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The effect of long-chain branching on the size of low-density polyethylene molecules in solution is demonstrated through solution viscosity and molecular weight measurements on fractionated samples. These well-characterized fractions are analyzed by gel permeation chromatography (GPC), and it is shown that the separation of the polymer molecules by this technique is sensitive to the presence of long-chain branching. By using fractions of branched polyethylene possessing differing degrees of branching, one observes that a single curve is adequate in relating elution volume to molecular weight. This calibration curve is applied in the GPC analysis of a variety of commercial low-density polyethylene resins and it is shown, by comparison with independent osmometric and gradient elution chromatographic data, that realistic values for molecular weight and molecular weight distribution are obtained. The replacement of molecular weight M by the parameter [η]M as a function of elution volume, leads to a single relationship for both linear and branched polyethylenes. This indicates that GPC separation takes place according to the hydrodynamic volumes of the polymer molecules. The comparison of data for polyethylene and polystyrene fractions suggests that this volume dependence of the separation will be observed for other polymer–solvent systems. 相似文献
3.
Michael L. Alessi Katie C. Bittner Sandra C. Greer 《Journal of Polymer Science.Polymer Physics》2004,42(1):129-145
We measured the cloud-point curves of eight-arm star polystyrene (sPS) in methylcyclohexane (MCH) for polymer samples of three total molecular masses [weight-average molecular weight (Mw) × 10−3 = 77, 215, or 268]. We found a downward shift of 5–15 K in the critical temperature (Tc) of the star polymer solutions with respect to linear polystyrene (PS) solutions of the same Mw. The shift in Tc became smaller as Mw increased. The critical volume fraction for eight-arm sPS in MCH was equal within experimental uncertainty (10–40%) to that of linear PS in MCH. For sPS of Mw = 77,000 in MCH, we studied the mass density (ρ) as a function of temperature (T). As for linear polymers in solution, the difference in ρ between coexisting phases (Δρ) could be described over t = (Tc − T)/Tc for 1.1 × 10−4 < t < 4.7 × 10−3 with the Ising value of the exponent β in the expression Δρ = B tβ. Both ρ(T) above Tc and the average value of ρ below Tc were linear functions of temperature; no singular corrections were observed. The measurements of the shear viscosity (η) near Tc for sPS (Mw = 74,000) in MCH indicated a strong critical anomaly in η, but the data were not precise enough for a quantitative analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 129–145, 2004 相似文献
4.
A new type of palladium chelate of β-diketone-based side chain liquid crystal polysiloxane (Pd-DKLCP) has been synthesized by chelation reaction of palladium dichloride with polymeric ligand, β-diketone polysiloxane (DKLCP), using THF as solvent at R.T.. The Pd-chelation results in greatly increasing the phase transition temperature T_K and the enthalpy change △H_K from crystal to liquid crystal state and making the temperature range of LC state △T(△T=T_(Cl)-T_K) widened. All these chelates Pd-DKLCP's do not show T_(Cl) until decomposition at 205℃. It is noteworthy that the Pd-chelation can exert more positive effect on the mesomorphic behaviour of the polymer ligand than the counterpart Cu-DKLCP does. It is probable due to the bigger size of disc-like mesogen formed from β-diketone and Pd~(+2) ion with 4d orbital. 相似文献
5.
Hakan Durmaz Aydan Dag Ceyda Onen Ozgul Gok Amitav Sanyal Gurkan Hizal Umit Tunca 《Journal of polymer science. Part A, Polymer chemistry》2010,48(21):4842-4846
Dendritic 2‐ and 4‐arm PMMA‐based star polymers with furan‐protected maleimide at their focal point, (PMMA)2n‐MI and (PMMA)4n‐MI were efficiently clicked with the peripheral anthracene functionalized multiarm star polymer, (α‐anthryl functionalized‐polystyrene)m‐poly(divinyl benzene) ((α‐anthryl‐PS)m‐polyDVB) through the Diels–Alder reaction resulting in corresponding multiarm star block copolymers: (PMMA)2n‐(PS)m‐polyDVB and (PMMA)4n‐(PS)m‐polyDVB, respectively. Molecular weights (Mw,TDGPC), hydrodynamic radius (Rh), and intrinsic viscosity (η) of the multiarm star polymers were determined using three‐detection GPC (TD‐GPC). The high efficiency of this methodology to obtain such sterically demanding macromolecular constructs was deduced using 1H‐NMR and UV–vis spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
6.
