Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002     

Modeling of polypropylene degradation during reactive extrusion with implications for process control

This paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.     

Multicomponent vapor deposition polymerization of poly(methyl methacrylate) in an axisymmetric vacuum reactor

An axisymmetric, multicomponent initiated chemical vapor deposition (i-CVD) apparatus was designed to study the vapor-phase growth of glassy poly(methyl methacrylate) (PMMA) films. Preheated monomer (methyl methacrylate) and initiator (t-butyl peroxide) vapors were metered into a pressure-controlled reaction chamber. Inside the chamber, gases pass through a high-temperature hot-zone where primary free radicals are formed. The gas mixture then condenses and polymerizes on a back-cooled target substrate. Key reactor operating parameters were systematically varied to understand film growth kinetics. These include the hot-zone temperature, reactor base-pressure, substrate temperature, and the monomer/initiator molar feed ratio. Polymer deposition requires good thermal contact between feed gases and the hot-zone. Packed with glass beads, the hot-zone reactor resulted in more efficient initiation and film growth. Experiments also show that polymer deposition rate is limited by thermal initiation of primary free radicals, transport of primary free radicals to the target substrate, and by monomer adsorption. Size exclusion chromatography of deposited polymers is used to relate molecular weight to the monomer-to-initiator feed ratio. The addition of a third vapor component, 1-butanol, was also found to affect polymer molecular weight.     

Free radical branching of polylactide by reactive extrusion

The reactive extrusion of polylactide (PLA) with a free radical initiator resulting in a branched polymer was accomplished. Reaction conditions were in the range of 160°C to 200°C with an initiator concentration between 0.0 and 0.5%. Triple detector size exclusion chromatography, melt flow index, thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis were used to characterize the polylactide polymers. PLA without initiator showed extensive degradation as was evidenced by a decrease in both molecular weight and melt viscosity. The optimum range for branching resulting in a high molecular weight and low melt flow index polylactide was found to be around 170°C to 180°C and 0.1 to 0.25% initiator.     

Oxidation of gamma‐irradiated ultrahigh molecular weight polyethylene

Ultrahigh molecular weight polyethylene (UHMWPE), the current polymer of choice in orthopedic prosthetic devices, is typically sterilized by exposure to Co‐60 gamma irradiation prior to packaging for long‐term storage. However, the exposure to Co‐60 irradiation generates free radicals along the polymer chain that can participate in a series of reactions commencing with the oxidation of the free radicals to form reactive peroxy radicals. This study was undertaken to identify the role of hydroperoxide species in shelf‐aged and accelerated aged UHMWPE samples by using a nitric oxide derivatization technique. It is shown that the concentration of hydroperoxides did not change appreciably with shelf aging. However, during accelerated aging the hydroperoxide concentration increased to a plateau and then decreased, suggesting its role as an intermediate in the process. By contrast, the concentrations of carbonyl species continued to increase during shelf aging and accelerated aging. The effects of several packaging materials on the oxidation characteristics were also investigated. A vacuum foil package is shown to be effective in preventing oxidation to a significant extent during accelerated aging. However, accelerated aging after removal from the foil pack resulted in oxidative degradation. Extended vacuum to remove dissolved oxygen and a 5‐week room‐temperature healing process in the foil pack were shown to be ineffective in reducing oxidative degradation. It also was shown that increased moisture content in the aging environment did not affect the degradation process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2525–2542, 2000     

Polymerization control through the free‐radical retrograde‐precipitation polymerization process

In this article, we present results of our work in a novel polymerization process [called the free‐radical retrograde‐precipitation polymerization (or FRRPP) process] that occurs at temperatures above the lower critical solution temperature. In this process, conversion‐time plots for styrene polymerization in ether show autoacceleration at the beginning, followed by a relatively long period of reduced conversion rate starting at conversions as low as 30% and at operating temperatures way below the glass transition of the reacting system. Molecular weight and polydispersity index data also indicate early autoacceleration (in the form of overshoots in these values), whereas the latter period of slow conversion rate is accompanied by stable levels of molecular weight and polydispersity index. Polymer radical concentration measurements show an initial sharp rise, followed by an asymptotic value, even after almost all the initiator molecules have already decomposed into radicals. With end‐group analyses of product polystyrene and polymer radical data, we calculate a proportion of live polymeric radicals to asymptote at levels of 80–84% of all polymeric species, even after almost all initiator molecules have already decomposed into radicals. All the data presented herein verify the postulate of a controlled polymerization mechanism for the FRRPP process. Our results have become the basis for an anti‐gel effect phenomenon that is derived from prior theoretical and experimental observations, in which phenomenological diffusivities vanish at the spinodal curve of the phase envelope. The universality of this behavior in FRRPP systems is manifested from similar observations in styrene polymerization in acetone and methacrylic acid polymerization in water. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 761–774, 1999     

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi‐implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized. POLYM. ENG. SCI., 47:667–674, 2007. © 2007 Society of Plastics Engineers.     

