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  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 25 (1987), S. 2221-2230 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Copolymers of ethyl acrylate (EA) with lithium acrylate (LiA) with relatively low contents of LiA units (up to 30%) were synthesized by alkaline hydrolysis of poly(EA). 13C-NMR spectra of these copolymers registered in a mixture of deuterated benzene with deuterated methanol (85:15 v/v) presented configurational splittings of the ester methylene, methylene main chain, and ester carbonyl group signals. Assignments of these splittings were made and Bernoulli statistics with a meso probability of 0.48 could fit both poly(EA) and poly(EA-co-LiA). Only the C=O signal of the copolymer was sensitive to sequence distribution and indicated that the LiA units have a tendency to be isolated on the chain. Two-dimensional HETCOR pulse sequence helped to assign the main chain proton spectrum.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 28 (1990), S. 1549-1568 
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two analogous series of ionomer precursors based on 4-substituted styrene copolymers were prepared with substituents R = -(CH2)nCO2Me (n = 1, 5, 10), or R = -O(CH2)nCO2Me (n = 1, 4, 10), and degrees of substitution from 10 to 15 mol%. The synthesis of the alkyl series compounds involved either chloromethylation of polystyrene or bromoalkylation via lithiation of a styrene-4-bromostyrene copolymer, followed by conversion to the nitriles. Methyl esters were then produced by reaction of the nitriles with methanol/HCl gas. The ether series compounds were obtained directly by reacting a styrene-4-hydroxystyrene copolymer with the methyl esters of the corresponding ω-bromoaliphatic carboxylic acids in a Williamson ether-type synthesis.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 25 (1987), S. 663-671 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: FTIR spectra of blends of lightly sulfonated polystyrene (PS-SSA) with polyurethanes (PU) containing a tertiary nitrogen in the chain extender were recorded. These blends exhibit a two-phase behavior, but the individual components are not phase separated. Earlier dynamic mechanical studies suggested the occurrence of proton transfer from the sulfonic acid to the tertiary nitrogen, which enhanced the miscibility via ionic interactions and resulted in the formation of a miscible blend between the PS-SSA and the hard segment of the PU, the soft segment being excluded. FTIR studies of these blends now confirm the proton transfer mechanism. A new absorption band at 3428 cm-1 corresponds to a stretching vibration of an N+-H bond. The 1012 cm-1 band of the SO3H group, which strongly depends on the degree of protonation, shifts to lower frequency. The symmetric stretching vibration of the SO3- group, which occurred at 1043 cm-1, shifts to lower frequency as well, suggesting a lower polarization of the S—O dipole due to the removal of H+.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1793-1805 
    ISSN: 0887-6266
    Keywords: rutile ; surface modification ; diblock copolymer ; inverse gas chromatography ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various functional diblock copolymers have been used as surface modifiers for rutile pigment in an effort to condition the solid for eventual use in multicomponent polymer systems. Coated surfaces were analyzed by inverse gas chromatography at infinite and finite dilution of the vapor phase, and by XPS. At high coverages (about 10% by weight of the pigment), the diblocks were randomly oriented at the air interface, effectively masking the surface of the rutile. At low diblock concentrations acid/base interactions dominated the orientation of the adsorbed molecule at the rutile interface, thereby also affecting the orientational states at the air interface. In this condition, the performance of the pigment in specified host polymer systems may be expected to vary with the selection of the diblock copolymer modifier. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1793-1805, 1997
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 36 (1998), S. 2877-2886 
    ISSN: 0887-6266
    Keywords: ionomers ; NIR ; chemometrics ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Near Infrared (NIR) spectroscopy coupled with chemometrics techniques were utilized to study the composition and properties of styrene-sodium methacrylate ionomers. Predictive models were obtained for mol % ionic content, as well as for the ionic cluster glass transition temperature, storage modulus, and tan δ peak parameters. The results illustrate the feasibility of using NIR and chemometrics algorithms as a property predictive tool, as well as the potential for the development of full calibration models. The chemometric parameters are discussed based on correlations with ionomer NIR spectral features and the role water molecules play as a probe for the associated structure of the ionomer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2877-2886, 1998
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1197-1212 
    ISSN: 0887-6266
    Keywords: block polyelectrolyte solutions ; micelles ; light scattering ; phase separation ; NaCl solutions ; extreme dilution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Micellar solutions of polystyrene-b-poly(sodium acrylate) copolymers in aqueous NaCl were studied by static light scattering (SLS). It was found that micellar solutions of the copolymer, at concentrations of NaCl at, or above, 2.0 mol dm-3, became turbid on dilution at constant salt concentration and at constant temperature. Turbidity arose from highly dilute solutions (typically at a concentration three orders of magnitude lower than the overlap concentration of the micelle, C*), but at concentrations above the expected critical micellization concentrations (c.m.c.s). The observed turbidity was attributed to the phase separation of the micellar phase. A systematic investigation of the phase separation phenomenon was performed. The effects of various parameters on the solution behavior of the micellar solutions were studied, including the effect of the concentration of NaCl, the