Characterization of branched polymers by size exclusion chromatography coupled with multiangle light scattering detector. I. Size exclusion chromatography elution behavior of branched polymers

The elution behavior of branched macromolecules during their separation by size exclusion chromatography (SEC) was studied. The elution behavior of branched polymers was investigated using samples of randomly branched polystyrene and star branched poly(benzyl methacrylate) of different levels of branching by means of a SEC chromatograph coupled with a multiangle light scattering detector. Abnormal SEC elution behavior was found to be typical for highly branched polymers. After a normal elution at small elution volumes the molar mass and root mean square radius of the eluting molecules increased with increasing elution volume. Several SEC experiments were carried out to find explanation for this effect and SEC separation was compared with the separation by thermal field flow fractionation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1588–1594, 2001     

Covalent immobilization of biological molecules to maleic anhydride and methyl vinyl ether copolymers—A physico‐chemical approach

The covalent grafting of biological molecules to copolymers of maleic anhydride and methyl vinyl ether (MAMVE) has been used in various applications in diagnostics. To tentatively elucidate the phenomena involved in the control of the immobilization of oligodeoxynucleotides and proteins, the physico‐chemical properties of MAMVE copolymers were investigated. Because the grafting mixture contains water, to allow dissolution of the biomolecules without loss of biological properties, the anhydride‐based copolymer evolves from a neutral to a negatively charged macromolecule due to hydrolysis of the anhydride moities. The properties of both hydrolyzed and nonhydrolyzed polymers were investigated. As demonstrated by light‐scattering measurements in batch, the copolymers showed some level of aggregation in DMF, DMSO, and aqueous DMSO. The presence of aggregates was confirmed by size‐exclusion chromatography in DMF. However, partial deaggregation occurred for the lowest molecular weight sample, on adding 1% w/v of LiBr. The nonhydrolyzed copolymers exhibited a rigid conformation in a 5% water/DMSO mixture, as well as their hydrolyzed counterpart at a low ionization degree. The rate of the hydrolysis reaction was shown to be dependent on the pH of the reaction medium and on temperature. The activation energy of the hydrolysis reaction was 14 kJ/mol, and the rate constant in the order of 10⁻⁴ s⁻¹. On the basis of these data, the effect on the grafting reaction of biomolecules of different parameters such as ionic strength and the nature of the solvent, along with some other results were interpreted in terms of interactions between the synthetic and bioactive macromolecules. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 927–936, 1999     

Reactive polymers in diagnostics: Syntheses and characterizations of nucleic acid probes and maleic anhydride-co-methyl vinyl ether polymers

Maleic anhydride-co-methyl vinyl ether copolymers were used as reactive polymers to link oligodeoxyribonucleotides (ODN) to make oligonucleotide-copolymer conjugates of potential applications in diagnostics. The anhydride moieties of the copolymers were used for the covalent binding, via the formation of a peptide bond, on reaction with DNA probes that were amino modified at the 5′ position. The best coupling yields were obtained by carrying out the reaction in a DMSO-borate buffer (95/5 volume ratio) mixture at high ionic strength. Copolymers and ODN-copolymer conjugates were characterized by size exclusion chromatography and multiangle laser light scattering detection. The average molecular weights of the formed conjugates were relatively high, in the 10⁶ g/mol range, resulting from the crosslinking of several copolymer molecules during coupling. Coupling DNA probes onto smaller molecular weight polymers did not result in the formation of very high molecular weight conjugates showing that copolymer chain interpenetration was a determining factor of the crosslinking process that occurs during the coupling reaction. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2567–2577, 1997     

