Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly(aryl ether sulfone) (PES-C) were characterized in CHCl₃ at 25°C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity–intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Λ) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 × 10⁻⁴)M^−0.553, which agrees with the calibration of D = (2.45 × 10⁻⁴)M^−0.55 previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f_w(M) for the two PES-C samples. The weight-average molecular weights calculated from f_w(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. © 1997 John Wiley & Sons, Inc.     

Light-scattering Characterization of the Molecular Weight Distributions of Some Intractable Polymers

Recent developments of using laser light scattering (LLS) to characterize the molecular weight distribution f(M) of special polymers such as Kevlar, Tefzel, Teflon, branched epoxy clusters, gelatin, dextran, segment copolymers and polymer mixtures, are reviewed. The basic principle of combining static (classic) and dynamic LLS results is outlined. In dynamic LLS, the line-width (or the translational diffusion coefficient) distribution G(Γ) can be obtained from the precisely measured intensity–intensity time correlation function. The key problem is transforming G(Γ) to a corresponding molecular weight distribution f(M) is to establish a calibration between D (the translational diffusion coefficient) and M. Typical examples were used to illustrate different calibration methods, including the methods of using a series of narrowly distributed polymer standards with different molecular weights, using two or more broadly distributed polymer samples, and one broadly distributed polymer samples plus an additional experimental method (e.g. viscometry or size exclusion chromatography). The advantages and disadvantages of the LLS method are discussed by comparison with size exclusion chromatography. © 1997 John Wiley & Sons, Ltd.     

Characterization of novel optically active conjugated polyarylenes and poly(aryleneethnylene)s by a combination of off-line static and dynamic light scattering with gel permeation chromatography

By combining the offline static and dynamic laser light scattering (LLS) and gel permeation chromatography (GPC) results of a broadly distributed polymer sample, we were able to characterize a series of chiral binaphthyl-based polyarylenes and poly(aryleneethnylene)s in THF at 25°C. For each of the samples, we obtained not only the weight-average molar mass M_w, the second virial coefficient A₂ and the z-average translational diffusion coefficient 〈D〉, but also two calibrations: V = A + Blog(M) and D = k_D M^−αD, where V, D, and M are the elution volume, the translational diffusion coefficient and the molar mass for monodisperse polymer chains, respectively, and A, B, k_D, and α_D are four calibration constants. Using these calibrations, we estimated the molar mass distributions of these novel polymers. We showed that using polystyrene to calibrate the GPC columns could lead to a smaller M_w. Our results indicate that all the polymers studied have a rigid chain conformation in THF at 25°C and the introduction of the —NO₂ groups into the monomer can greatly promote the polymer solubility in THF.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2615–2622, 1998     

Scalings of fluorine‐containing polyimides in cyclopentanone

Eight 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (6FDA‐OTOL) fractions and seven 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy) phenyl] propane dianhydride‐4,4′‐diamino‐3,3′‐dimethylbiphenyl (BISADA‐OTOL) fractions in cyclopentanone at 30 °C were characterized by a combination of viscometry and static and dynamic laser light scattering (LLS). In static LLS, the angular dependence of the absolute scattered intensity led to the weight‐average molar mass (M_w), the z‐average root mean square radius of gyration, and the second virial coefficient. In dynamic LLS, the Laplace inversion of each measured intensity–intensity time correlation function resulted in a corresponding translational diffusion coefficient distribution [G(D)]. The scalings of 〈D〉 (cm²/s) = 8.13 × 10⁻⁵ M_w^−0.47 and [η] (dL/g) = 2.36 × 10⁻³ M_w^0.54 for 6FDA‐OTOL and 〈D〉 (cm²/s) = 3.02 × 10⁻⁴ M_w^−0.60 and [η] (dL/g) = 2.32 × 10⁻³ M_w^0.53 for BISADA‐OTOL were established. With these scalings, we successfully converted each G(D) value into a corresponding molar mass distribution. At 30 °C, cyclopentanone is a good solvent for BISADA‐OTOL but a poor solvent for 6FDA‐OTOL; this can be attributed to an ether linkage in BISADA‐OTOL. Therefore, BISADA‐OTOL has a more extended chain conformation than 6FDA‐OTOL in cyclopentanone. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2077–2080, 2000     

