Influence of block molecular weight on the properties of styrene‐ethylenebutylene‐styrene block copolymers

Styrene‐ethylene butylene‐styrene (S‐EB‐S) block copolymers with similar polystyrene contents and varying molecular weights (S‐EB‐S‐1, molecular weight: 8833‐41223‐8833; S‐EB‐S‐2, molecular weight: 15844‐70534‐15844; S‐EB‐S‐3, molecular weight: 26133‐111067‐26133) were used in this study. The domain size of the polystyrene phase marginally increases with an increase in polystyrene segmental weight as observed by atomic force microscopy. Dynamic mechanical measurements of these polymers were carried out over a wide range of temperatures and frequencies. These polymers exhibited three peaks: α, β, and γ in the tan δ‐temperature curve. With increase in the molecular weight of the S‐EB‐S polymers, the α‐transition temperature shifted to higher values, while the β‐ and γ‐transitions remained unaltered. Also, the elastic modulus and storage modulus decreased with increase in the molecular weight. The rheological behavior of the various S‐EB‐S polymers was studied using a Monsanto Processability Tester. These systems exhibited pseudoplastic flow behavior. The shear viscosity of these S‐EB‐S polymers decreased with an increase in the molecular weight from S‐EB‐S‐1 to S‐EB‐S‐3 polymers because of the wall slip and plug flow. The activation energy of the melt flow process was found to vary between 4 and 0.6 kcal/mol in the range of shear rates studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1621–1628, 2000     

Thermoplastic polyheterocycles. I: Polyalkylene-benzoxazoles

Polyalkylenebenzoxazoles of high molecular weight (inherent viscosity values from 0.76 to 2.95) were prepared from 4,6-diaminoresorcinol dihydrochloride and aliphatic diacids in polyphosphoric acid by heating at 180 to 200°C for 3–5 h. Melting points of the polymers ranged from 148 to 423°C, depending on the length of the alkylene chain. Glass transition temperatures were relatively low, ranging from 50 to 100°C and did not show the pronounced odd/even effect noted for melting points. In all cases, rapid weight loss occurred above 400°C. No evidence for the formation of a molecular composite was observed in an attempt to prepare in situ a rod-like polybenzoxazole in a polyalkylenebenzoxazole.     

Relationship between molecular structure and zero‐shear viscosity of polymers

The relationship between molecular structure and zero‐shear viscosity of polymers was studied. In this study we propose a new equation, which is based on Berry and Fox's equation. This new equation is constructed from some molecular parameters, such as mean square length and average molecular weight of statistical skeletal unit, characteristic ratio, entanglement molecular weight, glass‐transition temperature, free volume fraction at glass‐transition temperature, and thermal expansion coefficient of free volume. It is proposed that some of these molecular parameters could be predicted by group contribution methods, except for the free volume parameters. We also propose new empirical relations between free volume parameters and molecular structures of polymers, which make it possible for free volume parameters to be obtained from molecular structure. Using these relationships, it is possible that the zero‐shear viscosity and its temperature dependence are obtainable from the molecular structure of polymers. We applied this formula to some polymers, including both amorphous and semicrystalline polymers. Comparison between the measured and calculated zero‐shear viscosity showed quite good agreement. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1609–1618, 2001     

Higher‐molecular‐weight hyperbranched polyethylenes containing crosslinking structures as lubricant viscosity‐index improvers

As a new grade of polyethylene materials with unique chain architectures, hyperbranched polyethylenes synthesized by chain walking ethylene polymerization have great potential for industrial application as novel viscosity index (VI) improver in lubricant formulation. Although high‐molecular‐weight hyperbranched polyethylenes (weight‐average molecular weight of about 10⁵ g/mol) possess high shear stability, their viscosity thickening properties are compromised due to their compact chain architectures. In this work, we aim at improving their viscosity thickening property by increasing polymer molecular weight. A range of hyperbranched polymers of various enhanced molecular weights were synthesized by chain walking ethylene polymerization in the presence of small amounts of 1,4‐butanediol diacrylate as a difunctional crosslinker. The molecular weight dependences of viscosity thickening power and shear stability of these polymers containing crosslinking structures were evaluated. It is found that, with the increase of molecular weight via crosslinking, these polymers showed consistently enhanced viscosity thickening power, but with the reduced shear stability. However, their shear stability was still significantly better compared to linear polymers. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Measurement of the elastic properties of polymer melts

A method and apparatus for measuring the elastic and other properties of polymers in the melt state is presented. The recoverable strain magnitude and the rate of strain recovery have been measured as a function of: applied shear rate, applied shear magnitude, temperature and molecular weight. The elastic properties indicate that there is an abrupt change or “transition” in the response of polystyrene melts at temperatures well above the glass transition. This abrupt change is found to be molecular weight dependent. The results are interpreted qualitatively in terms of molecular structure and practical processing operations. The possible relationship of this “transition” to T_u, is briefly discussed.     