Ji‐Hye Jung Aruna Kumar Mohanty Jihwa Ye Taeheon Lee Junyoung Ahn Yeong‐Gweon Lim Taihyun Chang Hyun‐Jong Paik 《Journal of polymer science. Part A, Polymer chemistry》2017,55(24):4020-4026
Covalent fixed multicyclic polystyrene conformers were synthesized from inconvertible polystyrene conformers based on p‐tert‐butylthiacalix[4]arene by azidation and subsequent click coupling. Selective 1D NOESY analyses confirmed that the spatial structures of star polystyrene precursors and multicyclic polystyrenes were preserved during the azidation and click coupling processes. The conformation of star polymers affected degree of decrease in the hydrodynamic volume after cyclization but had little effect on glass transition behavior. The rigid core of star polymer increased the Tg but in the case of multicyclic polymer, this influence of core structure was reduced. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 4020–4026 相似文献
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We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 105 ≤ Mw ≤ 3.0 × 106 Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (Mw ≥ 2.0 × 106 Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006 相似文献
8.
Maria A. Simonova Elvira V. Tarasova Marina M. Dudkina Andrey V. Tenkovtsev Alexander P. Filippov 《International Journal of Polymer Analysis and Characterization》2019,24(1):87-95
Properties of individual molecules of star-like polystyrene with calix[8]arene core in dilute chloroform solutions were studied using methods of static light scattering, translation diffusion, and viscometry. The solution behavior of the polymer investigated significantly differs from the properties of linear polymers. Star-like polystyrene macromolecules in solutions are characterized by compact structure—the hydrodynamic radius is not higher than 5.5?nm at M?=?125,000?g?mol?1. The shape of star-like polystyrene macromolecules differs slightly from spherical. 相似文献
9.
Nevin Binboga Duygu Kisakürek Bahattin M. Baysal 《Journal of Polymer Science.Polymer Physics》1985,23(5):925-931
The variation of refractive index increments with molecular weight has been studied using solutions of polystyrene (2.2 × 103 < Mw < 1.8 × 106), poly(ethylene glycol) (1.0 × 103 < Mw < 2.0 × 104), and poly(dichlorophenylene oxide) (3.3 × 103 < Mw < 4.8 × 105) in toluene and poly(propylene glycol) (1.2 × 103 < Mw < 4.0 × 103) in benzene. The refractive index increments of polyglycols containing aliphatic ether moieties are negative in these solvents. However, poly(dichlorophenylene oxide) polymers, which contain aromatic ether moieties, give positive values. Linear and branched halogenated poly(phenylene oxide)s show an asymptotic approach of the refractive index increment to the same limiting value, but the approach is more rapid for the branched polymer. 相似文献
10.
Jason A. Massey Kevin Kulbaba Mitchell A. Winnik Ian Manners 《Journal of Polymer Science.Polymer Physics》2000,38(23):3032-3041
A series of four well‐defined poly(ferrocenyldimethylsilane) (PFS) samples spanning a molecular weight range of approximately 10,000–100,000 g mol−1 was synthesized by the living anionic polymerization of dimethyl[1]silaferrocenophane initiated with n‐BuLi. The polymers possessed narrow polydispersities and were used to characterize the solution behavior of PFS in tetrahydrofuran (THF). The weight‐average molecular weights (Mw ) of the polymers were determined by low‐angle laser light scattering (LALLS), conventional gel permeation chromatography (GPC), and GPC equipped with a triple detector (refractive index, light scattering, and viscosity). The molecular weight calculated by conventional GPC, with polystyrene standards, underestimated the true value in comparison with LALLS and GPC with the triple detection system. The Mark–Houwink parameter a for PFS in THF was 0.62 (k = 2.5 × 10−4), which is indicative of fairly marginal polymer–solvent interactions. The scaling exponent between the radius of gyration and Mw was 0.54, also consistent with marginal polymer–solvent interactions for PFS in THF. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 3032–3041, 2000 相似文献
11.
