Mechanochemical degradation of an EPDM polymer

A mill-mastication study of an EPDM polymer (DuPont, Nordel 1070) was conducted in the mill-roll temperature range of 68–480°F. The extent of degradation was determined by dilute-solution viscosity measurements. The role of oxygen in the polymer mastication was followed by infrared spectroscopy. The breakdown of the EPDM polymer on the mill is minimum in the temperature range of 185–315°F. Up to 315°F. the increase in temperature leads to a decreased amount of degradation. During cold mastication mechanical breakdown occurs. The use of a free-radical acceptor shows that this type of breakdown is caused by the mechanical rupture of C? C bonds in the polymer chain. At and above 350°F. thermooxidative degradation becomes dominant, the polymer degrading drastically, and the higher the temperature, the greater the extent of degradation for the same period of mastication. Infrared spectroscopy shows that hot mastication results in decreased double-bond concentration and increased amounts of carbonyl and, possibly, anhydride and lactone groups. Of the carbonyl groups formed 30% are due to the oxidation of double bonds in terpolymer and 70% to the oxidation of the main chain. A mechanism is proposed to account for these observations.     

Three‐site mechanism and molecular weight: Time dependency in liquid propylene batch polymerization using a MgCl2‐supported Ziegler‐Natta catalyst

This article demonstrates that the molecular weight of propylene homopolymer decreases with time, and that the molecular weight distribution (MWD) narrows when a highly active MgCl₂‐supported catalyst is used in a liquid pool polymerization at constant H₂ concentration and temperature. To track the change in molecular weight and its distribution during polymerization, small portions of homo polymer samples were taken during the reaction. These samples were analyzed by Cross Fractionation Chromatograph (CFC), and the resulting data were treated with a three‐site model. These analyses clearly showed that the high molecular weight fraction of the distribution decreases as a function of time. At the same time, the MWD narrows because the weight‐average molecular weight decreases faster than the number‐average molecular weight. A probable mechanism based on the reaction of an external donor with AlEt₃ is proposed to explain these phenomena. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1035–1047, 2001     

Mechanical degradation of high molecular weight polymers in dilute solution

The mechanical shear degradation of polydisperse polyisobutene and monodisperse polystrene in oils of different viscosities in the concentration range of 0.1% to 1% was studied using a high-shear concentric cylinder viscometer under laminar and uniform well-defined shear field conditions. Molecular weight distributions (MWDs) were measured by gel permeation chromatography (GPC). Degradation of polydisperse polyisobutene solutions narrows the distributions principally through the breaking down of large molecules. Degradation of monodisperse polystyrene broadens the distributions at lower shear stress. At higher shear stresses, the distributions do not broaden as much but are still broader than those of the original polymer. The final M_w/M_n ratios are considerably different from the value of 2 expected for random degradation. Hence, the degradation is likely a nonrandom process. It was found that the extent of degradation has a negative concentration dependence coefficient at relatively high molecular weight and a positive concentration dependence at lower molecular weight. Competing mechanisms of “stretching” and “entanglements” for degradation were postulated to explain the results. The degradation data indicate that the shear stress is the controlling parameter, not the shear rate. The shear degradation is independent of initial molecular weight and viscosity of the solvent.     

Viscosity and Peel Strength of SMR 10-Based Pressure-Sensitive Adhesives

The viscosity and peel strength of a natural rubber-based pressure-sensitive adhesive was studied. One grade of natural rubber (SMR 10) and coumarone-indene resin were used as the elastomeric material and tackifier, respectively. Throughout the experiment, toluene was used as the solvent to prepare the adhesive. The effect of mastication time of rubber and tackifier concentration on the viscosity and peel strength of adhesive on various substrates was systematically investigated. The viscosity was measured using a HAAKE Rotary Viscometer. T-Test, 90° Adhesion To Steel (ATS), and 180° Adhesion To Steel (ATS) Tests were used to determine the peel strength of the adhesive. The results indicate that the viscosity of the adhesive increases with the resin content but decreases with mastication time. The peel strength generally increases with an increase in resin content except for the 20 min masticated sample. For all concentrations of the resin tackifier studied, the 10 min masticated sample exhibits the highest peel strength as compared to the corresponding values of the other masticated samples. This observation is attributed to the optimum wetting and formation of mechanical interlocking, and anchorage of the adhesive in pores and irregularities in the substrate for the former sample.     

