight of the copolymers decreases with increasing VBr in the feed. This indicates that VBr is a chain transfer agent in VC/VBr copolymerization systems. In accordance with the lower thermal stability of the vinylbromide homopolymer (PVBr), thermal degradation experiments show that the stability of the copolymers significantly decreases with increasing VBr content. It has been found that the initial rate of dehydrohalogenation is an exponential function of VBr content during thermal degradation of VC/VBr copolymers. In separate experiments, HBr evolved during degradation has been determined by a bromide selective electrode. The initial dehydrobromination rates of VC/VBr copolymers containing higher fractions of VBr are markedly higher than the initial dehydrochlorination rates. This clearly indicates the lower thermal stability of VBr monomer units compared with VC units. UV and visible spectra of degraded VC/VBr copolymers show that the absorption and the average length of polyenes are higher for samples with higher VBr content. Dehydrohalogenation curves obtained during photodegradation of VC/VBr copolymers show a faster initial phase followed by a slower stationary phase. The initial rate of dehydrohalogenation is higher for copolymers containing higher fractions of VBr, whereas these copolymers reach the slower stationary phases at lower extents of dehydrohalogenation.     

乙烯-醋酸乙烯-氯乙烯共聚树脂合成试验研究

介绍了在10L聚合釜中合成乙烯-醋酸乙烯-氯乙烯(EVA-g-VC)共聚树脂的试验情况。分别研究了EVA种类及用量、EVA的溶胀方法、助剂对聚合过程和树脂颗粒性能的影响规律,制得的EVA-g-VC共聚树脂的加工性能基本达到了国外同类产品水平。     

Studies on the thermal stability of poly/vinyl chloride/ and vinyl chloride - carbon monoxide copolymers

Thermal stability of vinyl chloride/carbon monoxide copolymers synthetized in the presence of different proportions of carbon monoxide was studied in nitrogen, oxygen or air stream at 180°C. Dehydrochlorination rate increases proportionally to the incorporated carbonyl content. Effect of air and oxygen on acceleration of the decomposition is higher for PVC samples of regular structure than for the vinyl chloride/carbon monoxide copolymers. In the infra-red spectra recorded after the thermal oxidative decomposition, a broad absorption band appears between 1600 and 1800 cm^?1. Two peaks show the most emphasized increase: one at 1720 to 1730 cm^?1 assigned to the carbonyl group and another at about 1770 cm^?1 of unidentified origin. Additional oxidation products from the polyene yield a “shoulder” in the spectrum between 1600 and 1690 cm^?1.     

Copolymerization of vinyl chloride with 1-olefins. Part IV. Investigation of rheological and mechanical properties of copolymers

Copolymers of vinyl chloride with propene, 1-butene, and 1-pentene having the same content of 1-olefin (4.0 ± 0.5 mol%) and various molar mass and copolymers with a comparable molar mass and the same composition were prepared. By measuring rheological and mechanical properties of this assembly of samples, which also included the reference vinyl chloride homopolymer, it was possible to estimate the effect of molar mass and of the individual comonomers. The copolymers under investigation possessed improved processing properties and did not suffer any deterioration of important mechanical properties.     

Effect of calcium carbonate on the mechanical and thermal properties of isotactic polypropylene/ethylene vinyl acetate blends

The effect of calcium carbonate (CaCO₃) on the mechanical properties (with heat treatment) and thermal properties of polypropylene and isotactic polypropylene (i‐PP)/ethylene vinyl acetate (EVA) blends was investigated. CaCO₃, in five different concentrations (3, 6, 9, 12l, and 15 wt %), was added to i‐PP/EVA (88/12) to produce ternary composites. The mechanical properties, including the yield and tensile strengths, elastic modulus, Izod impact strength for notch radii of 0.25 and 1 mm, and hardness with and without an annealing heat treatment, and the thermal properties, such as the melting point and melt‐flow index, of the composites were investigated. The annealing heat treatment was carried out at 100°C for three different holding times: 75, 100, and 150 h. On the basis of the results, attempts were made to establish a relationship between the CaCO₃ content, the annealing holding time, and the mechanical and thermal properties to obtain the best results. The tensile test results showed that the heat treatment was not effective for the ultimate tensile strength, and the yield strength and tensile strength decreased gradually as the CaCO₃ content increased. However, CaCO₃ was effective for higher elastic modulus, impact strength, and hardness values. A considerable increase in the elastic modulus was found with a 3% CaCO₃ concentration for a holding time of 100 h. The maximum impact strength for a notch radius of 1 mm was obtained with 3% CaCO₃ with annealing for a holding time of 100 h, whereas a 9% CaCO₃ concentration produced higher toughness values for a notch radius of 0.25 mm. The fracture surfaces also supported the results from the Izod impact tests. Similarly, hardness values increased with the annealing heat treatment and increasing CaCO₃ content. However, different holding times showed similar effects on the hardness values. The increased CaCO₃ content caused the melting point to increase 5°C, whereas the melt‐flow index showed a sharp decrease as the CaCO₃ content increased to 3%. Taking into consideration the mechanical and thermal properties and the annealing holding time, we recommend a CaCO₃ concentration of 3% with an annealing heat treatment for 100 h for optimum properties of such ternary composites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1126–1137, 2005     

Rheological and mechanical performance of ethyl‐vinyl acetate/poly(vinyl chloride) formulations

A range of powdered ethyl‐vinyl acetate (EVA) copolymers and poly(vinyl chloride) (PVC) formulations were compounded at PVC:EVA ratios of 100:0, 60:40, 50:50, 40:60, and 0:100. Two grades of EVA with 20% and 27% of vinyl acetate (VAc) (EVA I and EVA II) and two grades of PVC with K values of 56 and 71 (PVC I and PVC II) were used in the investigation. Mechanical analysis was performed on injection molded samples of these blends, and the results showed that the tensile and flexural moduli decreased significantly with increasing EVA concentration. Rheological analysis was performed by using dual capillary rheometry, and the results showed only slight changes in shear viscosity with increasing EVA content, even at lower shear rates. Dynamic mechanical thermal analysis showed partial miscib lity of the PVC and EVA over the range of concentrations studied.     

Effect of damp‐heat aging on the structures and properties of ethylene‐vinyl acetate copolymers with different vinyl acetate contents

We reported herein the damp‐heat aging of ethylene‐vinyl acetate copolymers (EVA) with different vinyl acetate (VAc) contents simultaneously for weeks. The aging was carried out under temperature of 40°C and relative humidity of 93% in air atmosphere. The changes of copolymers' structures and properties were investigated by means of FTIR, wide angle X‐ray diffraction (WAXD) and differential scanning calorimetry (DSC) and mechanical tests. CI values derived from ATR‐FTIR spectra have a decrease when aging time is 1 week and then increase during damp‐heat aging process which suggests the first loss then incorporation of O?C group. WAXD infer that the narrowing trend of FWHM and increase of crystal sizes may attribute to the melting and re‐crystallization of secondary crystallization, which is also confirmed by DSC results. Mechanical tests including Shore A and Shore D hardness, modulus at 100%, tensile strength and elongation at break, are all depending on the primary crystallization and influenced little by damp‐heat aging. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009