Development of gel permeation chromatography for polymer characterization. II. Universal calibration
K. A. Boni F. A. Sliemers P. B. Stickney 《Journal of Polymer Science.Polymer Physics》1968,6(9):1579-1591
GPC appearance volumes have been determined for a series of linear polyethylene, polystyrene, and polybutadiene fractions (Mw/Mn < 1.1) in trichlorobenzene at 130°C. and for the latter two series in tetrahydrofuran at 23°C. A polymer-type independent relationship between appearance volumes and the equivalent hydrodynamic radii of the polymer molecules has been demonstrated. The equivalent hydrodynamic radius is calculated from intrinsic viscosity data. It is proposed that this relationship can be used to construct a universal GPC calibration curve for polymers that assume a spherical conformation in solution. Methods for applying the universal curve to the determination of molecular weight averages and molecular weight distribution are described. In addition, a method is outlined by which the universal calibration curve can be empolyed for determining number-average Mark-Houwink constants from polydisperse samples. 相似文献
12.
J. D. Stenger-Smith J. W. Fischer R. A. Henry J. M. Hoover M. P. Nadler R. A. Nissan G. A. Lindsay 《Journal of polymer science. Part A, Polymer chemistry》1991,29(11):1623-1631
Poly[(4-N-ethylene-N-ethylamino)-α-cyanocinnamate] was prepared by solution esterification of (4-N-ethyl-N-(2-hydroxyethyl) amino)-α-Cyanocinnamic acid and by melt transesterification of ethyl (4-N-ethyl-N-(2-hydroxyethyl) amino)-α-cyanocinnamate. The melt transesterification generally yielded polymer with a number-average molecular weight of about 10,200 by gel permeation chromatography (GPC) versus polystyrene standards. The polymer was found to be amorphous with a glass transition temperature of about 103°C by differential scanning calorimetry (DSC). The solution esterification generally gave a polymer with a number-average molecular weight of about 2200 by GPC versus polystyrene standards. This polymer was found to have a glass transition temperature varying between 60 and 90°C by DSC. The infrared (IR) spectrum of the polymer made from both methods were analyzed in detail. The 1H- and 13C-NMR spectra of the meltsynthesized ethyl cinnamate derivative polymer are consistent with the reported structure. 相似文献
13.
M. R. Ambler R. D. Mate J. R. Purdon 《Journal of polymer science. Part A, Polymer chemistry》1974,12(8):1759-1770
The technique for determining branching in polymers by using a combination of GPC and intrinsic viscosity data has been extended beyond current methods. Equations used in these analyses are presented. The derivations are based upon the assumption that branching is present only when there is a measurable reduction in the intrinsic viscosity. Techniques for calculating the functionality of the star branch point in starbranched polymers are given. Three random-branching parameters are calculated from a knowledge of the average branching density, \documentclass{article}\pagestyle{empty}\begin{document}$ \bar \lambda $\end{document}: (a) the lowest molecular weight branched polymer that can be measured, M?*; (b) the average molecular weight between branch points, M?bp; (c) the weight percentage of polymer that is branched. The applicability of this technique is demonstrated by using an analysis of published data on characterized fractions of a randomly branched polystyrene. 相似文献
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Yuri M. Boiko Anders Bach Jørgen Lyngaae-Jørgensen 《Journal of Polymer Science.Polymer Physics》2004,42(10):1861-1867
Films of amorphous polystyrene (PS) with a weight-average molecular weight (Mw) of 225 × 103 g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (th) and healing temperature (Th). G was found to develop with (th)1/2 at Th = Tg-bulk − 33 °C (where Tg-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/Th at Tg-bulk − 43 °C ≤ Th ≤ Tg-bulk − 23 °C. The smallest measured value of G = 1.4 J/m2 was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<Tg-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below Tg-bulk. Close values of G = 8–9 J/m2 were measured for the symmetric interfaces of polydisperse PS [Mw = 225 × 103, weight-average molecular weight/number-average molecular weight (Mw/Mn) = 3] and monodisperse PS (Mw = 200 × 103, Mw/Mn = 1.04) after healing at Th = Tg-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004 相似文献
15.