Models of SEC elution curves for binary and multi‐component polymers

BACKGROUND: Frequently, the unimodal shape of size‐exclusion chromatography (SEC) elution curves is taken as evidence that the polymer sample being analysed contains no minority components in significant quantities. The legitimacy of this assumption, however, has never been checked systematically. RESULTS: An algorithm for the simulation of SEC elution curves of multi‐component polymer systems has been developed. Using the algorithm, the shapes of the overall SEC curves with a wide range of parameters describing binary systems were generated and scanned. The crucial parameters determining the shape of the elution curves are the ratio of the molecular weights of the components, the breadth of the molecular weight distribution of the components, the mass fractions of the components and the band broadening. CONCLUSION: A detailed inspection of the curves shows that the identification of the presence of minority components in such systems from the shapes of the elution curves is more difficult then generally assumed. The absence of peak irregularities, such as minima or inflection points, widely used as a proof of absence of minority components, is a highly unreliable criterion. Copyright © 2008 Society of Chemical Industry     

Aggregation in dilute solutions of high molar mass poly(ethylene) oxide and its effect on polymer turbulent drag reduction

We apply methods of dynamic light scattering (DLS) and fluid mechanics to quantitatively establish the role of aggregation in the turbulent drag reduction of high molar mass poly(ethylene oxide) (PEO) solutions. By means of DLS, we show that the dilute aqueous solutions of high molar mass PEO (M_w ∼ 4 × 10⁶ g/mol) are aggregated and that this aggregate structure can be manipulated by addition of the chaotropic salt guanidine sulfate (GuS) or the divalent salt magnesium sulfate (MgSO₄). In aqueous solution, we find Γ ∼ q^2.8±0.1, where Γ is the DLS correlation function relaxation rate and q is the scattering vector. This scaling is consistent with internal motions of a large coil or aggregate. Addition of salt progressively decreases the scaling to Γ ∼ q^2.0±0.1 (at 0.5 M of MgSO₄) consistent with center-of-mass diffusion of isolated coils. We further find that manipulating the aggregation state of PEO with MgSO₄ shifts the critical condition for onset of turbulent drag reduction at dilute concentrations in pipe flow by a factor of 2.5. Because this critical condition is inversely proportional to the viscoelastic relaxation time of the polymer solution, we conclude that the aggregation state and the turbulent drag reduction behavior of PEO are strongly correlated. This correlation definitively confirms prior speculation (Cox et al. Nature 1974;249; Vlachogiannis et al. Physics of Fluids 2003;15(12)) that the high molar mass PEO commonly used in literature studies of turbulent drag reduction is in a state of aggregation. Furthermore, the quantitative differences in quiescent DLS characterization and turbulent flow pressure drop measurements suggest that high molar mass PEO undergoes flow-induced de-aggregation in transport systems with shear stresses as low as 0.5 Pa.     

Solution properties of xanthan. Light scattering and viscometry on dilute and moderately concentrated solutions

Elastic and quasi-elastic light-scattering, viscometric and rheological studies are given for solutions of the microbial polysaccharide Xanthomonas campestris (xanthan) in aqueous 0.62N NaCl for polymer concentrations from 0.03 to 2.2 g kg⁻¹. The observed negative ∂ln[η]/∂ln T is interpreted as a decrease of the persistence length with increasing T. The behaviour in moderately concentrated solutions (2<[η]c<25) reveals intermolecular association, leading to gel formation in the extreme case. The effect of the association on the viscometric and light-scattering data is discussed. It is concluded that the early stages of association involve structure with the chain axes nearly parallel, but that larger, particulate-like structures develop with increasing c, eventually leading to gel formation under certain conditions.     