Effects of processing parameters and molecular weight distribution on the tensile properties of polypropylene fibers

The tensile properties of polypropylene fibers, produced in a short-spin line, are correlated with the parameters of the three processing stages (spinning, drawing, and annealing), and with the molecular weight distribution. In general, tensile stiffness and strength increase with increasing molecular orientation, while the elongation at break decreases. The degree of orientation is determined by the deformation ratios and temperatures of the first two stages. Tensil modulus and strength also increase with increasing annealing stage shrinkage ratio. All the tensile properties, including the elongation at break, increase with increasing average molecular weight. The mechanisms of crystallization and deformation are related to the molecular weight distribution in different ways. Hence, the tensile modulus is highest for broad distributions when the draw ratio is low, and for narrow distributions when the draw ratio is high. The tensile strength increases and the elongation at break decreases as the width of the molecular weight distribution decreases, for all combinations of processing parameters. The distribution of tensile strength, for fibers with high draw ratios, broadens as the molecular weight distribution narrows. The total draw ratio of fibers, as experienced during processing and testing, and the true stress at break, are discussed in terms of deformation rates and relaxation times. © 1994 John Wiley & Sons, Inc.     

Thermal degradation behavior of polypropylene in the melt state: molecular weight distribution changes and chain scission mechanism

In order to clarify the effect of thermal degradation on the structure of polypropylene materials, we investigated the changes in molecular weight distribution. The samples of polypropylene were degraded iso-thermally at 190 °C at different time intervals. The molecular weight distribution was significantly changed with thermo-degradation time, and the carbonyl index increased drastically for 40 min degraded samples, where the molecular weight distribution started splitting into two peaks. The results imply that heterogeneous degradation proceeded in this system. Sequentially, the weight distribution of the oligomeric products observed was discussed on the basis of chain scissions; these results indicate that there are some kinetically favored scissions occurring near the oxygen-centered radicals.     

The effect of the molecular weight on thermal degradation of fractionated PVC

A commercial PVC and another one prepared in bulk at 40°C were fractionated by means of fractional solution method using cyclohexanone-methanol mixtures. Both fractionations resulted in two sets of fractions. Their thermal degradation at 175, 180 and 185°C was followed by means of a conductivity cell which allows a continuous titration of the evolved HCl. The results showed that the lower the molecular weight the higher the degradation rate was; nevertheless, this relationship is only valid up to molecular weights of 60 000 to 90 000, from which the degradation rate appeared to be independent on the molecular weight. The UV-visible spectra of the degraded polymers suggest a similar polyene sequence distribution for all the fractions which accounts for a similar mechanism of degradation in contrast to what happens to fractions with different tacticity.     

Modeling of poly(L‐lactide) thermal degradation: Theoretical prediction of molecular weight and polydispersity index

A mathematical model to describe the molecular weight and polydispersity index (Q) in poly(L ‐lactide) (PLLA) thermal degradation has been developed. Based on the random chain scission mechanism, effects of temperature and time on the molecular weight and polydispersity index are included in this model. It incorporates the degradation and recombination reaction of PLLA thermal degradation, while taking into account the equal probability assumption. The developments of molecular weight and polydispersity index of PLLA polymer in the thermal degradation process were investigated at temperature ranging from 180–220°C, the experimental data show PLLA reaches its thermal degradation equilibrium in 2 h. The simulated results of this model are compared with the measured molecular weight and polydispersity index of the PLLA polymer. The changes of the molecular weight and polydispersity index in the PLLA thermal degradation can be predicted by this model. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2557–2562, 2003     

Comparison of similar narrow molecular weight polystyrenes

Discrepancies between the level of the viscosity at 200°C of the Dow series of polystyrenes and another narrow molecular weight distribution polystyrenes have been pointed out by Toosi, Porter, and Johnson in 1969. Penwell and Graessley have shown in 1974 that over a wide range in temperature one member of this series, S109, has a significantly lower viscosity than samples of similar molecular weight from other sources. Fetters has established the presence of high molecular weight tails in several of the much studied series. The investigation being reported here reveals the effect of the high molecular weight tail in the viscoelastic behavior of the S109 in the terminal zone of response. In addition, it is shown by an enhanced rate of creep in the glass to rubber-like dispersion that the glass temperature of the S109 is depressed by about 4°C.     

