Molecular characterization of a hyperbranched polyester. II. Small‐angle neutron scattering

A series of fractions of a hyperbranched polyester in deutero tetrahydrofuran solution were investigated by small‐angle neutron scattering. Concentrations of polymer from 2 to 5% w/v were used, and the molecular parameters were obtained from Zimm plots of the data. Second virial coefficients were positive, and these values were confirmed by dilute‐solution light scattering on a small number of fractions with deutero tetrahydrofuran as a solvent. The small‐angle neutron scattering data exhibited the general features predicted for the particle scattering functions of nonrandomly branched polymers, but an exact fit of the theoretical equation to the data could not be obtained for all fractions of the hyperbranched polymer, particularly those of high molecular weight. Excluded volume effects were cited as a possible cause for this disagreement. A fractal dimension of ～2.5 was obtained from the scattering vector dependence of the differential scattering cross section of the polymer in deutero tetrahydrofuran solution, which agreed with the scaling exponent for the dependence of the radius of gyration on weight‐average molecular weight. Hydrogenous tetrahydrofuran solutions of the hyperbranched polymer exhibited negative second virial coefficients that were attributed to isotopic influences on the thermodynamic properties of the polymer–solvent combination. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1352–1361, 2003     

Dilute solution properties of asymmetric six-arm star polystyrenes

Six-arm star polystyrenes having varying numbers of short and long arms attached to the same molecule have been synthesized by anionic polymerization. The molecules have been characterized by high resolution size exclusion chromatography using multiangle light scattering and viscosity detectors. This technique has allowed the radii of gyration and intrinsic viscosities to be measured for stars with each possible combination of arms. The branching parameters g and g′ are computed and compared with theoretical expectations. It is found that short arms add preferentially to the stars, because of reduced steric effects. The molecule with one long and five short arms exhibits behavior closest to that of a linear chain (largest branching ratios). The effect of arm polydispersity on solution properties of stars is discussed. © 1995 John Wiley & Sons, Inc.     

Dilute solution properties,chain stiffness,and liquid crystalline properties of cellulose propionate

The solution properties of cellulose derivatives are of interest from both technological and purely scientific aspects. At high concentrations these solutions form liquid crystalline structures. In dilute solution cellulosic chains can be described as semiflexible or wormlike with properties intermediate between random coils and rigid rods. A series of fractions of cellulose propionate have been examined by dilute solution viscometry, static and dynamic light scattering, and polarizing microscopy. Power law exponents are considerably larger than those observed for flexible chains and analysis of the intrinsic viscosity and hydrodynamic radii has yielded chain diameters and Kuhn statistical segment lengths. Corresponding aspect ratios from the hydrodynamic measurements are in good agreement with those obtained from polarizing microscopy, as analyzed in light of Flory's theory. Some aggregation and specific solvent effects have been observed, however separation of these effects has proven to be difficult. Results of these studies are compared to previous work for other cellulose derivatives. ©1995 John Wiley & Sons, Inc.     

Dilute solution characterization of a POLA polyester

Samples of poly(4,4′-isopropylidenediphenylene 1,1,3-trimethyl-3-phenylindan-4′,5- dicarboxylate) were fractionated by the column-elution, temperature-gradient technique. Selected fractions, covering a 10-fold range of molecular weight, were shown to have narrow molecular weight distributions by gel-permeation chromatography (GPC), i.e., M?_w/M?_n = 1.15 ± 0.10. The fractions were further characterized by viscometry, light scattering, and membrane osmometry. Characterization of the small samples (ca. 0.3 g) was facilitated by use of a low-volume light scattering cell. This allows measurements of refractive increment, light scattering, and viscosity to be performed on as little as 50 mg of sample. Molecular weights estimated by the GPC-viscometry technique were in good agreement with the values obtained by light scattering. Estimates of the perturbed coil dimensions (150–200 Å) were in satisfactory agreement with those observed experimentally. The polydispersities of the fractions, determined by osmometry and light scattering, were in fair agreement with GPC data; the latter are considered subject to less experimental uncertainty.     

