Poly(mono n-alkyl itaconic acid esters): Their preparation and some physical properties†
TL;DR: In this paper, a series of poly(mono n-alkyl itaconic acid esters), with ester chain lengths varying from methyl to decyl, were prepared by emulsion polymerisation.
Abstract: A series of poly(mono n-alkyl itaconic acid esters), with ester chain lengths varying from methyl to decyl, were prepared by emulsion polymerisation. The materials are all hard brittle glassy polymers at ambient temperatures and undergo a dehydration reaction in the range 430 K to 450 K. Dynamic mechanical measurements showed the presence of at least three other damping maxima: an Δ-transition at 90−95 K, a δ-transition at 190–200 K and a γ-transition at 240–260 K. The e is associated with motion in the hydrocarbon part of the side chain, while the δ and γ transitions are associated with relaxations involving the carboxyl and alkoxycarbonyl groups respectively. Glass transitions were only detectable in higher esters. The thermal stability of the polymers is also briefly discussed.
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TL;DR: In this article, a series of poly(mono n-alkyl itaconate) derivatives with more than 12 carbon atoms were shown to be able to crystallize in hexagonal lattices.
58 citations
TL;DR: In this article, the formation or inhibition of interpolymer complexes for these systems strongly depends upon the solvent medium, and the stoichiometry of the complexes prepared from methanol solutions has been calculated from elemental analysis, resulting in a stochastic ratio near a 1:1 ratio.
Abstract: This paper reports on the interpolymer complex formation and polymer blends between poly(monomethyl itaconate) (PMMI) and two polymer acceptors poly(N,N-dimethylacrylamide) (PDMA) and poly(ethyloxazoline) (PEOX). We have found that the formation or inhibition of interpolymer complexes for these systems strongly depends upon the solvent medium. The stoichiometry of the complexes prepared from methanol solutions has been calculated from elemental analysis, resulting in a stoichiometry near a 1:1 ratio. Specific interactions of PMMI/PDMA and PMMI/PEOX complexes and blends have been characterized by FTIR. Strong hydrogen bonding for complexes and blends has been found. Finally, a calorimetric and thermogravimetric study of the complexes and blends has been performed in a wide temperature range.
55 citations
55 citations
TL;DR: In this article, the reactivity ratios were estimated using the classical Fineman−Ross and Kelen Tudos procedures, starting from the values of r1 and r2 obtained by the linear procedures.
Abstract: Copolymers containing vinylpyrrolidone and mono and dialkyl itaconate units with different length in the side chains were synthesized and characterized. Copolymers of vinylpyrrolidone with three different compositions of monomethyl, monoethyl, monopropyl, monoamyl, dimethyl, diethyl, dipropyl, and diamyl itaconate were obtained by radical polymerization. The reactivity ratios was estimated by using the classical Fineman−Ross and Kelen Tudos procedures. These parameters were also estimated using a computer program based on nonlinear minimization algorithm, starting from the values of r1 and r2 obtained by the linear procedures. The copolymers can be considered as random. Fractionation of the copolymers were achieved by fractional precipitation. Fractions were characterized by viscometry and light scattering measurements. The unperturbed dimensions were determined using the Stockmayer−Fixman method. Higher rigidity indexes and characteristic ratios are observed in copolymers containing diitaconate units tha...
44 citations
TL;DR: In this article, the formation of interpolymer complex and polymer blends between poly(monoethyl itaconate) (PMEI) and poly(N-vinyl-2-pyrrolidone) (PVP) was found to depend upon the solvent medium.
Abstract: This paper reports on the interpolymer complex formation and polymer blends between poly(monoethyl itaconate) (PMEI) and poly(N-vinyl-2-pyrrolidone) (PVP). The formation of the interpolymer complex was found to depend upon the solvent medium. Stoichiometry of the complexes prepared from methanol solutions, as calculated from elemental analysis, is close to 1 : 1. Specific interactions of PMEI/PVP complexes and blends of these polymers have been characterized by FTIR. Strong hydrogen bonding for complexes and blends has been found. A calorimetric study of the complexes and blends has been performed over a wide temperature range.
37 citations
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TL;DR: In this paper, the authors summarize some of the general relationships between chemical structure and transition temperatures for polymers and make a preliminary attempt at some rational nomenclature and classification scheme for polymer transitions.
Abstract: The primary purpose of this paper is to summarize some of the general relationships between chemical structure and transition temperatures for polymers. In addition to the two primary transitions, the melting point Tm, and the glass transition TG, other transitions occurring either below TG or between TG and Tm are discussed. A secondary purpose of this paper is to make a preliminary attempt at some rational nomenclature and classification scheme for polymer transitions, especially in the case of polymers having multiple transitions. This article is not intended to be a complete review of the literature on transitions in polymers. Our paper was inspired by a comprehensive lecture on multiple transitions presented by Dr. Karl Wolf in Midland, Michigan, during the summer of 1960. The substance of this lecture has recently been published. Willbourn has also been concerned with the classification of multiple transitions. A recent comprehensive report by Saito, Okano, Iwayanagi and Hideshima called “M...
536 citations
TL;DR: A detailed investigation of the structure of polymethacrylic acid has been made by means of infra-red spectral analysis as mentioned in this paper, and the residual degradation product is shown to consist predominantly of linked six-membered anhydride rings with occasional crosslinks.
118 citations
TL;DR: In this article, a series of polymethacrylic and polychloroacrylic esters were measured over a wide temperature range at about 200 c.p.s. using a cantilever vibration method.
Abstract: Some dynamic mechanical properties of a series of polymethacrylic and polychloroacrylic esters have been measured over a wide temperature range at about 200 c.p.s. using a cantilever vibration method. The sharp changes in dynamic modulus, and the associated mechanical loss maxima, which occur at various temperatures are discussed in relation to the chemical structures of the polymers and in particular to the ester group in their side chains. The main softening region is shown to be influenced by the presence of polar atoms in both the main and the side chains and by the spatial size and flexibility of the side chains. The data further support the recently postulated view that a secondary dispersion occurring just below the main softening region is associated with rearrangements of the CO.Ogroup in the side chains. Some new low temperature transitions are reported, one of which at −30°C. is characteristic only of polycyclohexyl methacrylate and polycyclohexyl chloroacrylate; it is suggested that this is associated with intramolecular flexibility within the cyclohexyl ring. Another process occurring at about −150°C. is found for those polymers whose linear side chain alkyl components possess sufficient flexibility to enable them to take up more than one unique spatial configuration; such flexibility is characteristic of the n-propyl, n-butyl, and sec-butyl esters in both series and of the β-chloroethyl, neopentyl carbinyl, and stearyl esters in the polymethacrylic series. Finally, the strengths of the low temperature relaxation processes, defined in terms of the percentage modulus change, are compared and discussed.
117 citations
105 citations
TL;DR: In this article, the glass transition temperature of poly(acrylic acid) was found to be of the order of 103C and increases with increasing anhydride content, reaching an extrapolated value of 140C for the pure linear anhydric acid.
Abstract: : The kinetics of dehydration and decarboxylation as well as the glass transition temperature as a function of anhydride content were measured for poly(acrylic acid). It was found that the glass transition of PAA is of the order of 103C and increases with increasing anhydride content, reaching an extrapolated value of 140C for the pure linear anhydride. Anhydride formation is first order reaction, as is also decarboxylation, the latter being much slower than the former. Anhydride formation occurs primarily by an intramolecular process. (Author)
80 citations