Water‐soluble acrylamide copolymers. IX. Preparation and characterization of the cationic derivatives of poly(acrylamide‐co‐n,n‐dimethylacrylamide), poly(acrylamide‐co‐methacrylamide), and poly(acrylamide‐co‐n‐t‐butylacrylamide)

This article extends the preparative details of a series of nonionic copolymers of acrylamide with N,N‐dimethylacrylamide, methacrylamide, and N‐t‐butylacrylamide to the synthesis of cationic derivatives of these new copolymers. The described procedures gave products with cationicities of 14–26 mol %. We measured the mean squared radii of gyration and intrinsic viscosities of aqueous solutions of these products at several different pHs and NaCl concentrations to compare these values with those determined for the nonionic precursors and related commercial cationic polymers. Because the molecular weights of the examples measured varied widely, it was difficult to establish definite trends. However, the large values obtained for the mean squared radii of gyration and intrinsic viscosities, relative to the nonionic precursors of these polymers, demonstrated that the charged groups had a qualitatively greater effect on polymer extension than the nonpolar bulky groups. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2525–2535, 2001     

Polymers from 1,3-dipole addition reactions. The nitrilimine dipole from tetrazoles

Polymers containing pyrazole and triazole units in the polymer chain were obtained through the 1,3-dipolar addition reaction of bisnitrilimines generated from tetrazoles with diynes and dinitrile dipolarophiles. The reaction of 2,2′-diphenyl-5,5′-m- and p-phenyleneditetrazole with the dipolarophiles m- and p-diethynylbenzene, terephthalonitrile, tetrafluoroterephthalonitrile, perfluoroglutarylnitrile, and 4,4′-dicyanobiphenyl gave a series of thermally stable polymers of high molecular weight. The polypyrazoles were soluble in acid and in some cases in chlorobenzene or 1,2,4-trichlorobenzene and had intrinsic viscosities as high as 1.67, while the polytriazoles were soluble in 1,2,4-trichlorobenzene and chlorobenzene, but not in acid, and had viscosities ranging up to 0.40. The thermogravimetric analyses of the finely powdered polymers showed breaks near 500°C in air and nitrogen atmospheres.     

Solvodynamic Properties of Sodium Polystyrenesulfo-nate in Methanol-Water Mixed Solvent Media in Absence and in the Presence of a Salt Using Viscometric Method

Linear extrapolation of the reduced viscosity values of uncharged polymer solutions as the concentration approaches zero constitutes the basis for the traditional method for the determination of the intrinsic viscosities of polymer solutions. While this method works well for uncharged polymer solutions, it fails completely for polyelectrolyte solutions especially in absence and also in presence of small amount of an added electrolyte. A very convenient method has recently been proposed by Wolf (Wolf, Macromol. Rapid Commun. 2007, 28, 164) to determine the intrinsic viscosities of polyelectrolyte solutions on the basis of the laws of phenomenological thermodynamics applied to the viscosity of polymer solutions. In spite of the success and the convenience of this method, this has so far been applied to a limited number of polyelectrolyte systems by the Wolf group alone (Wolf, Macromol. Rapid Commun. 2007, 28, 164; Eckelt et al., Macromolecules 2008, 41, 912; Badiger et al., Macromol. Chem. Phys. 2008 , 209, 2087; Ghimici et al., J. Phys. Chem.B. 2009, 113, 8020). In order to improve the situation, we have measured the viscosities of an anionic polyelectrolyte, sodium polystyrenesulfonate, in methanol-water mixed solvent media both in absence and in the presence of an electrolyte, sodium chloride. The results show that the experimental data fit well with the Wolf model and thus allow the calculation of intrinsic viscosities, which provide important insight about the dependence of the polyion conformation on solvent composition as well as on the concentration of the added electrolyte. This new evaluation method, thus, proves to be very useful to a better understanding of the rheological behaviour of the polyelectrolyte system investigated.     