Thermal degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

The degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate), a member of the Nodax family of polymers, were investigated using transient constant shear rate and dynamic time sweep rheological tests. The rate of chain scission at several times and temperatures was correlated with viscosity data and verified using molecular weight determination of the degraded samples. The experimental results show that the molecular weight and the viscosity of Nodax decrease with time over the range of temperatures that were studied (155–175°C). The degradation kinetics, which exhibited first‐order behavior, were determined as a function of the flow history and thermal history. An apparent activation energy of 189 ± 5 kJ/mol for thermal degradation was found by modeling variations in the rate with temperature using an Arrhenius law model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 66–74, 2005     

Acceleration effect of sericin on shear-induced β-transition of silk fibroin

Although silk sericin (SS) occupies 25% of silk protein, its importance has often been overlooked in the natural silk spinning process and in the formation of the crystalline structure of silk fibroin (SF). In this study, we elucidated the role of SS in the crystallization process of SF under shear using SF/SS blend solutions. In order to apply shear stress to the blend solution, a rotating glass rod was inserted into a glass tube filled with the solution and the shear rate was determined to be in the range of 598–724 s⁻¹. After shearing, SF aggregates were formed and the amount of the aggregates increased with shearing time. Additionally, it was observed that the aggregate formation and β-sheet transition of SF were enhanced when a proper amount of SS was in the blend solution. Consequently, the SS considerably contributes to the structural transition of SF under shear. The SS can improve the shear-induced β-sheet transition and crystallization of SF.     

Viscoelastic properties of poly(ethylene-co-styrene) copolymers

The viscoelastic properties of narrowly distributed linear poly(ethylene-co-styrene) copolymers with different mole fractions of styrene (x_S = 0–20.5 mol %) and molecular weights (M_w = 64–214 kg/mol) were analyzed in the molten state at different temperatures by means of oscillatory rheometry. Analyzing the thermorheological properties of the polymers, we found that the time temperature superposition principle is fulfilled. The corresponding shift factors follow up to 16.5 mol % of styrene units the Arrhenius behavior of neat polyethylene. For a styrene content of about 20 mol %, the polymers no longer crystallize and a transition from Arrhenius to WLF behavior of pure polystyrene was observed. The zero shear viscosity, η₀, of the polymers was derived from the mastercurves. The determination of the plateau modulus by the well-known tan δ-min criterion is not possible due to the beginning crystallization in the corresponding temperature range. An approximate calculation of this value is based on the characteristic relaxation time λ_x = 1/ω_x, corresponding to the crossover of G′ and G′. Indeed, the characteristic modulus G_px calculated as η₀/λ_x is a good approximation for the plateau modulus G_p. The viscosity–molecular weight and relaxation time–molecular weight scaling relations were established for three copolymers with different molecular weights and nearly the same styrene content. For both material parameters, the scaling exponent is around 3.4, confirming the linear architecture of the investigated polymers. The mixing rules describing the change of such material parameters like zero shear viscosity or plateau modulus independent of styrene content are of logarithmic linear character using the weight fraction of styrene units instead of the mole fraction. The relations found allow the prediction of melt state properties for polymers with arbitrary styrene content. In the future, when catalysts with sufficient activity for the synthesis of high styrene content copolymers are available, these predictions will have to be checked. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:209–215, 1997     

Effect of molecular weight and polymer concentration on the triple temperature/pH/ionic strength-sensitive behavior of poly(2-(dimethylamino)ethyl methacrylate)

Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) samples were synthesized via aqueous atom transfer radical polymerization with DP_n of 35, 151, 390, and 546 and dispersity of 1.13, 1.17, 1.20, and 1.18, respectively. All samples were exposed to temperature and pH variations at different concentration of polymer and salt (NaCl). Results indicated that cloud point (T_cl) can be controlled by changing DP_n, polymer concentration, and ionic strength of solution. According to results, T_cl of the PDMAEMA chains shifted to lower temperatures with increasing solution pH at all molecular weight ranges due to deprotonation of tertiary amine groups in polymer structure. However, higher molecular weight polymers were more sensitive to pH variation especially in alkaline media. Also, higher polymer concentration acted as driving force to decrease cloud point of samples and formation of aggregates that was more predominant for higher molecular weights at alkaline media. T_cl of PDMAEMA chains decreased with increasing ionic strength even at low pH values for low molecular weight polymers.     