激光光散射表征聚N－异丙基丙烯酰胺的分子量分布

采用自由基聚合法合成了聚N-异丙基丙烯酰胺(PNIPAAM)样品,由激光光散射法(LLS),包括绝对累积散射光强的角度依赖性(静态LLS)和线宽分布的角度依赖性(动态LLS)表征了合成的PNIPAAM样品的分子量分布。通过对动态光散射测得的电场-电场时间相关函数的拉普拉斯变换,求得平动扩散系数分布G(D);结合静态和动态光散射测量的结果,即M_w和G(D),确定了PNIPAAM样品的平动扩散系数D对分子量M的标定关系式D=2.84×10^-4M^-0.55,并将G(D)转换成分子量分布F_w(M).     

Laser light-scattering investigation of the density of pauci-chain polystyrene microlatices

The average density (〈ρ〉) of the pauci-chain polystyrene microlatices (PCPS), which contains a few linear polystyrene chains, was investigated by laser light scattering (LLS) including both angular dependence of absolute integrated scattered intensity (static LLS) and of the line-width distribution G(Γ) (dynamic LLS). In static LLS, the weight-average particle mass (M_w) and the z-average radius of gyration (R_g) were measured; and simultaneously in dynamic LLS, the hydrodynamic radius distribution was obtained from Laplace inversion of very precisely measured intensity-intensity time correlation function. A combination of both the static and dynamic LLS results leads us to a value of 〈ρ〉. For comparison, we also determined 〈ρ〉 of conventional multichain polystyrene latex (MCPS) by following the same LLS procedure. It was found that 〈ρ〉_MCPS = 〈_bulk〉 = 1.05 g/cm^3, but 〈ρ〉_PCPS = 0.92 g/cm^3. This difference in density suggests that the intersegmental distance in MCPS or bulk polystyrene is smaller than that in PCPS, even the chains in PCPS are confined to a smaller volume. This might attribute to the fact, namely the intersegmental approaching inside PCPS is mainly the intrachain crossing which is more difficult in comparison with the interchain crossing inside MCPS or bulk polystyrene.     

Reaction parameters in the RAFT mediated dispersion polymerization of styrene

Monodisperse polystyrene (PS) particles were prepared by a living radical dispersion polymerization with a reversible addition‐fragmentation chain transfer (RAFT) agent in an ethanol medium. In the presence of RAFT agent, the effects of various reaction parameters on the characteristics of PS particles were systematically investigated. When no RAFT agent was involved, the number‐average molecular weight (M_n) of the PS particles increased from 17,800 to 30,000 g/mol, but the weight‐average diameter (D_w) decreased from 2.54 to 2.06 μm with the increase of poly(N‐vinylpyrrolidone) content from 4.0 to 16.0 wt %. No correlation between the M_n and the coefficient of variation (CV) was observed. However, when the RAFT concentration varied from 0 to 2.0 wt %, all of the conversion, M_n, D_w, CV, and polydispersity index (M_w/M_n) decreased. This indicates that the RAFT agent alters the inverse behavior between the molecular weight (MW) and particle size shown in the conventional dispersion polymerization. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 872–885, 2008     

Polydispersity effects in polymer self-diffusion measured by small-angle neutron scattering

The small-angle neutron scattering (SANS) method for measuring the self-diffusion coefficient D has been analyzed for effects of polydispersity in degree of polymerization for the case of linear polymers diffusing by reptation. Polydispersities corresponding to M_w/M_n = 1.0?10 were considered. It is shown that in all cases a meaningful effective diffusion coefficient D_e can be obtained from the short time recovery of the SANS intensity. This quantity D_e ≤ 1.3 D(M_w), where D(M_w) is the diffusion coefficient of a monodisperse polymer having molecular weight M = M_w. The method relies on SANS intensities extrapolated to zero scattering angle; realistic extrapolation is shown to give rise to quite acceptable errors on the order of 0.05 D_e.     