Characterization of branched polymers by SEC coupled with a multiangle light scattering detector. II. Data processing and interpretation

This study deals with the characterization of branched polymers by means of size-exclusion chromatography coupled with a multiangle light scattering detector (SEC-MALS). The application of SEC-MALS is demonstrated on several randomly branched polystyrene and star-branched poly(benzyl methacrylate) samples. Various methods of the data processing are compared. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 454–460, 2001     

Molar mass distribution by size exclusion chromatography: Comparison of multi-angle light scattering and universal calibration

Series of polymers of various molar mass, chemical composition, and molecular architecture was analyzed by size exclusion chromatography (SEC) coupled with a multi-angle light scattering (MALS) photometer and an online viscometer. The molar mass averages were determined from the signal of MALS or calculated from the intrinsic viscosity and universal calibration. The comparison of the obtained results showed significant differences between the two methods. The MALS detection was shown to be more accurate for the determination of the weight-average molar mass and less vulnerable to the spreading of polymer peak by band broadening. The universal calibration can yield more accurate estimation of the number-average molar mass of branched polymers. It is also significantly more accurate for the characterization of fluorescent polymers than MALS with a regular laser of 660 nm. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47561.     

Modified bead-spring theory of dilute polymer solutions. II. Effects of polydispersity and comparison with experiment

A constitutive equation, previously derived for dilute, monodisperse solutions of linear macromolecules, is extended to include polydisperse solutions. This result, which represents a coupling of continuum and molecular theory, realistically portrays the effects of molecular weight and molecular weight distribution on mechanical behavior. Intrinsic viscosity–shear rate data are well described, and with certain semiempirical modifications the equation also fits normal stress and dynamic viscosity data for slightly more concentrated solutions. Some unusual effects associated with the characterization of macromolecular degradation, in studies of turbulent drag reduction, are also explained.     

Molecular characterization of statistical copolymers: 1. Potential and limitations of full adsorption–desorption procedure in separation of statistical copolymers

Dynamic integral desorption isotherms for a series of poly(methyl methacrylate) homopolymers and poly(methyl methacrylate)–polystyrene statistical copolymers were measured. Nonporous silica was the full adsorption–desorption (FAD) column packing and various adsorption‐promoting and desorption‐promoting liquids were used. The aim of this study was to evaluate the applicability of the FAD approach for separation of statistical copolymers. The effects of the adsorbing liquid and desorbing liquid nature were demonstrated on the positions and shapes of desorption isotherms. The desorption isotherms also strongly depended on both (co)polymer molar mass and copolymer chemical composition. This indicates large fractionation potential of the FAD procedure. Simultaneously, the interference of both above parameters prevents the direct use of FAD for fractionation of the copolymers. It is anticipated that the fractionation and/or reconcentration potential of the FAD procedure can be very effectively utilized in combination of FAD with size‐exclusion chromatography and/or with gradient elution liquid adsorption chromatography. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 857–864, 2000     

Static and dynamic light scattering studies of the crystallization of poly(ethylene oxide) from dilute solutions

We have monitored in situ the self-seeded crystallization of poly(ethylene oxide) from dilute toluene solutions by dynamic light scattering. In supercooled dilute solution, the radii (R) of the crystals grow linearly with time. the rate constant obtained from the slope of the plot R versus time depends on the temperature and the molecular weight of the polymer, both of which determine the degree of the supercooling. The maximum crystal size obtained from solutions of fixed concentration also depends on the temperature and the polymer molecular weight. It appears that crystal growth is limited because of molecular weight fractionation. Static light scattering from suspensions of stable crystals provides information on the crystal morphology. A comparison of experimental and theoretical particle scattering functions suggests that the crystals form short cylinders and that the crystal growth from the seeds is primarily two-dimensional. Some comparisons to melt crystallization are possible. The preparation and use of tiny seed crystals is critical to the success of these studies.     