Concentration Effects in Sec for Polymer/Polymer/Solvent Systems

Abstract

A model quantitatively describing the experimental shifts in elution volumes of polymeric solute A in the presence of another polymer B is developed. The concentration-dependent shrinkage of A coils has been evaluated from the intrinsic viscosity displayed by polymer A in the ternary solution formed by itself at c_A concentration + polymer B at c_B concentration + solvent. Resulting concentration effects depend on both polymer concentrations (c_A and c_B), on the intrinsic viscosities of both polymers in the solvent (|η|A and |η|B), on the Huggins' coefficients k_A and k_B, and on the quadratic concentration coefficients in the polynomial expansion of ηsp/c, namely k^′ _A and k^′ _B. Predicted elution volumes are compared with experimental ones for two different types of literature systems: those studying polymer A elution at diverse c_A concentrations in eluents consisting of mixtures of polymer B + solvent and those in which polymer A + polymer B mixtures are injected at once in the pure solvent used as eluent. In order to eliminate experimental uncertainties about k_i and k^′ _i (i=A, B) values, applied k^′ _i values were those obtained from the empirical correlation k^′ _i + 0.122 = k_i ² whereas k_i ones were obtained from Imai's equation.     

Synthesis and properties of polyimides from 4,4′-binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride

4,4′-Binaphthyl-1,1′,8,8′-tetracarboxylic dianhydride was synthesized from 4-chloro-1,8-naphthalic anhydride and polymerized with aromatic and pliphatic diamines in m-cresol or N-methyl-2-pyrrolidinone (NMP). The polyimides, except for two derived from p-phenylenediamine and hydrazine, are soluble in 1,1,2,2-tetrachloroethane and NMP. Their intrinsic viscosities ranged from 0.36 to 2.20 dL/g. The polymers showed excellent thermal and thermooxidative stabilities and displayed weak glass transition temperatures. Young's moduli of some polymer films were in the range of 2.5 and 5.4 GPa at 30°C. The aliphatic polyimides exhibited a stronger fluorescence than the aromatic polyimides. © 1995 John Wiley & Sons, Inc.     

Phase Behavior of Polymer Blends

The present report deals with some results on phase behavior, miscibility and phase separation for several polymer blends casting from solutions. These blends are grouped as the amorphous polymer blends, blends containing a crystalline polymer or two crystalline polymers. The blends of PMMA/PVAc were miscible and underwent phase separation at elevated temperature, exhibited LCST behavior. The benzoylated PPO has both UCST and LCST nature. For the systems composed of crystalline polymer poly(ethylene oxide) and amorphous polyurethane, of two crystalline polymers poly(-caprolactone) and poly[3,3,-bis-(chloromethyl) oxetane], appear a single T_g, indicating these blends are miscible. The interaction parameter B's were determined to be –14 J cm^–3, –15 J cm^–3 respectively. Phase separation of phenolphthalein poly(ether ether sulfone)/PEO blends were discussed in terms of thermal properties, such as their melting and crystallization behavior.This revised version was published online in November 2005 with corrections to the Cover Date.     

Application of the flory-mandelkern equation to individual unfractionated polymer samples

A method is developed for the application of the Flory-Mandelkern equation to the determination of the weight-average molecular weights of individual, broad, unfractionated polymer samples. The method includes appropriate averaging of the sedimentation constants and of the intrinsic viscosity of an unfractionated polymer sample in a θ solution from the velocity sedimentation data. By means of the method, individual samples of polystyrene, poly(isooctyl methacrylate) and of the copolymer of styrene with 20% isooctyl methacrylate prepared under the same emulsion polymerization conditions from commercial monomers have been investigated. Appropriate θ solvents have been found by the Elias method. Equations for the dependence of the sedimentation constants and of the intrinsic viscosities in the θ solvents on the molecular weights have been established for the polymers without fractionation. Osmometric and light-scattering measurements as well as Archibald experiments have shown that by the proposed method the molecular weight cut-off effect is eliminated in the above equations and in the polydispersity parameter M _w/M _n. Molecular weight distributions have been determined for the polymer samples.     