The solution phase characterization of poly(ferrocenyldimethylsilane)s by small‐angle neutron scattering

A series of monodisperse (M_w/M_n < 1.1) poly(ferrocenyldimethylsilane)s was prepared with number‐averaged degrees of polymerization, 〈z〉_n, of 9, 33, 206, and 506 ( 2 – 5 , respectively), as determined by gel permeation chromatography (GPC). The polymers were studied by small‐angle neutron scattering (SANS) in solution with the aim of obtaining the radius of gyration, R_g, the weight‐averaged molecular weight, M_w, and the polydispersity index, M_w/M_n. Data were collected over the range 0.008 < Q/Å^?1 < 0.5 and for a series of concentrations (weight fraction, w = 0.0063, 0.0125, 0.025, and 0.05). The scattered intensity, I(Q), was fitted to a model based on a Schultz–Zimm distribution of isolated chains with excluded volume. A comparison of the molecular weight and size data determined by GPC and SANS indicated an acceptable agreement between the values for R_g, M_w and M_w/M_n. The results of this study demonstrate the potential utility of SANS to fully characterize metallopolymers, and other polymer systems where traditional methods cannot be applied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4011–4020     

Light-scattering characterization of poly(ethylene terephthalate)

By using a closed-circuit filtration system, we have succeeded in clarifying poly(ethylene terephthalate) (PET) dissolved in hexafluoroisopropanol (HFIP). Such static properties as the radius of gyration R_g, the weight-average molecular weight M_w, and the second virial coefficient A₂ and such dynamic properties as the translational diffusion coefficient D, or its equivalent hydrodynamic radius R_h, and the second (diffusion) virial coefficient k_d were determined for several PET samples of different molecular weights by using light-scattering intensity and linewidth measurements. An empirical relation between D_o (or R_h) and M_w was established: R_h = (1.77±0.15)X10^?2 M with R_h and M_w expressed in units of nanometers and grams per mole, respectively. The empirical exponent α_D(ca. 0.58±0.01) is in good agreement with the less precisely determined intrinsic viscosity/molecular weight exponent α_η (ca. 0.71±0.02). Several intensity correlation functions were measured very precisely using long accumulation times. A Laplace inversion was performed using the singular-value decomposition technique. The approximate molecular weight distribution (MWD) determined by light-scattering spectroscopy was in reasonable agreement with a completely independent determination of MWD using gel permeation chromatography (GPC). It was interesting to note, though not surprising, that GPC showed emphasis on lower-molecular-weight fractions, while light-scattering emphasized higher-molecular-weight fractions. The agreement further strengthens some complementary aspects of the two techniques.     

Dynamic and electrophoretic light scattering of poly(dimethyldiallylammonium chloride) in salt-free solutions

Dynamic and electrophoretic light scattering were used to study the diffusion and electrophoretic mobility of poly(dimethyldiallylammonium chloride) as a function of polymer molecular weight in salt-free solutions. Two relaxation modes characterized as fast diffusion (D_f) and slow diffusion (D_s) were obtained from dynamic light scattering. Although the slow diffusion coefficient D_s strongly depends on molecular weight (M_w), the fast diffusion coefficient D_f was found to be independent of M_w over the range in the study. The fast diffusion was considered as the diffusion of a part of the polymer chain; the slow diffusion was interpreted by multichain diffusion. Electrophoretic light scattering results in the salt-free solution show that the electrophoretic mobility of the polymer is independent of M_w. © 1996 John Wiley & Sons, Inc.     

Molecular architecture and conformation of macromolecules of novel polysilanes

Molecular-weight parameters of new silane homo- and copolymers were analyzed. For all polymers, theM _w values are close ((6.0–8.6)·10⁴), the curves of molecular weight distribution are unimodal, andM _w/M _n=2−2.5. Cyclic fragments or those containing the −C=C− groups make the major contribution to the polysilane chain rigidity. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2430–2433, December, 1998.     