Cooking schedule of alkyd resin preparation. Part II. Effect of cooking schedule on molecular weight distribution of alkyd resin

The effect of cooking schedule on the molecular weight distribution of an alkyd resin was investigated. At the molar ratio of 1.03/0.43/1.00 for glycerin, lauric acid, and phthalic anhydride, two kinds of alkyd resin were prepared, one by maintaining the reaction temperature at 170°C for an hour and then raising it up to 230°C (sample I), the other by raising the temperature up to 230°C at a uniform rate of 33°C per 10 min. (Sample II). Sample I and sample II were fractionated into seven or eight fractions by adding n-heptane to 5 wt-% toluene solution at 30°C. Acid valued, hydroxyl value, intrinsic viscosity [η], and the number-averagè molecular weight M?_n were determined. The result showed that the molecular weight distribution curve obtained from sample I was much narrower than that from sample II. In addition, a relation was found between [η] and M?_n conforming to the equation [η] = KM^α, where different values of K and α were obtained for sample I and sample II. Based on the differences in the molecular weight distribution curves and in the rate constants for the esterification reactions, glycerin/lauric acid and glycerin/phthalic anhydride at 170°C and 230°C, the mechanism of condensation reaction of short oil alkyd resin was discussed.     

Sample pretreatment for aggregate-free PVC molecular weight measurement by size-exclusion chromatography

The procedure of aggregate-free poly(vinyl chloride) (PVC) solutions for size-exclusion chromatography (SEC) at room temperature using tetrahydrofuran (THF) as the mobile phase is proposed. PVC was dissolved in 1,2,4-trichlorobenzene (TCB) at 130 or 140°C for 6 h, precipitated in methanol, filtrated, and dried. The pretreated PVC was again dissolved in THF and SEC measurements were performed at room temperature. High molecular weight (MW) PVC required a higher pretreatment temperature of 140°C. The existence of aggregates sometimes could not be observed by a refractive index detector, but a light-scattering detector attached to the SEC columns could detect them clearly. The slope of the relationship between the MW and retention volume at the high MW region was steep compared with that at the other part of the peak and it was also a good indicator of the existence of aggregates. The pretreatment of PVC resulted in the decrease in MW averages, which was attributed to the disappearance of aggregates and not to the degradation of PVC. The pretreatment at 150°C resulted in the degradation of PVC. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1801–1809, 1998     

Functionalization of low molecular weight atactic polypropylene Part II. Thermal and molecular weight studies

Summary Number average molecular weight (M_n), intrinsic viscosity ([η]) and glass transition temperature (T_g) of low molecular weight atactic polypropylene (APP) grafted with 4-allyl-1,2-dimethoxybenzene (DMAB), 4-allyl-2-methoxyphenol (eugenol) and 4-propenylanisole (trans-anethole) in the presence of dicumyl peroxide (DCP) at 170°C were determined. The influences of reaction time, concentration and extent of grafting on M_n, [η] and T_g of APP were examined. The data were discussed with the mechanism of grafting reactions. Received: 6 June 2000/Revised version: 23 July 2000/Accepted: 4 September 2000     

