Interpolymer interactions and miscibility in poly(n-butyl methacrylate-co-methacrylic acid)/poly(styrene-co-N,N-dimethyl acrylamide) blends (original) (raw)
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Macromolecular Symposia, 2008
Random copolymers of styrene with acrylic acid (SAA) and with N, Ndimethylacrylamide (SAD) of different compositions were prepared and characterized. Depending on the nature of the solvent and the densities of interacting species incorporated within these polystyrene matrices, novel materials as soluble interpolymer complexes in THF or precipitates from butan-2-one were elaborated when SAA and SAD copolymers are mixed together due to the presence of specific interpolymer interactions. These specific intermolecular interactions were evidenced by ATR/FTIR spectroscopy, qualitatively from the appearance of new bands in the 1800-1550 cm À1 region and quantitatively using adequate spectral curve fitting for the determination of the fraction of the different species. The DSC analysis showed that all these materials as soluble or precipitate interpolymer complexes exhibited one composition-dependence glass transition temperature T g , indicating that they are homogenous on a 20-40 nm scale. Information about the mixing at a smaller scale obtained by solid state proton NMR, provided from measurements of proton spin relaxation times T 1 (H) and T 1 r (H) in the laboratory and rotatory frames carried out for SAA-27, SAD-17 and their (70/30 and 50/50) mixtures as cast from THF or butan-2-one, confirmed similar phase behaviour promoted by a solvatation effect. The single T 1 (H) observed in the pure components and their blends as cast from both THF and butan-2-one confirm that these blends are homogeneous on the scale of 20-40 nm. Furthermore, the T 1 r (H) recoveries indicate that the blends were homogeneous on the scale of 2-3 nm only when cast from THF, while composite recovery curves T 1 r (H) were however observed with SAA-27 and its mixtures of different ratios below 120 8C when butan-2-one is the casting medium.
Thermochimica Acta, 2010
The miscibility and phase behaviour of poly (isobutyl methacrylate-co-4-vinylpyridine) containing 20 mol% of 4-vinylpyridine (IBM4VP20) and poly (styrene-co-acrylic acid) containing 27 or 32 mol% of acrylic acid (SAA27 or SAA32) mixtures were investigated by DSC, TGA and FTIR spectroscopy in the 25-180 • C temperature range. The results showed that sufficient specific carboxyl-pyridine hydrogen bonding interactions occurred between these copolymers and led to miscible blends as cast from THF and to inter-polymer complexes of significantly improved thermal stability when butan-2-one is the common solvent. The self-association effect on the inter-polymer interactions was evidenced by the decrease of complexation yields, observed when the carboxylic content is increased above 27 mol% as with SAA32.
Journal of Macromolecular Science, Part A, 2007
The acrylamide monomer, N-(4-bromophenyl)-2-methacrylamide (BrPMAAm) has been synthesized by reacting 4-bromoaniline with methacryloyl chloride in the presence of triethylamine(NR 3) at 0-5°C. Copolymers of N-(4-bromophenyl)-2-methacrylamide (BrPMAAm), with glycidyl methacrylate (GMA) were synthesized in 1,4-dioxane solution at 70 ± 1°C using 2,2 0-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The copolymers were characterized by FTIR, 1 Hand 13 C NMR spectroscopy. The copolymer composition was evaluated by nitrogen content (N for BrPMAAm-units) in polymers led to the determination of reactivity ratios. The monomer reactivity ratios for BrPMAAm (M 1)-GMA (M 2) pair were determined by the application of conventional linearization methods such as Fineman-Ross (r 1 = 0.2893; r 2 = 0.7114), Kelen-Tü dö s (r 1 = 0.3361; r 2 = 0.8645) and extended Kelen-Tü dö s (r 1 = 0.3096; r 2 = 0.8577) as well as by a non-linear error variables model (EVM) method using a computer program, RREVM (r 1 = 0.3453; r 2 = 0.8606). The mean sequence lengths determination indicated that the copolymer was statistically in nature. The polydispersity indices of the polymers determined using gel permeation chromatography suggest a strong tendency for chain termination by disproportionation. Thermal decomposition of the polymers occurred in three stages in the temperature range of 100-500°C and the glass transition temperature (T g) range of 94-165°C.