CHARACTERIZATION OF MOLECULAR MASS OF SIX WATER-SOLUBLE POLYSACCHARIDE -PROTEIN COMPLEXES FROM GANODERMA TSUGAE MYCELIUM

Six water-soluble polysaccharide-protein complexes coded as GM1, GM2, GM3, GM4, GM5 and GM6 wereisolated from the mycelium of Ganoderma tsugae by extracting with 0.2 mol/L phosphate buffer solution at 25, 40 and80℃, water at 120℃, 0.5 mol/L aqueous NaOH solution at 25 and 65℃, consecutively. Their chemical components wereanalyzed by using IR, GC, HPLC and ~(13)C-NMR, and some new results were obtained. The four samples GM1, GM2, GM3and GM4 are heteropolysaccharide-prote in complexes, in which, α- (1→3) linked D-glucose is the major monosaccharidewhile galactose, mannose and ribose are the secondary ones. GM5 and GM6 are β-(1→3)-D-glucan-protein complexes. Theprotein content increased from 32% to 69% with the progress of isolation. Weight-average molecu1ar mass M_w and theintrinsic viscosity [η] of the GM samples in 0.5 mol/L aqueous NaCl solution at 25℃ were measured systematically by laserlight scartering (LLS), size exclusion chromatography (SEC) combined with LLS, and viscometry. The M_w of GM1 to GM6are 35.5, 46.8, 58.9, 41.6, 3.3 and 22.0×10~4, respectively. The conformation and molecular mass of the two fractions of sample GM5 were characterized satisfactorily by SEC-LLS without further fractionation.     

Ionic interaction behavior and facilitated olefin transport in poly(n‐vinyl pyrrolidone):Silver triflate electrolytes; Effect of molecular weight

Interactions of cation/anion and cation/polymer in poly(N‐vinyl pyrrolidone) (PVP):silver triflate (AgCF₃SO₃) electrolytes with different weight‐average molecular weights (M_w's) of 1 × 10⁶ (1 M), 3.6 × 10⁵ (360 K), 4 × 10⁴ (40 K), and 1 × 10⁴ (10 K) have been studied with IR and Raman spectroscopies. According to the change of the C?O peak, coordination of silver ions by C?O in a low M_w (10 or 40 K) PVP matrix tend to be always thermodynamically favorable than high M_w (1 M or 360 K) PVP, demonstrating that the polymer matrix of low M_w dissolves silver salts more effectively. In addition, silver cations interact with both larger SO and smaller CF₃ to form ion pairs, and the former interaction is stronger than the latter in a monomer or low M_w polymer matrix (40 K, 10 K), as demonstrated by theoretical ab initio calculation or experimental spectroscopy, respectively. However, CF₃ interacts more favorably with silver cation than SO in high M_w (1 M and 360 K) PVP, which is ascribed to the steric effect of the bulky SO anion by highly entangled polymer chains. Despite the superior dissolving property of the low M_w polymer matrix, the membranes consisting of low M_w PVP and AgCF₃SO₃ exhibited poor separation performance for propylene/propane mixtures in comparison with those of high M_w, presumably because of the poor mechanical property for membrane formation in low M_w PVP. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1813–1820, 2002     

一种新的标定体积排除色谱（SEC）的方法

基于体积排除色谱中测得的淋出体积和动态激光光散射中测得的平动扩散系数都直接依赖于高分子的流体力学体积这一事实，本文在理论上提出了一种把淋出体积分布和平动扩散系数分布二者结合起来标定体积排除色谱的新方法，并且在实验上通过对宽分布的聚苯乙烯标准样品的测试证实了该方法的可行性．     

Thermal diffusion and molecular weight calibration of poly(ethylene-co-vinyl acetate)s by thermal field-flow fractionation

Copolymer characterization is accomplished with respect to measurement of thermal diffusion coefficient (D_T) and molecular weight determination by thermal field-flow fractionation. The examined copolymers are the eight poly(ethylene-co-vinyl acetate)s [P(E-V)] having different compositions of vinyl acetate ranging from 25 to 70% and the molecular weight from 110,000 to 285,000, and three polyvinyl acetate standards as component homopolymer. The carrier solvents are tetrahydrofuran, toluene, and chlorobenzene which have different viscosities and thermal conductivities. Measured D_T values vary from 1.36 × 10^?8 to 5.97 × 10_?8 cm²/(s . K) which are dependent on the composition of copolymers and types of carriers. These values increase linearly with the increase of weight percent of vinyl acetate. It is possible to estimate D_T values of polyethylene from the extrapolated intercept in the plots of D_T vs. vinyl acetate wt % of copolymer. Tetrahydrofuran is found to be the appropriate carrier solvent for the separation of P(E-V) copolymers since D_T varies greatly with the increase of wt % in THF. Attempts are made to correlate the measured retention data with molecular sizes of copolymers for the construction of the molecular weight calibration curve. Good correlations (r² ≥ 0.931) are found in which D/D_T values of polymers vary inversely with the product of hydrodynamic volume by weight ratio of vinyl acetate. Based on this relationship, the unknown molecular weight of copolymer sample can be determined from component homopolymers for which standards are readily available. © 1995 John Wiley & Sons, Inc.     