Effect of multiple feeds on a termination-free polymerization in continuous stirred tank reactors

The effect of monomer and initiator feeds to each of a series of continuous stirred tank reactors (CSTR) on the molecular weight distributions, average molecular weight, polymer production rate, and initiator and monomer conversions is studied for the termination-free polymerization system. For initiator feed concentrations less than 0.001 mole/liter, the distribution becomes narrower as the polymer progresses from reactor 1 to reactor 3. But for concentrations of initiator of 0.01 mole/liter, the distribution may be broadened from reactor 1 to reactor 3. The broadening of the distribution results in the production of a lower molecular weight polymer.     

Process control for polypropylene degradation during reactive extrusion

This paper describes the development of process control schemes for the free radical initiated (reactive) degradation of polypropylene in an extruder (reactive extrusion). The objective of the work was to control the amount of degradation in order to produce polypropylene with a specified molecular weight. The die pressure drop was used as a measure of the amount of degradation (the measured variable) and the initiator concentration was used to control the amount of degradation (the manipulated variable). The reactive degradation process was modeled empirically to determine the dynamic relationship between the input degradation initiator concentration and the output die pressure drop. Several control schemes were evaluated for controlling the die pressure drop (amount of degradation) with emphasis placed on schemes designed to overcome the non-linear process gain and dead time.     

Deformation processing of PMMA into high-strength fibers

Poly(methyl methacrylate) was drawn into fibers by melt extrusion followed immediately by a transient temperature drawing process. By varying five processing variables, fibers ranging from 0.635 mm to 25 μm in diameter were produced. Heat-induced relaxation of the aligned structure was used to determine the draw ratio of the resultant fibers and therefore the degree of polymer chain alignment imposed by the deformation process. The resulting changes in length and diameter were measured and it was found that draw ratios of 5–20 had been achieved under the varying processing conditions. It was also observed that fiber diameter immediately after drawing is a good predictor of the degree of orientation present in the fiber irrespective of the processing conditions. To test the effect molecular orientation has on material properties, fibers with varying degrees of orientation were tested in tension. As expected, increasing alignment resulted in increasing tensile strength. The maximum observed true ultimate tensile strength was 225 ± 53 MPa and was seen in fibers with a draw ratio equal to 18.7 ± 4.5. Fibers with a lower degree of alignment, while not as strong in tension, exhibited significantly increased ductility. True strains of as high as 25% were observed.     

Crystalline-state extrusion of low density polyethylenes

Three low density polyethylenes, one long branched (A) and two linear (B and C), have been solid-state-extruded at several constant temperatures from ambient to 80°C and to draw ratios ? 8. The initial densities and melt indices of A, B, and C are 0.920, 0.920, and 0.935 g/cm³, and 1.9, 0.8, and 1.2, respectively. Melt-crystallized cylindrical billets were extruded through conical dies in an Instron Capillary Rheometer. The linear polymers were found to draw by extrusion more readily than the branched; all three strain-harden. Density, birefringence, tensile, and thermal properties have been evaluated as functions of extrusion temperature and draw ratio. Despite a measured loss via die swell, substantial orientation takes place during solid-state extrusion as evidenced by increases in transparency, birefringence, and tensile modulus (up to 4.5 times that of the original isotropic polymer). Depending on the polymer and the draw temperature, density does go through a minimum or shows a monotonic increase with draw by extrusion. A minimum in modulus is also observed at low draw and at all draw temperatures for all three polymers. The highest tensile moduli achieved are 0.73, 0.46, and 1.5 GPa for A, B, and C, respectively, at their highest draw ratio. The melting point for polymer B decreases with extrusion draw ratio, whereas it remains constant after a small initial drop, for the two others. For all three low density polyethylenes, birefringence increases rapidly with extrusion draw and then levels off at high draw. The birefringence limit is similar for A and B, i.e., 0.046 ± 0.004, but higher for C, i.e., 0.068 ± 0.009. This work extends beyond others in that it studies the effect of short as well as long branches in solid-state extrusion by comparing the linear and long branched LDPE polymers and LDPE with prior evaluations of HDPE.     