Express Polymer Letters, 2007
The miscibility behavior of poly(styrene-co-cinnamic acid) (PSCA) with poly(methyl methacrylate) (PMMA), poly[(methyl methacrylate)-co-(4-vinylpyridine)] (PMMA4VP) and poly[(methyl methacrylate)-co-(2-vinylpyridine)] (PMMA2VP) was studied. DSC measurements indicated that PSCA23 containing 23 mol% of carboxylic acid units was miscible with PMMA, PMMA2VP and PMMA4VP as established from the observation of a single composition dependent glass transition temperature. Miscibility was induced via hydrogen bonding as evidenced by IR frequency shifts of the hydroxyl stretching vibrations of the acid copolymer in the blends. Interpolymer hydrogen bonding formation within the binary systems was also investigated by viscosimetric study of dilute solutions in toluene. For PMMA/PSCA5 blends the viscosity of the mixtures was close to the weight average viscosities of the individual polymer while for blend solutions of PSCA5 with PMMA2VP and PMMA4VP, the interactions were sufficiently strong to form interpolymer complexes with a decrease in viscosity in comparison to the additivity rule.
European Polymer Journal, 1999
The miscibility of poly(styrene-co-methacrylic acid)(SMA) with poly(isobutyl methacrylate) (PIBMA), or poly[isobutyl methacrylate-co-2-(N,N-dimethyl amino)ethyl methacrylate] (IBMDAEM), or poly(isobutyl methacrylate-co-4-vinylpyridine) (IBM4VP), has been studied. Poly(isobutyl methacrylate) is immiscible with SMA copolymers even at a relatively high content of methacrylic acid (45 mol%), as evidenced by dierential scanning calorimetry (DSC), from the observation of two glass transition temperatures (T g s), and by viscometry. However, these SMA copolymers containing between 12 and 45 mol% of methacrylic acid are miscible with IBMDAEM containing 12 or 20 mol% of (N,N-dimethyl amino)ethyl methacrylate, or IBM4VP containing 10 mol% of 4vinylpyridine as evidenced by DSC, viscometry and inverse gas chromatography (IGC). #
Polymer Bulletin, 1995
The miscibility of blends of poly(c~-methyl styrene-co-methacrylic acid) (PtxMSMA) with various aikyl methacrylate polymers or poly(alkyl methacrylate-co-4-vinylpyridine) was studied by differential scanning calorimetry and Fourier transform infra red spectroscopy.PetMSMA is immiscible with poly(methyl methacrylate), poly(ethyl methacrylate) and poly(n-butyl methacrylate). The introduction of 4-vinylpyridine by random free radical copolymerization within these alkyl methacrylate polymer chains enhanced the miscibility of these copolymers with Pc~MSMA as a result of specific interactions that occurred between the carboxylic and pyridine groups, evidenced from the significant changes observed by FTIR in the carboxyl and pyridine ring regions. The density of interacting groups required for miscible blends depends on the size of the pendant group.
Thermochimica Acta, 1996
The miscibility of poly(isobuty1 methacrylate) with poly(styrene-co-acrylic acid) and of poly(isobuty1 methacrylate-co-acrylic acid) with poly(styrene-coN ,N-dimethyl aminoethyl methacrylate) was studied by differential scanning calorimetry and inverse gas chromatography. Poly(styrene-co-acrylic acid), containing 20 or 32 mol% acrylic acid, and poly(isobuty1 methacrylate) were immiscible, as were blends of poly(isobuty1 methacrylate-co-acrylic acid) containing 10.5 mol% acrylic acid with poly(styrene-coN ,N-dimethyl aminoethyl methacrylate) containing 6 mol% of the basic comonomer. However, as a result of a higher level of favorable specific interactions between moieties in the two copolymers, the same isobutyl methacrylate copolymer or copolymers with a greater content of acrylic acid are miscible with the styrene copolymer containing 12 mol% N,N-dimethyl aminoethyl methacrylate, as suggested by the negative values of the apparent polymer-polymer interaction parameters.