Nitroxide mediated synthesis of low dispersity random copolymers for low‐loss optical waveguides

Candidate materials for low‐loss optical waveguides based on poly(glycidyl methacrylate‐ran‐pentafluostyrene) [P(GMA‐ran‐PFS)] copolymers were synthesized by nitroxide mediated polymerization (NMP) initiated with BlocBuilder^® [N‐(2‐methylpropyl)‐N‐(1‐diethlphosphono‐2,2‐dimethylpropyl)‐O‐(2‐carboxylprop‐2‐yl) hydroxylamine] bearing a succinimidyl ester group (NHS‐BlocBuilder) at 90 °C in 1,4 dioxane. The copolymerizations yielded copolymers with low dispersity M_w/M_n between 1.2 and 1.4. The core structure of single‐mode channel waveguides was fabricated by direct UV lithographic patterning. The copolymers with low M_w/M_n resulted in line width roughness (LWR) of about 0.16 μm, whereas LWR of copolymers with M_w/M_n=3.5 but similar compositions was about 0.5 μm. The improvement in microstructural control allotted by NMP permitted finer pattern replication for copolymers desired for optical waveguides, as suggested for photoresist polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2970–2978     

Regulation of Molecular Weight Characteristics and Microtacticity of Polyhexene Produced over Highly Active Supported Titanium–Magnesium Catalysts

The data on the effect of polymerization temperature of 1‐hexene within the 30–70 °C range in the presence of a highly active supported titanium–magnesium catalyst on molecular weight characteristics and microtacticity of polyhexene, with cocatalyst composition being additionally varied (AlEt₃ or Al(i‐Bu)₃), in the absence and presence of an external stereoregulating electron‐donating compound and hydrogen, are reported. Polymerization conditions, making it possible to specifically regulate molecular weight and molecular weight distribution of polyhexene over a broad range ((M_w = 7 × 10⁴–2.2 × 10⁶ g mol⁻¹; M_w/M_n = 3.7–33) and regulate isotacticity of polyhexene (content of mmmm pentads from 56% to 96%), while retaining high catalyst activity, are determined.     

SIZE EXCLUSION CHROMATOGRAPHIC COLUMN PACKED WITH REGENERATED CELLULOSE GELS*

Microporous regenerated cellulose gel particles were prepared by mixing cellulose cuoxam with silk fibroin aspore former, and the mean pore size and pore volume of the pallicles were 525 nm and 7.27 mL g~(-1), respectively. Apreparative size-exclusion chromatography (SEC) column (550 mm×20 mm) packed with the cellulose gel particles wasused for the fractionation of two polysaccharides Dextran 07 (M_w = 7.14×10~4, d= 1.7) and Dextran 50(M_w = 50.5×10~4,d = 3.8) in water phase. The fractionation range of the stationary phase covered M_w from 3×10~3 to 1.1×10~6. The dailythroughput was 2.9 g for Dextran 07 (D07) and 4.3 g for Dextran 50 (D50) with a flow-rate of 1.5 mL min~(-1). The fractionsobtained by using the SEC were analyzed by an analytical SEC combined with laser light scattering (LLS), and thepolydispersity indices of fractions for Dextran 07 and Dextran 50 were determined to be 1.34-1.57 and 1.53-3.36,respectively. The preparative SEC is a simple, rapid, and suitable means not only for the fractionation of polysaccharides inwater but also for other polymers in organic solvents.     

Aqueous RAFT polymerization of acrylamide: A convenient method for polyacrylamide with narrow molecular weight distribution

Controlled and homogeneous free-radical polymerization of acrylamide(AM) in aqueous phase was realized by using S,S'-bis(α,α'-dimethyl-α'-acetic acid)-trithiocarbonate as a reversible addition-fragmentation transfer(RAFT) agent. Linear increases in molecular weight with conversion and narrow molecular weight distribution were observed for polyacrylamide(PAM) throughout the polymerization. By this method, PAMs with controlled molecular weight(up to 1.0 × 10~6) and narrow molecular weight distribution(M_w/M_n 1.2) were prepared. This study provides an effective method for synthesis of PAMs with narrow molecular weight distribution under environmentally friendly conditions.