Synthesis,characterization, and optoelectronic properties of hyperbranched polyfluorenes containing pendant benzylether dendrons

Linear polyfluorenes with low generation of side benzylether dendrons ( PLG0 , PLG1 ) and hyperbranched polyfluorenes with 1,3,5‐benzene branch unit ( PHG0 and PHG1 ) were prepared by the Suzuki coupling reaction to investigate the structural effect on optoelectronic properties. Their optical properties, both in solution and film state, were investigated using absorption and photoluminescence (PL) spectra. The excimer emission of polyfluorene at about 530 nm, induced by thermal annealing, was completely suppressed by the hyperbranched structure, but the suppression was not obvious by the side benzylether dendrons. The optoelectronic performance of the EL devices (ITO/PEDOT:PSS/polymer/Ca/Al) was strongly dependent upon chemical structures of the emitting polyfluorenes. The hyperbranched PHG0 with zero generation of benzylether side groups revealed the best device performance, with maximal luminance and maximal luminance efficiency of 2350 cd/m² and 0.33 cd/A, respectively. The results suggest that incorporation of branch units with low generation of benzylether dendrons is an effective way to improve annealing stability and EL performance of the polyfluorenes. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5945–5958, 2008     

Hydrophobically modified polyelectrolytes I. Dilute solution properties of fluorocarbon-containing poly (acrylic acid)

Dilute solution viscosity of fluorocarbon‐containing hydrophobically modified poly (acrylic add) was measured in aqueous solutions of various NaCl concentrations. The intrinsic viscosity ([η]) and Huggins coefficient (k_H) were evaluated using Huggins equations. It is found that, at low Nacl concentration, the modified polymers exhibit values of intrinsic viscosity ([η]) and Huggins coefficient (k_H) similar to those of unmodified polymers. For both of the modified and unmodified polymers, the intrinsic viscosity decreases with increase of NaCl concentration, while the Huggins coefficient increases upon addition of NaCl. But the variation of [η] and k_H is more significant for the modified polymers, which reflects the enhanced intra‐ and intermolecular hydrophobic association at higher Nacl concentration.     

Dilute solution properties of a polyurethane. I. Linear polymers

A linear polyurethane of high molecular weight was prepared in solution by the polyaddition of equimolar amounts of ethylene glycol and methylene bis(4-phenyl isocyanate). The polymer was fractionated by using a direct sequential extraction procedure, with a solvent–nonsolvent system consisting of N,N′-dimethylformamide (DMF) and acetone (A). The resulting fractions were characterized by viscosity and lightscattering measurements. The relationship between the intrinsic viscosity and molecular weight was found in DMF at 25°C. to be [η] = 3.64 × 10^?4M^0.71. The unperturbed polymer chain dimensions were determined from intrinsic viscosity measurements carried out under experimentally determined theta conditions.     

Surface properties and swelling behaviour of hyperbranched polyester films in aqueous media

Thin films of hydroxyl (POH) and carboxyl (PCOOH) terminated aromatic hyperbranched polyesters (HBPs) were prepared by spin coating on silicon wafers and subsequently annealed above their glass transition temperature (T_g). The surface properties and the swelling behaviour of these films in aqueous buffer solutions were studied as a function of annealing time using contact angle measurements and ellipsometry. Non-annealed films were hydrophilic with surface free energies of 51 mJ/m² for POH and 49 mJ/m² for PCOOH, respectively. The swelling behaviour of the polymer films in buffer solution with pH 7.4 was described in terms of changes of the thickness and effective refractive index of the swollen layer. Under identical conditions a lower water uptake was found for hydroxyl terminated HBPs (POH) which were annealed more then 2 h. The lower water uptake correlates with the surface properties of the films. The annealed films were less hydrophilic. Their surface free energy was 38 mJ/m² independent of the annealing. Films of carboxyl terminated HBPs (PCOOH) showed similar surface properties after annealing. However, these films were unstable under the same conditions in aqueous solutions. Stable PCOOH films were obtained by additional covalent binding to the substrate using an epoxy silane as a coupling agent.     