Sabrina Paillet Armelle Roncin Gérald Clisson Gaëlle Pembouong Laurent Billon Christophe Derail Maud Save 《Journal of polymer science. Part A, Polymer chemistry》2012,50(14):2967-2979
Branched and star‐branched polymers were successfully synthesized by the combination of two successive controlled radical polymerization methods. A series of linear and star poly(n‐butyl acrylate)‐co‐poly(2‐(2‐bromoisobutyryloxy) ethyl acrylate) statistical copolymers, P(nBA‐co‐BIEA)x, were first synthesized by nitroxide‐mediated polymerization (NMP at T > 100 °C). The subsequent polymerization of n‐butyl acrylate by single electron transfer‐living radical polymerization (SET‐LRP at T = 25 °C), initiated from the brominated sites of the P(nBA‐co‐BIEA)x copolymer, produced branched or star‐branched poly(n‐butyl acrylate) (PnBA). Both types of polymerizations (NMP and SET‐LRP) exhibited features of a controlled polymerization with linear evolutions of logarithmic conversion versus time and number‐average molar masses versus conversion for final Mn superior to 80,000 g mol?1. The branched and star‐branched architectures with high molar mass and low number of branches were fully characterized by size exclusion chromatography. The Mark–Houwink Sakurada relationship and the analysis of the contraction factor (g′ = ([η]branched/[η]linear)M) confirmed the elaboration of complex PnBA. The zero‐shear viscosities of the linear, star‐shaped, branched, and star‐branched polymers were compared. The modeling of the rheological properties confirmed the synthesis of the branched architectures. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
16.
Depolarization ratios ρ have been measured over ranges of temperature T and molecular weight M for polystyrene (PS) dissolved in cyclohexane (1002 cm?1 Raman band) and for poly(dimethyl siloxane) (PDMS) dissolved in benzene (2907 cm?1 Raman band). The ranges in the case of PS are 15 < T < 65°C and 2 × 103 < M < 4 × 105 and in the case of PDMS are ?3 < T < 60°C and M = 104. Measurements were also made of PDMS radii of gyration using conventional light scattering. The results are interpreted in terms of a theory connecting rotational isomeric populations with polymer extension. In the case of PDMS, an experimental value of the proportionality constant for trans isomers (D2 = ?3.9 ± 0.9) is deduced. This is closer to the theoretical value than previous estimates but there is still some discrepancy. In the case of PS the isomeric changes resulting from extension are independent of M for M > 104. Deviations are observed for lower M. 相似文献
17.