Stability of electrical properties of carbon black‐filled rubbers

Conducting composites were prepared by melt mixing of ethylene–propylene–diene terpolymer (EPDM) or styrene‐butadiene rubber (SBR) and 35 wt % of carbon black (CB). Stability of electrical properties of rubber/CB composites during cyclic thermal treatment was examined and electrical conductivity was measured in situ. Significant increase of the conductivity was observed already after the first heating–cooling cycle to 85°C for both composites. The increase of conductivity of EPDM/35% CB and SBR/35% CB composites continued when cyclic heating‐cooling was extended to 105°C and 125°C. This effect can be explained by reorganization of conducting paths during the thermal treatment to the more conducting network. EPDM/35% CB and SBR/35% CB composites exhibited very good stability of electrical conductivity during storage at ambient conditions. The electrical conductivity of fresh prepared EPDM/35% CB composite was 1.7 × 10⁻² S cm⁻¹, and slightly lower conductivity value 1.1 × 10⁻² S cm⁻¹ was measured for SBR/35% CB. The values did not significantly change after three years storage. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Experimental study on the effect of molecular weight and chemical composition distribution on the mechanical response of high-density polyethylene

This article aims to appraise the effect of microstructure comprising molecular weight distribution and chemical composition distribution on the mechanical properties of high-density polyethylene (HDPE). HDPE resins were synthesized using several titanium–magnesium-supported Ziegler–Natta catalysts in the industrial gas phase reactor under the same polymerization condition. Gel permeation chromatography and crystallization elution fractionation (CEF) were conducted on the resins to characterize the molecular weight and comonomer distribution. Crystallization, thermal and rheological behavior were evaluated following differential scanning calorimetry, polarization light microscopy, and rheometric mechanical spectrometry. The resins with higher soluble fraction in trichlorobenzene below 80°C (highly branched low molecular weight chains) exhibited longer crystallization time based on the crystallization kinetic obtained from the Avrami model. Rheological determination of the molecular weight between entanglements (M_e) and the average lamella thickness based on the Gibbs–Thomson equation revealed that the entanglement density and impact strength decreased, and the average lamella thickness increased with an increase in the ratio of CEF eluted fraction below 80°C to the crystallizable fraction in the range of 80–90°C.     

Effects of shear stress and subcritical water on devulcanization of styrene–butadiene rubber based ground tire rubber in a twin‐screw extruder

The devulcanization reaction of styrene–butadiene rubber (SBR) based ground tire rubber (GTR) in GTR/ethylene–propylene–diene monomer rubber (EPDM) blend was investigated through a compound‐induced reaction by increasing screw rotation speed and being in the presence of subcritical water. The effects of temperature, pressure, screw rotation speed, or promoting agents on the gel content, Mooney viscosity, and Fourier transform infrared spectra of the sol of the devulcanized blends (devulcanized ground tire rubber (DGTR)/EPDM) were measured, and the mechanical properties and microstructures of the revulcanized blend ((DGTR/EPDM)/SBR) were characterized. The results show that subcritical water as a swelling agent and reaction medium promotes the devulcanization reaction, increases the selectivity of the crosslink breakage, keeps the extrusion material from oxidative degradation, reduces the gel particle size of the devulcanized blends, and significantly improves the mechanical properties of the revulcanized SBR/(DGTR/EPDM) blends. In subcritical water, the suitable promoting agents (alkylphenol polysulfide 450, hydrogen peroxide H₂O₂, or 450/H₂O₂) accelerate the devulcanization reaction, keep the double bond content, and lead to further decrease of the gel content and Mooney viscosity of the devulcanized blends and further increase of the mechanical properties of the revulcanized SBR/(DGTR/EPDM) blends. Especially the compound promoting agent (450/H₂O₂) improves the selectivity of the crosslink breakage in devulcanization of SBR‐based GTR. When 450/H₂O₂ is added as a compound promoting agent at the best reaction condition in subcritical water (200°C, 1.6 MPa and 1000 rpm), the tensile strength and elongation at break of the revulcanized SBR/(DGTR/EPDM) blends reach to 85.4% and 201% of vulcanized SBR (24.0 MPa, 356%), respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1845–1854, 2013     

Melt fracture behavior of polypropylene‐type resins with narrow molecular weight distribution. I. Temperature dependence