Hydrodynamic Properties of “Pseudo-Dendrimer”

Summary: Hyperbranched polycarbosilane with terminal butyl groups is obtained by chemical modification of hyperbranched polyallylcarbosilane using the reaction of hydrosilylation with methyldichlorosilane, followed by treatment of the polychlorosilyl derivative with butyllithium. Its hydrodynamic and conformational properties are studied by the methods of light scattering, sedimentation-diffusion analysis, and viscosimetry in dilute solutions of methyl-tert-butyl ether, hexane, THF, chloroform, and toluene. The results obtained are compared with the data for the initial polyallylcarbosilane and carbosilane dendrimer with butyl terminal groups. It is demonstrated that branching regularity is the decisive factor determining the solution properties at fixed degree of the branching.     

Encapsulation and controlled release of a hydrophobic drug using a novel nanoparticle-forming hyperbranched polyester

An amphiphilic, hyperbranched polymer suitable for use in controlled drug delivery is reported. This polymer was obtained by modification of the hyperbranched aliphatic polyester Boltorn H20 (H20) with succinic anhydride and then glycidyl methacrylate, and formed nanoparticles in aqueous solution. The critical association concentration was 7.4 x 10(-3) g . L(-1), as determined by fluorescence spectroscopy using pyrene as a molecular probe. A static/dynamic laser light scattering (LLS) study revealed that the average particle size was 39.4 nm with a low particle size distribution (PDI=0.04), and that each particle was composed of about 350 amphiphilic molecules. Daidzein, a hydrophobic traditional Chinese medicine, was encapsulated during particle formation and the release properties were determined. The optimal feeding concentration of daidzein to hyperbranched polyester was 4.9 x 10(-5) g . mL(-1) to 5.0 x 10(-3) g . mL(-1) with a loading efficiency of 76.1%. In the presence of the enzyme Lipase PS, the drug loaded nanoparticles degraded in a random one-by-one manner and released the drug over a few days. This system is therefore a novel controlled drug release system based on nanoparticles formed of hyperbranched polyester. Encapsulation of daidzein by hyperbranched polyester particles.     

Viscoelastic properties of dilute nematic mixtures containing cyclic and hyperbranched liquid crystal polymers dissolved in a nematic solvent

The twist and bend viscosities of dilute solutions of cyclic and hyperbranched liquid crystal polymers (LCP) dissolved in low molar mass nematic solvents were determined via dynamic light scattering analysis. These results were compared to those of linear chains with similar chemical repeat structures. The nematic solvent used was 4′-pentyloxy-4-cyanobiphenyl (50CB). The cyclic LCP oligomers, Cy TPB10, have a mesogenic group, 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl) butane, separated by flexible decamethylene spacers. The twist viscosity of the cyclic Cy-TPB10 oligomers increases with molecular weight more strongly than the linear, TPB-10, suggesting that the hydrodynamic behavior of Cy-TPB10 is closer to that of a rigid rod than TPB10. Surprisingly, the intrinsic bend viscosity [η_bend] of Cy-TPB10 decreases with molecular weight, in contrast to the positive dependence for linear TPB10. This may reflect the higher strain energy in the smaller ring sizes. The hyperbranched LCP, TPD-b-8, is also based on the mesogen 10-bromo-1-(4-hydroxy-4′-biphenyl)-2(4-hydroxyphenyl) decane but with octyl groups at the chain ends. We compare the viscoelastic behavior of dilute nematic solutions of TPD-b-8 in 50CB against that of a linear main-chain LCP, TPB7, with the same mesogenic group but with heptamethylene spacers. The viscometric properties of TPD-b-8/50CB and TPB7/50CB are quite different. The results suggest that each chain is prolate (i. e., R_∥ > R_⊥) but that TPD-b-8 has a smaller chain anisotropy than that of TPB7. © 1995 John Wiley & Sons, Inc.     