The reactive modification of polyethylene. II: Mathematical modeling

In Part I of this work, experimental data showed that the effect of low concentrations of free radical initiator injected into polyethylene during extrusion depended upon the degree of unsaturation and branching in the feed as well as the molecular weight. This paper shows attempts to quantitatively explain these reactive extrusion results through development of two kinetic models based upon the rate equations for reactions considered dominant. The first model developed incorporated unsaturation via consideration of simultaneous crosslinking-endlinking reactions. It contains two variable parameters: the overall initiator efficiency and a ratio of two rate constants reflecting the reactivity of the unsaturated bonds. The model was able to fit the changes in molecular weight distribution of both the low density and linear low density polyethylene but not the high density polyethylene samples. In addition to fitting the molecular weight distribution, this model also provided reasonable values of initiator efficiencies for crosslinking, endlinking, and chain extension reactions, as well as the number of terminal vinyls of the products. The second model is a special case of the first: it neglects the presence of unsaturation in the feed. This second model is actually the usual “crosslinking” model widely known from a derivation based upon statistical arguments. It was not able to fit most molecular weight distributions obtained. However, the model was shown to be useful for accounting for observed molecular weight distribution for a high density polyethylene sample of low initial unsaturation. Also, it was able to explain the amount of gel formed as a function of initiator concentration.     

Nitroxide mediated living radical polymerization of styrene in miniemulsion—modelling persulfate-initiated systems

Recently we have constructed a mechanistic model describing the nitroxide mediated miniemulsion polymerization (NMMP) of styrene at 135°C, using alkoxyamine initiators to control polymer growth (Nitroxide-Mediated Polymerization of Styrene in Miniemulsion. Modeling Studies of Alkoxyamine-Initiated Systems, 2001b). The model has since been expanded to describe styrene NMMP at 135°C using TEMPO and the free radical initiator, potassium persulfate (KPS). The model includes mechanisms describing reactions in the aqueous and organic phases, particle nucleation, the entry and exit of oligomeric radicals, and the partitioning of nitroxide and styrene between the aqueous and organic phases. Predicted monomer conversions, number average molecular weights and polydispersities were in agreement with experimentally measured values. Model simulations revealed that for systems employing high ratios of TEMPO:KPS, the consumption of TEMPO by polymer radicals derived from KPS decomposition and styrene thermal initiation (using the accepted literature kinetic rates) is not sufficient to lower TEMPO concentrations to levels where polymer growth can occur. By accounting for the consumption of TEMPO by acid-catalyzed disproportionation, TEMPO concentrations are significantly reduced, allowing for accurate model predictions of monomer conversion, number average molecular weight and polydispersity at every experimental condition considered.     

The weatherability of polypropylene monofilaments. Effects of fiber production conditions

From a comparison of the photo-and γ-irradiation-initiated oxidations of monofilaments and films, polypropylene oxidation rates and product ratios were found to be independent of sample morphology and orientation. Filament sensitivity to photo-oxidation was, however, drastically affected by extrusion and draw conditions, photosensitivity increasing with increasing draw speed and decreasing draw temperature. Draw effects were minimized by the exclusion of oxygen, indicating that free radicals produced by backbone cleavage during draw react with oxygen to give chromophoric oxidation products. The most important product detectable after drawing was probably the polypropylene hydroperoxide. A phenolic antioxidant reduced hydroperoxide formation, although sufficient hydroperoxide was still produced to accelerate photodegradation as compared with a similarly stabilized undrawn filament. Melt oxidation within the extruder was concluded to be much more important than thermal oxidation of the extruded filament as it cooled on the spinline.     

The reactive modification of polyethylene. I: The effect of low initiator concentrations on molecular properties

Commercial samples of high density, linear low density, and low density polyethylene were modified by injection of low concentrations of free radical initiator during extrusion. Molecular properties monitored included molecular weight distribution, degree of unsaturation, and branching. When the polyethylene teed to this reactive extrusion process had similar values of M_w, but varying polydispersity, degree of branching and degree of unsaturation, the magnitude of the change in molecular weight distribution was found to be in the following order: HDPE 1 > LDPE2 > LLDPE. In general, terminal vinyls enhanced molecular weight increase, and branching promoted degradation. However, for a second high density polyethylene sample with M_w = 154,000 (rather than the previous sample's M_w of 85,600), the change in molecular weight distribution was small and located at the lower molecular weight end. This work provided data for the kinetic model development detailed in Part II.     