Kalpana Viswanathan Timothy E. Long Thomas C. Ward 《Journal of polymer science. Part A, Polymer chemistry》2005,43(16):3655-3666
The synthesis of trimethoxysilane end‐capped linear polystyrene (PS) and star‐branched PS and subsequent silicon (Si) surface modification with linear and star polymers are described. Trimethoxysilane terminated PS was synthesized using sec‐butyl lithium initiated anionic polymerization of styrene and subsequent end‐capping of the living anions with p‐chloromethylphenyl trimethoxysilane (CMPTMS). 1H and 29Si NMR spectroscopy confirmed the successful end‐capping of polystyryllithium with the trimethoxysilane functional group. The effect of a molar excess of end‐capper on the efficiency of functionalization was also investigated, and the required excess increased for higher molar mass oligomers. Acid catalyzed hydrolysis and condensation of the trimethoxysilane end‐groups resulted in star‐branched PS, and NMR spectroscopy and SEC analysis were used to characterize the star polymers. This is the first report of core‐functionalized star‐shaped polymers as surface modifiers and the first comparative study showing differences in surface topography between star and linear polymer modified surfaces. Surface‐sensitive techniques such as ellipsometry, contact angle goniometry, and AFM were used to confirm the attachment of star PS, as well as to compare the characteristics of the star and linear PS modified Si surfaces. The polymer film properties were referenced to polymer dimensions in dilute solution, which revealed that linear PS chains were in the intermediate brush regime and the star‐branched PS produced a surface with covalently attached chains in the mushroom regime. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3655–3666, 2005 相似文献
18.
Two kinds of fishbone-like, β-diketone-based liquid crystalline polysilsesquioxanes(FBDKLCP'S), homopolymeric (H-FBDKLCP) and copolymeric (C-FBDKaLCP) have been first synthesized via the hydrosilylation reaction of a vinyl-terminated β-diketone with the homopolymeric ladderlike polyhydrosilsesquioxane (LPHSQ) and random copolymethylhydrosilsesquioxane (LRPMHSQ) respectively. These new kinds of FBDKLCP with M of 10~4 is thermotroic liquid crystalline polymer and its clearing temperatures T_i's and mesophase range △T's are much higher than those of the corresponding comb-like β-diketone liquid crystalline polysiloxane (DKLCP) by about 200℃. Similar results have been observed with the comparison of the two different structure Cu-coordinating compounds The significant increases in T_((?))'s and △T's of the FBDKLCP and Cu-FBDKLCP are mainly attributed to the great rigidity of the ladderlike polysilsesquioxane backbone. 相似文献
19.
Diffusion of Nanoparticles in Semidilute Polymer Solutions: A Multiparticle Collision Dynamics Study 下载免费PDF全文
The diffusion of nanoparticles immersed in semidilute polymer solutions is investigated by a hybrid mesoscopic multiparticle collision dynamics method. Effects of polymer concentration and hydrodynamic interactions among polymer monomers are focused. Extensive simulations show that the dependence of diffusion coefficient D on the polymer concentration c agrees with Phillies equation D-exp (-αcδ) with a scaling exponent δ≈0.97 which coincides with the experimental one in literature. For increasing nanoparticle size, the scaling prefactor α increases monotonically while the scaling exponent always keeps fixed. Moreover, we also study the diffusion of nanoparticle without hydrodynamic interactions and find that mobility of the nanoparticle slows down, and the scaling exponent is obviously different from the one in experiments, implying that hydrodynamic interactions play a crucial role in the diffusion of a nanoparticle in semidilute polymer solutions. 相似文献
20.
Francesco Babudri Stefania R. Cicco Gianluca M. Farinola Francesco Naso Alberto Bolognesi William Porzio 《Macromolecular rapid communications》1996,17(12):905-911
Soluble poly(2,5-dialkoxy-1,4-phenylenevinylene) has been prepared via Stille coupling reaction between 2,5-dialkoxy-1,4-diiodobenzene and E-1,2-bis(tributylstannyl)-ethene in the presence of palladium complexes. Characterization of this material by means of 1H and 13C nuclear magnetic resonance (NMR), ultraviolet/visible (UV/VIS) and infrared (IR) spectra is described. Molecular weights, determined by means of gelpermeation chromatography (GPC) analysis and referred to standard polystyrene, were in the range number-average molecular weights M n = 2061–2544 and weight-average molecular weights M w = 3347–3878. X-ray diffraction (XRD) analysis of the polymer showed semicrystalline structure. Tg = 57°C, transition to a stable smectic mesophase at 115°C and clearing point at 210°C were revealed by differential scanning calorimetry analysis, optical microscopy observation and XRD of the annealed polymer. 相似文献