Physicochemical Characterization of Two Polysulfon-Amides in Dilute Solution

Summary: As one class of high temperature resistant aromatic polymers, polysulfonamides (PSA) are widely used in industry, physicochemical properties and conformation in solution have not been disclosed yet. In this work, the dilute solution behaviour of poly(m-diphenylsulphone terephthal amide) (m-PSA) was investigated by laser light scattering (LLS) and viscometry. The results showed that the m-PSA exists as single chains both in dimethylsulfoxide (DMSO) and dimethylformamide (DMF). The value of radius of gyration to hydrodynamic radius (s/R_h) indicats that the m-PSA has a random coil conformation in solution. Both the persistence length a and the characteristic ratio C_∞ indicate that the m-PSA chain is flexible in solution. The Mark-Houwink equation of m-PSA in DMSO was determined as [η] = 1.62 × 10⁻⁵M, and the exponent of 0.87 supports the assumption that m-PSA forms random coils in DMSO-solution at 25 °C. It was found that the flexibility of the PSA was affected when 4,4'-diphenylsulphone terephthalamide monomer was incorporated in backbone. The PSA random copolymer (r-PSA) with a comonomer ratio of 3:1 (4,4′-diaminodiphenyl- sulfone to 3,3′-diaminodiphenylsulfone) also had a random coil conformation in DMF; the rigidity increased, while the mobility of the chain was maintained.     

Dilute solution properties of epoxy resins

Number-average molecular weights of fractions of epoxy resins were estimated by vapor-pressure osmometry and size exclusion chromatography coupled with multiple-angle light scattering. Potential reasons for differences between the two sets of data are examined. The molecular weight dependences of the intrinsic viscosity in tetrahydrofuran and chloroform are discussed in terms of theories which take into account the low-molecular weight character of poly(hydroxy ether) chains. The polymer-solvent interaction parameter is estimated. The impact of the presence of branched chains on the results of size exclusion chromatography is examined. It is shown that the universal calibration of size exclusion chromatographic columns by polystyrene is reliable at molecular weights above 2000 only.     

Behavior of cellulose in NaOH/Urea aqueous solution characterized by light scattering and viscometry

Cellulose was dissolved in 6 wt % NaOH/4 wt % urea aqueous solution, which was proven by a ¹³C NMR spectrum to be a direct solvent of cellulose rather than a derivative aqueous solution system. Dilute solution behavior of cellulose in a NaOH/urea aqueous solution system was examined by laser light scattering and viscometry. The Mark–Houwink equation for cellulose in 6 wt % NaOH/4 wt % urea aqueous solution at 25 °C was [η] = 2.45 × 10^?2 weight‐average molecular weight (M_w)^0.815 (mL g^?1) in the M_w region from 3.2 × 10⁴ to 12.9 × 10⁴. The persistence length (q), molar mass per unit contour length (M_L), and characteristic ratio (C_∞) of cellulose in the dilute solution were 6.0 nm, 350 nm^?1, and 20.9, respectively, which agreed with the Yamakawa–Fujii theory of the wormlike chain. The results indicated that the cellulose molecules exist as semiflexible chains in the aqueous solution and were more extended than in cadoxen. This work provided a novel, simple, and nonpollution solvent system that can be used to investigate the dilute solution properties and molecular weight of cellulose. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 347–353, 2004     

Association,emulsifying, and solubilization properties of amphiphilic hyperbranched poly(acrylic acid) with short polystyrene stickers

Amphiphilic hyperbranched copolymer chains made of large hyperbranched poly(acrylic acid) cores grafted with short polystyrene stickers (HB‐PAA_n‐g‐PS_{n + 1}) with different n values (n = 1, 10, 47) were well prepared and confirmed by size exclusion chromatography, Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. The study on the interchain association behavior of these amphiphilic chains indicates that larger HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymer chains have a less tendency to undergo interchain association. Moreover, the simple vial‐inversion and rheological experiments show that the apparent critical gel concentration (C_g) decreases with n, but no sol–gel transition was observed for triblock PS‐PAA‐PS even when the concentration is up to 200 g L^?1. Further transmission electron microscopy study of the latex particles prepared with HB‐(PAA)_n‐g‐(PS)_{n + 1} as surfactant reveals that the latex particles are spherical and narrowly dispersed; while the measured latex particle number (N_p) indicates the surfactant efficiency of HB‐(PAA)₄₇‐g‐(PS)₄₈ is poorer than that of triblock PS‐PAA‐PS (n = 1). Finally, pyrene solubilization measurement shows the solubilization efficiency of HB‐(PAA)_n‐g‐(PS)_{n + 1} copolymers decreases with n, consistent with the previous observed interchain association result. The present study demonstrates that both the chain topology and the styrene weight fraction dominates the final solution properties of amphiphilic HB‐(PAA)_n‐g‐(PS)_{n + 1} chains in aqueous solution. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 128–138     