Synthesis and characterization of lactose based resorcinol resin

Resorcinol‐lactose resin was synthesized using phosphoric acid as the catalyst at 95°C. ¹³C‐NMR measurements proved that the chemical reaction is initiated at the 4‐ or 6‐carbon position in benzene ring. Sample separation by size‐exclusion chromatography (SEC) technology indicated that the resin consists of reacting mixtures of oligomer of lactose, glucose, and galacose with resorcinol. The resin, using a by product of diary industry as a main component, could be potentially applied as a novel adhesive to the wood process industry. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2581–2585, 2002     

Effect of the MMA content on the emulsion polymerization process and adhesive properties of poly(BA‐co‐MMA‐co‐AA) latexes

In the past work, the shear resistance of pure poly(n‐butyl acrylate) was low, even incorporation of inorganic filler, silica in the composition. It is well‐known that the copolymerization of n‐butyl acrylate (BA) with methyl methacrylate (MMA) will increase the glass transition temperature, and enhance the shear resistance of acrylic polymers. In the current work, the preparation of a series of acrylic water‐borne pressure‐sensitive adhesives (PSAs) with the controlled composition and structure for the copolymerization of BA and acrylic acid (AA) with different MMA contents, poly(BA‐co‐MMA‐co‐AA) was reported and its effects on adhesive properties of the latices were investigated. The latices of poly(BA‐co‐MMA‐co‐AA) were prepared at a solid content of 50% by two‐stage sequential emulsion polymerization, and this process consisted of a batch seed stage giving a particle diameter of 111 nm, which was then grown by the semicontinuous addition of monomers to final diameter of 303 nm. Dynamic light scattering (DLS) was used to monitor the particle diameters and proved that no new nucleation occurred during the growth stage. Copolymerization of BA with MMA raised the glass transition temperature (T_g) of the soft acrylic polymers, and had the effect of improving shear resistance, while the loop tack and peel adhesion kept relatively high. The relationship between pressure‐sensitive properties and molecular parameters, such as gel content and molecular weight, was evaluated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water‐soluble polymers. LXXXII. Shear degradation effects on drag reduction behavior of dilute polymer solutions

Drag reduction measurements were conducted on extensively characterized poly(ethylene oxide) and poly(acrylamide) utilizing a fully automated rotating disk rheometer equipped with an optical tachometer, torque transducer, and software allowing real‐time data acquisition. The instrument sensitivity allowed the study of concentrations as low as 0.1 ppm. In addition, previously immeasurable concentration‐ and time‐dependent shear degradation effects were readily observed. A power law equation was shown to adequately correlate the percentage of drag reduction and the volume fraction for each polymer. Furthermore, an empirical shift factor was utilized to superimpose data from all the systems that were studied. By conducting measurements in the proper concentration and time domains, it was possible to extract the minimal concentration for the maximum drag reduction efficiency in the absence of shear degradation. The resulting values were significantly higher than those previously reported by our laboratories for poly(ethylene oxide) and poly(acrylamide). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1211–1221, 2001     

Characterization by dilute solution and rheological methods of polystyrene and poly(methyl methacrylate) produced with a tetrafunctional peroxide initiator

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) samples produced by the bulk homopolymerization of styrene and methyl methacrylate with a tetrafunctional peroxide initiator (JWEB50) are characterized in detail by various solution and rheological methods. For comparison purposes, “linear” PS and PMMA samples were produced under similar conditions with a monofunctional initiator (TBEC). The four sample types were characterized by size exclusion chromatography (SEC) setups to determine molecular weight, radius of gyration, and intrinsic viscosity distributions. Contraction factors were calculated and indicated evidence of branching for polystyrene produced with JWEB50 while no such effects were observed with PMMA. The rheological behavior of the samples was subsequently investigated by performing oscillatory shear and creep experiments. Compared to the “linear” material, samples produced with JWEB50 exhibited a reduction in zero‐shear viscosity that was attributed to long‐chain branching. Retardation spectra were calculated based on creep data and converted to dynamic compliances that were then combined with the oscillatory data. This provided master curves spanning a much wider frequency range than could be obtained experimentally. Examination of various viscoelastic functions showed evidence of long‐chain branching for both polystyrene and poly(methyl methacrylate) samples produced with JWEB50. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1340–1355, 2007     

Determination of thermodynamic interaction in mixed polymer solutions by a rapid and precise osmotic method. The system dextran/polyvinylpyrrolidone/water