Complete miscibility of ternary aryl polyesters demonstrating a new criterion and horizon for miscibility characterization

A ternary miscible blend system comprising only crystallizable aryl polyesters [poly(ethylene terephthalate), poly(trimethylene terephthalate), and poly(butylene terephthalate)] was characterized with the criteria of thermal analyses, microscopy, and X‐ray characterizations. The reported ternary miscibility (in the quenched amorphous state of blends of the three aryl polyesters) was truly physical and under the condition of no chemical transesterifications; this justified that transesterification was not a necessary condition for miscibility in polyester blends in this case. This study further proposed and tested a novel concept of a new criterion for miscibility characterization for polymer blends of only crystallizable polymers. A single composition‐dependent cold‐crystallization‐temperature (T_cc) peak in blends of only semicrystalline polymers was taken as an indication of an intimate mixing state of miscibility. The theoretical background for establishing the single composition‐dependent T_cc peak as a valid miscibility criterion for crystallizable polymer blends was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2394–2404, 2003     

Miscible blends of amorphous polymers

Thirty-five polymethacrylate/chlorinated polymer blends were investigated by differential scanning calorimetry. Poly(ethyl), poly(n-propyl), poly(n-butyl), and poly(n-amyl methacrylate)s were found to be miscible with poly(vinyl chloride) (PVC), chlorinated PVC, and Saran, but immiscible with a chlorinated polyethylene containing 48% chlorine. Poly(methyl) (PMMA), poly(n-hexyl) (PHMA), and poly(n-lauryl methacrylate)s were found to be immiscible with the same chlorinated polymers, except the PMMA/PVC, PMMA/Saran, and PHMA/Saran blends, which were miscible. A high chlorine content of the chlorinated polymer and an optimum CH₂/COO ratio of the polymethacrylate are required to obtain miscibility. However, poly(methyl), poly(ethyl), poly(n-butyl), and poly(n-octadecyl acrylate)s were found to be immiscible with the same chlorinated polymers, except with Saran, indicating a much greater miscibility of the polymethacrylates with the chlorinated polymers as compared with the polyacrylates.     

Synthesis and properties of conjugated enyne polysulfones

High-molecular-weight polysulfones that contained 1,3-enyne linkages in the polymer backbone were prepared by the reaction of potassium salts of (E)-1,3-bis(3-hydroxyphenyl)-1-buten-3-yne and 4,4′-dihydroxybiphenyl with 4,4′-dihalodiphenylsulfones in DMSO-sulfolane solvent mixtures. The polymers were soluble in methylene chloride and exhibited intrinsic viscosities as high as 0.74 (in DMAC at 30°C) with glass transition temperatures ranging from 179 to 214°C. It was postulated that on heating the polymers would cure via a intramolecular cycloaddition reaction to from a 2-phenylnaphthalene fused ring system along the polymer backbone. Thermal analytical data studies on cured polymer films and investigations of the products obtained from the thermal reactions of model compounds indicated that the primary curing reaction was intermolecular rather than intramolecular in nature. Additional data from testing fabricated composites indicated that the enyne polysulfones have suitable properties for use as high-temperature thermoplastic composite materials.     

Associative Organotin Polymers. 2. Solution Properties of Symmetric Trialkyltin Fluorides

The solubilities and viscosities of four novel symmetric tri-n-alkyltin fluorides in various organic solvents were studied. It is shown that these compounds do behave as transient polymers. Increasing the length of the n-alkyl chain beyond n-butyl imparts considerable solubility to this class of associative polymers and offers no steric hindrance to polymer chain formation. The effects of concentration, solvent type, temperature, and brine on the solution viscosities were also studied. These associative polymers effectively viscosify compressed gases (having liquid-like densities), such as propane and n-butane. They can therefore be used in enhanced oil recovery operations as well as in fracturing of oil wells.     