The ring-opening polymerization of D,L-lactide in the melt initiated with tetraphenyltin

Melt polymerization conditions for D ,L -lactide initiated with tetraphenyltin were studied with regard to polymer molecular weight and weight distributions. “Single” polymerization, “multiple” polymerization (four or eight reactions at the same time), and time-dependent studies are described. Single polymerizations using constant initiator concentrations resulted in a broad scattering of nonreproducible molecular weight values. Multiple polymerizations at constant initiator concentrations, however, resulted in nearly identical molecular weight profiles. Multiple polymerizations at different initiator concentrations did not show an inverse dependency of initiator concentration on polymer molecular weight. Both the single and multiple melt polymerizations resulted in rather broad molecular weight distributions. The presence of hydrolysis products of lactide during the melt polymerization most likely has a detrimental effect on molecular weight. After a short induction period the rather slow polymerization of D ,L -lactide resulted in a maximal molecular weight followed by a slight decrease in molecular weight to a constant value. It is concluded that the polymerization of D ,L -lactide in the melt initiated with tetraphenyltin does not proceed through a “living” mechanism.     

Polyurethane elastomers from post-grafted polymer–polyol systems

Certain homopolymer–polyol mixtures, after treatment with a free-radical generating agent or ionizing radiation, will produce polyurethane elastomers of nearly twice the stiffness and tensile properties compared to control elastomers made with untreated mixtures. Specific examples of these mixtures include the homopolymers of acrylonitrile and vinyl chloride with a poly(oxypropyl) triol of about 3000 molecular weight as the polyol in each case. The marked improvement in the stiffness and tensile properties of elastomers made with the treated mixtures over those of the untreated controls indicates a grafting process occurring between the polyol and homopolymer upon the generation of free radicals. In the present work, grafting could occur by a chain-transfer hydrogen-abstraction mechanism, whereby a free-radical site is generated on both the homopolymer and polyol chains. Coupling of these two free-radical sites would thus result in the establishment of a polymer–polyol graft bond.     

Orientation development in solid‐state extrusion and hot forming of polypropylene tubes

The use of high‐strength polymer in automotive structural components is limited by insufficient understanding of microscopic aspects of deformation for accurate numerical predictions of the mechanical behavior during forming processes. One approach to meeting these critical data needs is a careful examination of the structure property relationships that directly influence formability. Different hot forming processes (solid‐state extrusion, axial feed hot oil tube forming, and biaxial ball stretching test) are utilized in this work for investigating the effect of process conditions on the molecular orientation of polypropylene (PP) tubes. White‐Spruiell representation of orientation factors based on the results form X‐ray diffraction (XRD) patterns is utilized to analyze the development of orientation under extrusion and various forming conditions. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Investigation on dry spinning process of ultrahigh molecular weight polyethylene/decalin solution

The relationship between the draw‐down ratio in the dry spinning process of ultrahigh molecular weight polyethylene/decalin solution and the fiber performance through maximized after‐drawing was investigated. The structural development during the after‐drawing process was analyzed by scanning electron microscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, sonic velocity, and FTIR measurements. An optimum draw‐down ratio was found in the multihole dry spinning process, which may be explained by molecular disentanglement and the composite effect of entropy and the viscosity component. The as‐spun fiber by draw‐down had an obvious shish kebab morphology, lower crystallinity, and a higher melting temperature compared with a free extrusion sample, and higher crystallinity and melting temperature compared with the fiber by first‐stage after‐drawing. During the subsequent after‐drawing process, the crystallinity, melting temperature, X‐ray diffraction, and sonic velocity orientation factors increased slowly in the higher after‐drawing ratio region, which was not consistent with the rising tendency of the tensile properties. The polarized and unpolarized IR spectra reflected the variations of the orientation and the content of the folded chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 474–483, 2005     

Sensitized photodegradation of polyisobutylene film by addition of tris(α-thiopicolinanilide)–cobalt(III)

The photodegradation of polyisobutylene (PIB) film in air at a temperature where volatile formation is negligible was studied by means of light scattering, chemical actiometry, and spectrophotometric techniques. The degradation is accelerated by addition of tris(α-thiopicolinanilide)—cobalt(III) (TPAC). The sensitization and the course of the degradation were determined by weight-average molecular weight, energy of activation, and quantum yield of the photolysis of the polymer film with 254-nm light. The plots of molecular weight, weight-average chain scission, and degree of degradation vs. irradiation time are linear and confirm the random nature of chain scission of the polymer. The unsaturation produced is proportional to the time of irradiation. Ultraviolet and infrared absorption spectra have been employed to substantiate a mechanism of the degradation process which does not involve hydrogen abstraction from the polymer, but direct cleage of the polymer backbone and addition of initiating radicals of TPAC at the sites of scission.