An accurate and simple osmotic method for determination of thermodynamic interaction in ternary solutions (polymer A/polymer B/solvent) is described. The equipment consists of a membrane osmometer of a special design with small chambers and a pressure-sensing device to monitor the pressure difference across the membrane. A procedure has been developed to measure osmotic pressures up to rather high concentrations in both quasi-binary and quasi-ternary systems. The osmotic method is compared with results from light scattering. Different methods are utilized to extract ordinary virial coefficients as well as mixed virial coefficients from the primary data. The system dextran/polyvinylpyrrolidone/water (two different molecular weights of dextran) was chosen as a model.     

Fractionation and Analysis of an Impact Poly(propylene) Copolymer by TREF and SEC‐FTIR

TREF fractionation was combined with SEC‐FTIR analysis to measure the compositional heterogeneity within a commercial impact PP copolymer. The chemical composition of all fractions was determined as function of their molecular weight distribution. This approach proved to be highly successful at identifying different constituents within fractions exhibiting bimodal molecular weight distributions. Furthermore, the determination of ethylene and propylene crystallinity distribution across the molecular weight distribution confirmed the morphological nature of each of the components of the bimodal distribution. It is demonstrated that the combination of TREF and SEC‐FTIR provides a simple alternative to more time‐consuming conventional ways of characterising impact PP copolymers of complex heterogeneity.

     

Automated batch characterization of polymer solutions by static light scattering and viscometry

Using a programmable mixing pump, light scattering flow chamber, refractive index detector, and single capillary viscometer, the batch (unfractionated) characterization of polymers in solution has been automated. Three different schemes to produce polymer concentration gradients were used, and values for weight average mass M_w, root mean square radius of gyration 〈S²〉^1/2, second virial coefficient A₂, and intrinsic viscosity [η] were determined for a broad distribution sample of poly(vinyl pyrrolidone) (PVP) and a narrow fraction of poly(ethylene oxide) (PEO). High concentration experiments on the PVP also allowed determination of the third virial coefficient A₃. The method has several advantages over traditional manual methods in terms of accuracy, sample preparation, and amount of labor required. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2359–2368, 1999     

Hybrids formed between polyvinylpyrrolidone and an A3B porphyrin dye: behaviour in aqueous solutions and chemical response to CO2 presence

This study reports the incorporation of an A₃B mixed functionalized porphyrin, namely 5‐(4‐pyridyl)‐10,15,20‐tris(4‐phenoxyphenyl)porphyrin (PyTPOPP), into polyvinylpyrrolidone (PVP), a biocompatible polymer, with the purpose of preparing water‐soluble polymer–dye (PVP‐PyTPOPP) hybrids. The hybrids were obtained in two variants, differing by molar ratios, and their molecular characteristics and aggregation in dilute aqueous solutions were investigated using static and dynamic light scattering and analytical ultracentrifugation methods. The hybrids were characterized using ¹H NMR, UV‐visible and Fourier transform infrared spectroscopies, atomic force microscopy (AFM) and transmission electron microscopy (TEM). A study of the influence of acidic media on the electronic spectra was carried out, evidencing the similar behaviour of the hybrids and the bare porphyrin. The interaction between CO₂ and the PVP‐PyTPOPP hybrids was studied using UV‐visible spectroscopy and a continuous hypochromic response of the Soret band in direct relationship with increased CO₂ concentration was noticed. Based on the UV‐visible spectral differences between the PVP‐PyTPOPP hybrids in acidic media and during CO₂ exposure, we can presume that the mechanism of CO₂ detection is not based on pH changes of the solution but on chemisorption phenomena which modify the surface properties as confirmed by TEM and AFM. These porphyrin–PVP hybrid nanomaterials offer the possibility for achieving optical and colorimetric sensors for monitoring CO₂ and are also promising for biomedical applications. © 2015 Society of Chemical Industry