Preparation and characterization of polyisoprenes and polybutadienes having 1,2- and 3,4-linkages preferentially

Polyisoprenes (PI) and polybutadienes (PB) both having vinyl-type side chains preferentially were prepared and characterized. Both polymers were anionically polymerized with cumyl potassium or pottassium naphthalenide as initiators in a polar solvent, tetrahydrofuran, at low temperature. From the ¹H NMR measurement, the PI contains 3,4- and 1,2-microstructures and PB does 1,2-microstructure preferentially. All the samples covering the molecular weight range of 37 k ≤ M_w ≤ 724 k for PI and 35 k ≤ M_w ≤ 197 k for PB were confirmed to have narrow molecular weight distribution. Measured glass transition temperatures, i.e., 11.0 °C for PI and ?0.7 °C for PB are both considerably high compared with those of 1,4-microstructure-rich analogues. Intrinsic viscosity measurements in 1,3-dioxane for PI and 2-octanol for PB were carried out, and the segment lengths of the 3,4-/1,2-rich PI and 1,2-rich PB were estimated to be 0.60 nm and 0.59 nm, which are both considerably shorter than the values for two polydienes having 1,4-microstructures preferentially, i.e., 0.66 nm for both 1,4-rich PI and PB. Furthermore plateau moduli of both polymers are determined by dynamic viscoelastic measurements.     

Rheological and chemorheological studies of cyclic aryl ether ketone and aryl ether thioether ketone oligomers containing the 1,2-dibenzoylbenzene moiety

The melt stability, shear rate, and temperature dependence of steady-state shear viscosity of molten cyclic aryl ether ketone and thioether ketone oligomers containing the 1,2-dibenzoylbenzene moiety have been investigated. The isothermal chemorheology of the ring-opening polymerization of cyclic oligomers 4 and 9 in the presence of a nucleophilic initiator was also conducted. The cyclic aryl ether ketone oligomers are thermally stable in the melt, and their melt viscosity is several orders of magnitude lower than their high molecular weight linear counterparts. At a given temperature, the steady-state shear viscosity of the molten cyclics initially undergoes shear thinning as the shear rate increases, and once the shear rate is above 10 s⁻¹, the molten cyclic oligomers behave like Newtonian fluids. For the amorphous cyclic oligomers studied, the steady-state shear viscosity at 100 s⁻¹ at a given temperature only depends on their glass transition temperature. The cyclic aryl thioether ketone oligomers are thermally unstable in the melt and undergo ring-opening polymerization in the absence of an initiator to form high molecular weight linear polymers with a concomitant rapid increase in viscosity. The rate of change in viscosity increases with temperature and is promoted by the addition of a catalytic amount of elemental sulfur or a disulfide such as 2,2-dithiobis(benzothiazole). It is hypothesized that the ring-opening polymerization is initiated by the in situ generated thiyl radical(s) and proceeds via a free radical route. © 1996 John Wiley & Sons, Inc.     

Influence of molecular weight on the domain coarsening rates in linear polyethylene–poly(ethylene‐co‐1‐octene) blends

The coarsening rates of the two‐phase morphologies of linear polyethylene/poly(ethylene‐co‐1‐octene) blends were determined as functions of molecular weight. Samples with cocontinuous morphologies that were prepared through solution blending were annealed in the melt state for various times, and, subsequently the length scales of the morphologies were determined with a line‐intersection method. Length‐scale data were multiplied by a function that normalized for the effects of differences in zero‐shear‐rate viscosity and thermal energy; after normalization, the data largely fell on one trend line within the bounds of experimental error. This indicated that the principal effect of increasing molecular weight was to slow the coarsening rate through an increase in melt viscosity, with little effect from the thermodynamic compatibility of the two polymers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1655–1661, 2003     