Introduction of a Reliable Method for Determination ofIntrinsic Viscosity for Any Polymer with High Precision简

Intrinsic viscosities for a given polyelectrolyte in salt free and low-salt solvents reported in literatures are normally not comparable, because of inadequate valuation procedures. This article describes a theoretically justified reliable method, which is free of any model assumptions： The so called Wolf plot （logarithm of the relative viscosity as a function of polymer concentration） enables the unequivocal determination of intrinsic viscosities for all kinds of macromolecules, irrespective of whether they are chain molecules of different architecture or globular polymers, whether they are charged or uncharged. The validation of the method was examined by evaluation of the viscosities of a polyelectrolyte, some uncharged polymers of different architectures, uncharged polymer blends, and some literature data.     

Synthesis of polyphenylquinoxaline copolymers via aromatic nucleophilic substitution reactions of an A‐B quinoxaline monomer

A self‐polymerizable quinoxaline monomer (A‐B) has been synthesized and polymerized via aromatic nucleophilic substitution reactions. An isomeric mixture of self‐polymerizable quinoxaline monomers—2‐(4‐hydroxyphenyl)‐3‐phenyl‐6‐fluoroquinoxaline and 3‐(4‐hydroxyphenyl)‐2‐phenyl‐6‐fluoroquinoxaline—was polymerized in N‐methyl‐2‐pyrrolidinone (NMP) to afford high molecular weight polyphenylquinoxaline (PPQ) with intrinsic viscosities up to 1.91 dL/g and a glass‐transition temperature (T_g) of 251 °C. A series of comonomers was polymerized with A‐B to form PPQ/polysulfone (PS), PPQ/polyetherether ketone (PEEK), and PPQ/polyethersulfone (PES) copolymers. The copolymers readily obtained high intrinsic viscosities when fluorine was displaced in NMP under reflux. However, single‐electron transfer (SET) side reactions, which limit molecular weight, played a more dominant role when chlorine was displaced instead of fluorine. SET side reactions were minimized in the synthesis of PPQ/PS copolymers through mild polymerization conditions in NMP for longer polymerization times. Thus, the T_g's of PES (T_g = 220 °C), PEEK (T_g = 145 °C), and PS (T_g = 195 °C) were raised through the incorporation of quinoxaline units into the polymer. Copolymers with high intrinsic viscosities resulted in all cases, except in the case of PPQ/PEEK copolymers when 4,4′‐dichlorobenzophenone was the comonomer. © 2001 John Wiley & Sons, Inc. J Polym Sci A Part A: Polym Chem 39: 2037–2042, 2001     

Two reaction routes for the preparation of aromatic polyoxadiazoles and polytriazoles: Syntheses and properties

Two reaction routes for the preparation of aromatic poly-1,3,4-oxadiazoles and poly-1,2,4-triazoles are studied and their influence on the physical properties, i.e., inherent viscosity, glass transition, degradation temperature, and film integrity of the final products are discussed. Aromatic poly-1,3,4-oxadiazoles are prepared by means of a polycondensation reaction of terephthaloyl chloride and isophthalic dihydrazide yielding a precursor polymer, poly(p, m-phenylene) hydrazide, which is converted into the corresponding poly-1,3,4-oxadiazole by means of a cyclodehydration reaction. Poly-1,3,4-oxadiazoles are also prepared by means of a polycondensation reaction between terephthalic and isophthalic acid and hydrazine yielding poly-1,3,4-oxadiazoles with higher inherent viscosities. Flexible poly-1,3,4-oxadiazole films are obtained only if the inherent viscosities of the polymers used are higher than 2.7 dL/g. The thermal stability is found to increase with increasing content of p-phenylene groups in the polymer backbone. Aromatic poly-1,2,4-triazoles are prepared using polyhydrazides with alternating para- and meta-phenylene groups and poly-1,3,4-oxadiazoles with a random incorporation of para- and meta-phenylene groups in the main chain as precursor polymers. The glass transition temperatures are found to increase with increasing content of p-phenylene groups in the main chain of these polymers. Cold crystallization is observed only for the alternating polymer. © 1994 John Wiley & Sons, Inc.     