超支化分子桥联受阻酚抗氧化剂的合成与表征

以正十八胺为核的1.0代超支化大分子和β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为原料,通过酰胺化缩合反应,合成了一种具有长链烷基和2个受阻酚基团的新型超支化分子桥联受阻酚类抗氧化剂.通过正交实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成体系为:3,5-丙酰氯为酰化剂、K_2CO_3为缚酸剂、苯和水为反应溶剂.通过条件优化实验确定了超支化分子桥联受阻酚类抗氧化剂的最佳合成条件为:3,5-丙酰氯与1.0代超支化大分子的物质的量比为6∶1、反应温度为25 ℃、反应时间为12 h、体系苯与水体积比为6∶1、3,5-丙酰氯与缚酸剂K_2CO_3的物质的量比为1∶1,在此条件下,超支化分子桥联受阻酚类抗氧化剂的收率高达75.5%.FT-IR和1H NMR证实了合成抗氧化剂的化学结构与其理论结构相符.超支化分子桥联受阻酚类抗氧化剂在聚乙烯树脂中的抗氧化性能优于抗氧化剂1076,且随着烷基链长度的增加,抗氧化性能增强.     

Molecular chain properties of poly (N-isopropyl acrylamide)

A series of poly( N-isopropyl acrylamide) (PNIPAM) samples with molecular weight ranging from 2.23×10~4 to 130×10~4 and molecular weight distribution M_w/M_n≤1.28 were obtained by free radical polymerization and repeat precipitation fractionation. The molecular weight M_w, second virial coefficient A_2 as well as the mean-square-root radius of gyration 〈S~2〉 for PNIPAM samples in tetrahydrofuran (THF) were determined by light scattering, and the relations were estimated at A_2 ∞ M_w~0.25) and 〈S~2〉~(1/2)=1.56×10~(-9) M_w~(0.56). The intrinsic viscosity for THF solution and methanol solution of PNIPAM samples was measured and the Mark-Houwink equations were obtained as [η]=6.90×10~(-5) M~(0/73) (THF solution) and [η]=1.07×10~(-4) M~(0.71) (methanol solution). The above results indicate that both THF and methanol are good solvents for PNIPAM. The limit characteristic ratio C_∞ for PNIPAM in the two solutions was determined to be 10.6 by using Kurata-Stockmayer equation, indicating that the f     

Dilute solution properties of a polybenzimidazole

Light scattering and viscometric studies have been carried out on dilute solutions of a polybenzimidazole in N,N-dimethylacetamide. The data, which span the molecular weight range 2.9 ≦ 10^?4M_w ≦ 23.3, and the temperature range 290 ≦ T/K ≦343, yield the dependence of the mean-square radius of gyration 〈s²〉_LS, the second virial coefficient A₂, and the intrinsic viscosity [η] on molecular weight M_w and temperature. The unperturbed mean-square radius 〈s〉_LS was calculated using experimental values of 〈s²〉_LS and A₂. It was found that excluded volume effects on 〈s²〉_LS are very small. The unperturbed hydrodynamic chain dimension 〈s〉_η was estimated by considering draining effects. A small value of the draining parameter was obtained. Analysis of the temperature dependence of A₂ and [eta;] leads to the conclusion that this system approaches a lower theta temperature with increasing temperature. The steric factor σ = 〈s〉/〈s〉f, based on the value of 〈s〉_f calculated for the polymer chain with free rotation, is nearly unity. Most of these properties can be interpreted in terms of long rotational units within the main chain.     

超支化聚芴的合成与性能研究

采用2,7-二(4-羟基苯基)-9,9-二烷基芴(A2)与四对甲基苯磺酸季戊四醇酯(B4)通过A2+B4型缩聚反应合成了一系列共轭型超支化聚合物.利用紫外和荧光谱对聚合物予以表征,结果表明,此类聚合物均可发出稳定、纯正的蓝光.DSC和TGA显示,4种聚合物在150℃以下没有明显的相态变化,300℃以内无明显的热分解现象,这表明此类聚合物具有良好的热稳定性,有利于材料的发光效率及发光稳定性.