Effect of annealing time and molecular weight on melt memory of random ethylene 1‐butene copolymers

The effects of annealing time and molecular weight on the strong melt memory effect observed in random ethylene 1‐alkene copolymers are analyzed in a series of model ethylene 1‐butene copolymers with 2.2 mol% branches. Melt memory is associated with molten clusters of ethylene sequences from the initial crystals that remain in close proximity and are unable to diffuse quickly to the randomized melt state, thus increasing the recrystallization rate. Melt memory persists even for greater than 1000 min annealing indicating a long‐lived nature of the clusters that only fully dissolve at melt temperatures above a critical value (>160 °C). Below the critical melt temperature, molecular weight and annealing temperature have a strong influence on the slow kinetics of melt memory. For the copolymers analyzed, slow dissolution of clusters is experimentally observed only for M_w < 50 000 g mol^?1. More stable clusters that survive higher annealing temperatures display slower dissolution rates than clusters remaining at lower temperatures. The threshold crystallinity level to enable melt memory (X_c,threshold) decreases with increasing molecular weight and decreasing annealing temperature similarly to the variation of the chain diffusivity in the melt. The process leading to melt memory is thermally activated as the variation of X_c,threshold with temperature follows Arrhenius behavior with high activation energy (ca 108 kJ mol^?1) that is independent of molecular weight. © 2018 Society of Chemical Industry     

A unifying approach for melt rheology of linear polystyrene

Several studies of melt rheological properties of polystyrene have been conducted over the past 50 years. Several approaches, including empirical models, have been developed to understand the behavior of materials using simple equations. The existing melt rheology models are best suited for high‐molecular‐weight polymers whose T_g does not vary. In this work, a semiempirical viscosity equation has been derived, including the effect of T_g dependence on molecular weight, to describe the melt rheology of low‐molecular‐weight polymers. The equation is derived based on a combination of well‐known concepts, such as the effects of free volume and molecular dynamics on polymer rheology. This provides a better understanding of the rheological behavior in the low‐molecular‐weight regime with respect to temperature and molecular weight. Because of the industrial trend towards lower molecular weight materials for applications such as high solids coatings, this unifying approach, based on the free volume theory with a simple expression, is of extreme practical significance. This equation can predict the zero shear viscosity behavior for different molecular weights, including low‐molecular‐weight regions, and temperatures. Viscosity calculations using the empirical equation agree with published experimental data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2597–2607, 2007     

Structure‐property relationships of blends of polycarbonate

Three grades of bisphenol‐A polycarbonate—high molecular weight linear, high molecular weight branched and low molecular weight linear—and their blends have been studied by GPC, DMTA, DSC, rheometry and impact measurements. The molecular weight distribution of the blends agred with that predicted from the component's distributions, indicating that no transesterification reactions had occurred during melt blending. The T_g of the blends varied with blend composition according to the Fox equation and was related to the reciprocal molecular weight predicted by the Flory‐Fox equation. The low shear rate viscosity of the blends agreed with a logarithmic rule of mixtures and showed power‐law dependence on the weight average molecular weight. At higher shear rates, shear thinning was observed. The steady shear viscosity correlated well with the dynamic viscosity, as suggested by the Cox‐Merz relation. The stress relaxation behavior of the melt was very sensitive to the blend composition and molecular weight and correlated well with the real modulus. Temperature studies of the dart impact energy showed that only the low molecular weight polymer underwent a brittle‐duetile transition at ea ?30°C and that all the blends were tough at room temperature. The enhanced stress triaxiality inherent in the notched lzod test caused the impact strenght at room temperature to decrease almost linealy with blend composition.     

Glass transition temperatures of poly(alkyl α-cyanoacrylates)

The glass transition temperatures of the poly(alkyl α-cyanocrylates) were determined by the dilatometric technique, and some of the values were checked by differential thermal analysis. The data indicate that the T_g's appear to decrease with increase in the size of the alkyl group, for a given molecular weight range. It was also found that the T_g of poly(methyl or butyl α-cyanoacrylate) increased with molecular weight. All cyanoacrylates, excepting methyl and ethyl esters, formed only low molecular weight polymers in aqueous surroundings. Therefore, they have characteristic low glass transition temperatures, causing coalescence at low temperatures.     