Poly[bis(phosphinatoalanyl)phosphonates]

A series of coordination polymers, poly[bis(phosphinatoalanyl)phosphonates], [X(Y)AlOP(R)(O)OAl(Y′)(X′)]_n, were synthesized in which the terminal alanyl substituents (X,Y,X,′Y′) consisted of phosphinato (OPRR′O) or fluoro (F) moieties. The properties of the polymers were primarily dependent upon the type of terminal substituent and the hydrocarbon moieties (R,R′) on phosphorus. Polymers with four phosphinato moieties gave molecular weights M?_n to 120000 with intrinsic viscosities [η] from 1.5 to 18; the corresponding solids were partially crystalline, melted before decomposition, and were film-forming when larger phosphorus substituents were incorporated. Sequential replacement of the phosphinato moieties with fluorine resulted in molecular weights below 10000 and low viscosities. The properties of the polymers are examined, and the roles of substituents on probable structures are discussed.     

Interpenetrating Polymer Networks

Besides mechanical blending and copolymerization there is a third possible way in which two polymers can be combined. Each polymer forms its own network, while both networks interpenetrate each other. There are no covalent bonds between the polymers. Such interpenetrating networks have been synthesized sequentially (from polymer A and monomer B) and simultaneously (from monomer A and monomer B). It is preferable that the polymers be of different chemical type; usually, an elastomer and a glass are combined, e.g. a polyurethane and a polyacrylate. Depending upon the ratio of component polymers either a strengthened elastomer or a glass having impact strength is formed. So far, there are no direct methods for establishing the degree of interpenetration.     

Evaluation of a Commercial Differential Viscometer as a GPC Detector and Its Application to Polymer Characterization

Abstract

When used as a GPC detector, Viscotek's differential viscometer (DV) measures specific viscosities at each elution volume across the chromatogram. With the addition of a concentration detector, intrinsic viscosities may be calculated. As a result, true molecular weights can be calculated via the universal calibration method.

It was found that true molecular weights and branching analysis obtained using DV for acrylate polymers initiated by VAZO and benzoyl peroxide show excellent agreement with those from low angle laser light scattering (LALLS) measurement. Moreover, comparison of intrinsic viscosities for different polymers at the same molecular weights can be made from the DV technique. In general, linear polymers will have a higher IV than branches ones and the concept has been verified for acrylate polymers in this work.

A comparison between DV and LALLS in terms of capabilities, ease of use, and maintenance is also included.     

Phenylated polyimides: Diels-Alder reaction of biscyclopentadienones with dimaleimides

A series of phenylated polydihydrophthalimides has been synthesized by the Diels-Alder reactions of 3,3′-(oxydi-p-phenylene)bis(2,4,5-triphenylcyclopentadienone) and 3,3′-(p-phenylene)bis(2,4,5-triphenylcyclopentadienone) with N,N′-o-, -m-, and -p-phenylenedimaleimide. The polydihydrophthalimides were soluble in dimethylformamide (DMF) and had intrinsic viscosities that ranged from 0.33 to 1.01, the polymers were dehydrogenated thermally and chemically to afford the corresponding phenylated polyphthalimides. The totally aromatic polyimides were also soluble in DMF but had intrinsic viscosities only as high as 0.41. The thermogravimetric analyses of the polyphthalimides showed breaks near 530°C in air and in nitrogen atmospheres.     

Grafting of living poly(ethylene oxide) onto polystyrene via aromatic nucleophilic displacement of activated nitro groups

Polystyrene of M?_ω = 2.2 × 10⁴ was alkylated with 4-nitrophthalimidomethyl groups as grafting sites. Several backbone polymers with various degrees of grafting sites (G = 2–100%) were prepared and characterized by elemental analysis, IR, ¹H- and ¹³C-NMR, and viscosity measurements. “Living” poly(ethylene oxide) with narrow molecular-weight distribution was prepared in the presence of 15-crown-5, and grafted onto the 4-nitrophthalimidomethylated polystyrene. The nitro displacement reaction was fast and the grafting yield was quantitative (100%). The graft copolymers are highly soluble in water and in organic solvents. The intrinsic viscosities of the graft copolymers are higher than those of the backbone polymers. The intrinsic viscosities show an initial increase followed by a decrease as the degree of grafting increase.