Polypropylene (PP)‐type resins with narrow molecular weight distribution, such as PP‐type thermoplastic elastomer PER and controlled‐rheology PP (CRPP) made by peroxide degradation of high molecular weight PP, have a problem of easy generation of skin roughness at extrusion. To examine the present state, the occurrence of skin roughness in PER and CRPP at extrusion was investigated with a capillary rheometer in a shear rate range of 12–6100 s^?1 and a temperature range of 180–280°C. A homo‐PP (HPP) and a block‐PP (BPP) with usual molecular weight distributions were used for comparison. HPP and BPP with usual molecular weight distributions show smooth extrudates at low shear rates and abruptly generate severe skin roughness “elastic failure” originating at the die entrance at a higher shear rate. PER and CRPP with narrow molecular weight distributions easily generate “sharkskin” melt fracture originating at the die exit, from a shear rate nearly one decade lower than rates of elastic failure of HPP and BPP. The sharkskin becomes more severe, with increasing shear rate, and attains to the elastic failure. The critical shear rate at which sharkskin occurs increases with increasing extrusion temperature. The critical shear rate is about 20 s^?1 at 180°C and about 120 s^?1 at 280°C, which is in the range encountered by the molten resin at extrusion processing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2111–2119, 2002     

EPDM/silicone blend layered silicate nanocomposite by solution intercalation method: Morphology and properties

Ethylene–propylene–diene terpolymer (EPDM)/silicone blend nanocomposites are prepared by solution method for the first time. EPDM and silicone rubber in their 50:50 (by weight) blend is intercalated within the silicate sheets of organically modified montmorillonite. Organic modification to the pristine sodium montmorillonite (Na‐MMT) surfaces is carried out by ion‐exchange reaction using hexadecyl ammonium chloride. The incorporation of such organic functional group makes Na‐MMT hydrophobic and expands the interlayer spacing between silicate sheets. The intercalated structure of EPDM/silicone blend nanocomposites is characterized by the X‐ray diffraction. Transmission electron microscopic characterization visualized the presence of both exfoliated and intercalated layered silicate in the polymer nanocomposites. The mechanical properties of the nanocomposites show a maximum improvement in tensile strength and elongation at break of 23 and 68%, respectively, compared with EPDM/silicone blend. The dielectric measurement demonstrates the increase in relative permittivity for the nanocomposite than the pure blend. The increase in the onset temperature of the thermal degradation of nanocomposites (∼52°C) corresponding to 1 wt% decomposition indicates the enhancement of thermal stability of (EPDM)/silicone blend due to interaction with silicates. POLYM. COMPOS., 35:1834–1841, 2014. © 2014 Society of Plastics Engineers     

Solubility of high molecular weight,sterically hindered amines in polypropylene

The dissolution of four sterically hindered amines with molecular weights from 1364 to 2758 was studied in polypropylene in the interval, 60–130°C. The solubility of the additives at 100°C passes through a maximum during time and the maximum solubility increases with increasing additive molecular weight. The rearrangement of the polymer structure during additives dissolution is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 883–889, 2000     

The influence of thermal history on the properties of poly(3-hydroxybutyrate-co-12%-3-hydroxyvalerate)

The influence of thermal history on the properties of commercial P(3HB-co-12%-3HV) was studied. Thermogravimetric analysis and differential scanning calorimetry revealed that the plasticizer evaporated at 140°C or higher. The loss of plasticizer during thermal treatment at 170 and 180°C resulted in a slight increase of the melting temperature of the polymer. The processing time and temperature, as well as the cooling procedure influenced the thermal behaviour of the material. A decrease in molecular weight with time was found at the temperatures investigated and this significantly affected the mechanical properties of the polymer prepared at 180 and 200°C. The rate constant k_d of thermal degradation was slightly higher for samples during a shape-forming process in a Minimax apparatus than during a quiescent heating process (DSC) and its value increased with temperature. Limiting the processing at 170°C to 2 min gave a material with useful properties but increasing the residence time resulted in a decrease in strength, elongation at break, molecular weight and viscosity although it did not significantly influence the modulus of elasticity. Materials prepared at 180 or 200°C were more brittle and longer residence times resulted in a deterioration of the mechanical properties. © 1996 John Wiley & Sons, Inc.