Properties of random and block copolymers of butadiene and styrene. II. Melt flow

Flow curves, log (rate of shear) versus log (shear stress), as functions of temperature were obtained for several butadiene-styrene copolymers of fixed (25%) styrene content, differing in monomer sequence distribution. A random copolymer of constant composition along the polymer chain and narrow molecular weight distribution (MWD) exhibited behavior similar to linear, narrow MWD polybutadienes; the flow was Newtonian at low shear stresses, and the flow curves for various temperatures were accurately superimposable by a shift along the log (shear rate) axis. In a random copolymer varying in composition along the polymer chain, non-Newtonian behavior was more pronounced, and temperature-shear rate superposition did not succeed, a trend further perpetuated in copolymer of a single long styrene block sequence. The latter resemble branched polymers, as would be expected from association of the styrene blocks. With two styrene blocks, association produces network structures below the glass transition of polystyrene with consequent loss of flow. Disruption of these associations above T_g (styrene) imparts the greatest thermoplasticity to these elastomers. There is evidence, however, that some of the associations persist at temperatures well in excess of T_g (styrene).     

Increasing viscosity in entangled polyelectrolyte solutions by the addition of salt

The viscosity of several polyelectrolytes is measured in both salt free solutions and solutions in the high salt limit. At low polymer concentrations, the zero shear rate viscosity decreases as much as 100-fold upon addition of a monovalent salt, namely NaCl. However, as polymer concentration increases, the viscosity difference between polymer in salt free and in monovalent salt solution diminishes. Further, the zero shear rate viscosity becomes independent of added monovalent salt at the critical polyelectrolyte concentration c_D. Above c_D, the addition of monovalent salt increases the zero shear rate viscosity of the entangled polyelectrolyte solutions. The viscosity increase agrees with viscosity scaling theory for polyelectrolytes in the entangled regime. Polyelectrolytes exhibiting an increase in viscosity above c_D in the presence of monovalent salt include three natural anionic polyelectrolytes (xanthan, carrageenan, welan), one synthetic anionic polyelectrolyte (hydrolyzed polyacrylamide), and one natural cationic polyelectrolyte (chitosan). Generally, these polyelectrolytes are relatively high molecular weight (>1 M Dalton), which makes c_D experimentally accessible (e.g., c_D = 0.2 wt% for xanthan). The magnitude of the viscosity increase is as high as 300% for xanthan and nearly independent of monovalent salt concentration in the high salt limit. The increase in viscosity in monovalent salt solution and magnitude of c_D appear to be heavily influenced by the molecular characteristics of the polymers such as monomer weight, molecular structure, and chain conformation.     

Influence of melt stability on the crystallization of bis(4-aminophenoxy)benzene-oxydiphthalic anhydride based polyimides

Novel high performance semicrystalline polyimides, based on controlled molecular weight phthalic anhydride (PA) endcapped 1,4-bis(4-aminophenoxy)benzene (TPEQ diamine) and oxydiphthalic dianhydride (ODPA), were synthesized. They exhibited excellent thermal stability in nitrogen and air atmospheres as determined by thermogravimetric analysis (TGA). The glass transition temperatures (T_g) for these polymers ranged from 225°C for the 10,000 M_n (10K) polymer, to 238°C for the 30,000 (30K) M_n material. The observed melting temperatures for all the polymers were ∼420°C. The crystallization behavior of these polymers showed a strong molecular weight dependence, as illustrated by the observation that the 10K and 12.5K polymers crystallized with relative ease, whereas the 15K, 20K, and 30K polymers showed little or no ability to undergo thermal recrystallization. The thermal stability of these polymers above T_m was investigated by studying the effect of time and temperature in the melt on the cold crystallization and melting of these polymers. Increased time and temperature in the melt resulted in lower crystallinity because of melt state degradation, such as crosslinking and branching, as evidenced by an increase in melt viscosity, which was more prominent for the higher molecular weight polymers.     

Rheograms of cellulosic polymers from the melt flow index

Data on the variation of melt viscosity over a wide range of shear rates and temperatures are necessary in the processing of cellulosic polymers. An effective method has been proposed to estimate the viscosity vs. shear rate flow curves of a cellulosic resin at temperatures relevant to the processing conditions, from its melt flow index and glass transition temperature. The method involves the use of a master curve obtained by coalescing the rheograms of various grades in terms of a modified viscosity, η˙MFI, and a modified shear rate, γ˙/MFI. Master curves have been reported for cellulose esters and ethers.