effect of temperature, and the effect of the length of the hydrophilic, corona-forming poly(sodium acrylate) block. Phase separation was attributed to the presence of a very large excess of NaCl in the dilute micellar solutions. It was proposed that phase separation arose because of the reduced hydration of the polyion, the decreased electrostatic repulsion between the micelles, and the increase in the amount of ion binding, which occur in highly dilute salt solutions. © 1996 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 569-580 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dynamic mechanical properties of partly sulfonated (8.1 mole%) polystyrene were investigated at a frequency of ca. 1 Hz, following neutralization with various low molecular weight flexible and rigid amines. IR spectroscopic evidence suggested that the protonated amine units were possibly H-bonded to the sulfonate anion. Neutralization with flexible amines was found to result in a decrease in the glass transition temperature Tg by an amount proportional to the number of carbon atoms in the amine, while neutralization with rigid amines was found to result in an increase in Tg. It was also observed that the amines were more miscible with the sulfonated material than with polystyrene. It was concluded that the changes in properties observed upon neutralization are similar to those expected from a graft.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 1841-1857 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Direct ion-ion interactions in ionomer blends are achieved through microion elimination by mixing the two ionomers, poly (styrene -co-tetraalkylammonium methacrylate) and poly (ethyl acrylate-co-Nmethyl-4-vinyl pyridinium. iodide), in a benzene/ methanol mixture. The pyridiniumcarboxylate ionion interactions are compared with pyridinium-sulfonate interactions which were described before. It is shown that carboxylate ions are much less effective than sulfonate ions in enhancing miscibility in the polystyrene/ poly (ethyl acrylate) system. Complete miscibility is not attained for this polymer pair even with up to 10 mol % ions. In another system, ion pair-ion pair blends were prepared by mixing poly (styrene-co-sodium styrenesulfonate) with poly (ethyl acrylateco-N-methyl-4-vinyl pyridinium iodide), also in a benzene/ methanol mixture. The results show that ion pair-ion pair associations are also a much weaker driving force for miscibility enhancement in this polymer pair than the corresponding direct pyridinium-sulfonate ion-ion interactions. A ranking is presented of the relative strengths of the various ionic interactions in their effect on miscibility enhancement, which also includes ion-dipole interactions (sodium sulfonate-pyridine).
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 197-209 
    ISSN: 0887-6266
    Keywords: ionomer ; mechanical properties ; moisture ; annealing ; degree of neutralization ; cation type ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study was undertaken of the effect of sample preparation conditions, especially moisture content, annealing conditions, and degree of neutralization, on the dynamic mechanical properties of poly(styrene-co-sodium methacrylate) ionomers. Water plasticizes the ionic cores; however, very small amounts of water do not affect the cluster glass transition mechanism. The study of the annealing effect showed that the morphology of ionomers is fixed during sample molding. No clustering was observed in samples below a degree of neutralization of 50%, possibly due to a decrease in the lifetime of the multiplets. The 50 and 75% neutralized samples showed weak clustering, with the cluster tan δ peaks shifting to higher temperatures with increasing degree of neutralization. The addition of neutralizing agents causes an increase in the size of multiplets; as a result, the strength of the electrostatic interaction between ion pairs increases. The 100-150% neutralized samples showed identical tan δ peaks and also very similar SAXS peaks. Therefore, it is speculated that excess NaOH resides in or near the multiplets and does not affect the electrostatic interaction between ion pairs. The 200-300% neutralized samples showed increased flow above the cluster Tg, as well as a strong small-angle upturn in the SAXS profile. In agreement with previous results, it appears that in these materials, the excess NaOH resides in the hydrocarbon phase in the form of NaOH crystals, which can act as sites on which the carboxylate ion pairs can reside temporarily; the binding, however, is believed to weaken at high temperatures, which allows flow to occur. The 200% overneutralized Ba2+ sample showed the cluster Tg at much higher temperatures than the 100% neutralized sample, which implies that, for this sample, the stability of the multiplets is higher. © 1995 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 495-503 
    ISSN: 0887-6266
    Keywords: ionomer ; blends ; polyamide ; miscibility ; ion-polymer ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Blends of polyamide-6 with lithium ionomers of 9.8 and 5.4 mole percent sulfonated polystyrene, formed by combining solutions of these polymers, are miscible over a wide compositional range, but those with the equivalent sodium ionomers are not. The molecular origin of this difference is addressed by studying the far infared and infrared spectra of the blends and pure materials to follow changes in the interactions between the cations and their surroundings, and changes in the interactions between functional groups. Based on analysis of these spectra, a molecular level interpretation of the blending is proposed. The initial step involves both the interaction of one amide carbonyl with an Li+ ion and simultaneous hydrogen bonding between an amide N—H and a sulfonate group. This eventually leads to formation of an Li(〉CO)+n(n ∼ 4) entity while the sulfonates are converted to the acid form through hydrogen bonding to the amide N—H groups. The Na+ ion does not interact strongly enough with the amide groups to leave its sulfonate environment to a significant extent. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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